JP2005255921A - Expandable fireproof composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an expandable fireproof composition having an excellent molding processability which has been especially a problem in the composition which forms a carbonized layer by expansion and foaming on heating, exhibiting the effect of protecting combustibles from fire and preventing smoke, flame and gases generated by combustion from flowing out to the outside. <P>SOLUTION: The use of the expandable fireproof composition comprising (A) a thermoplastic resin, (B) a phosphorous compound, (C) a multifunctional alcohol, (D) a metal oxide and (E) a processability improving agent can markedly improves the molding processability while maintaining excellent water resistance and expandability by heating. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a foam-type fireproof composition, and more particularly, applied to a covering of general building components, inner and outer walls, joints of openings, gaps, holes, etc., and when exposed to fire, a foamed carbonized layer It is related with the foam-type fireproof composition which has the effect of preventing flammable materials, such as wood, and preventing the outflow of smoke, a flame, the gas generated by combustion, etc. to the exterior.

  Conventionally, in order to improve the fireproof performance of a building, it has been performed to cover a beam, a steel column, a partition wall, etc. of the building with a fireproof material. The current fireproof coating is mainly sprayed with a semi-wet refractory material (such as rock wool). However, in this method, the material tends to diverge at the time of work, and curing is necessary to prevent this, and problems such as work at a high place remain in terms of work safety.

  In addition, as a means for solving these problems, a plate-like fireproof / fireproof board made mainly of calcium silicate, gypsum, or the like may be used. However, since these fireproof / fireproof boards are brittle, they are often damaged such as cracks when transported from the board creation site to the construction site, and are not easily cut out at the construction site. On the other hand, various fireproof / fireproof sheets made of inorganic compounds such as ceramics and nonwoven fabrics have been proposed. However, these fireproof and fireproof sheets have poor stretchability and remarkably inferior displacement followability, and because of their thickness, they have little mobility and are transported at a time. It was not suitable for use because the amount that could be produced was limited.

On the other hand, a fire resistant rubber composition that can be processed into a sheet and has elasticity has been proposed. That is, although it is a foaming fireproof composition comprising a thermoplastic elastomer, a phosphorus compound, a polyfunctional alcohol, a metal oxide, a plasticizer, and an amino group-containing compound (Patent Document 1), in this case, a blended composition is used. However, there was a problem with its moldability. That is, when the blended composition is processed, so-called heat kneading is performed, but there is a problem in its melting characteristics, and there is a problem in the resin take-up property in extrusion molding and in the roll kneading.
JP2003-066461

  In view of the above-mentioned problems of the prior art, the object of the present invention is to form a carbonized layer that is expanded and foamed by heating, thereby preventing flammables from being fired, or smoke, flame, gas generated by combustion, etc. to the outside. An object of the present invention is to provide a foam-type fireproof composition excellent in molding processability, which is particularly regarded as a foam-type fireproof composition having an effect of preventing outflow.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention is characterized by containing (A) a thermoplastic resin, (B) a phosphorus compound, (C) a polyfunctional alcohol, (D) an inorganic filler, and (E) a processability improver. It relates to the foaming type fireproofing composition.

  As a preferred embodiment, the present invention relates to (E) a foam-type fireproof composition, wherein the processability improver is an organic polymer material.

As a preferred embodiment, the present invention relates to (E) a foam-type fireproof composition, wherein the processability improver is an organic polymer material.

As a preferred embodiment, the present invention relates to (E) a foam-type fireproof composition, wherein the processability improver is an organic polymer material.

  As a preferred embodiment, the present invention relates to a foam-type fireproofing composition characterized by further containing (F) a plasticizer.

  As a preferred embodiment, the present invention relates to a foam-type fireproof composition characterized by further containing (G) an amino group-containing compound.

A preferred embodiment relates to (A) a foam-type fireproofing composition in which the thermoplastic resin is a thermoplastic elastomer.

In a preferred embodiment, the thermoplastic elastomer is a block copolymer composed of a polymer block composed of an aromatic vinyl compound and a polymer block composed of a monomer mainly composed of isobutylene. The present invention relates to a foam-type fireproof composition.

  In a preferred embodiment, the thermoplastic elastomer is a block copolymer composed of a polymer block composed of an aromatic vinyl compound and a polymer block composed of a monomer mainly composed of isobutylene. The present invention relates to a foam-type fireproof composition.

  As a preferred embodiment, the present invention relates to a foam-type fireproofing composition characterized in that (B) the phosphorus compound is a polyphosphate and / or a polyphosphate amide.

In a preferred embodiment, the present invention relates to a foam-type fireproofing composition characterized in that the polyphosphate and / or polyphosphate amide is a coated phosphorus compound.

A preferred embodiment relates to (D) a foam-type fireproof composition characterized in that the inorganic filler is titanium oxide.

  As a preferred embodiment, the present invention relates to (F) a foam-type fireproofing composition characterized in that the plasticizer is at least one selected from polyα-olefin and polybutene.

  The present invention also relates to a foam-type fireproof sheet laminate characterized by laminating a woven fabric or a nonwoven fabric made of inorganic fibers on at least one surface of a foam-type fireproof sheet-like molded body.

  As a preferred embodiment, the present invention relates to a foam-type fireproof sheet laminate, wherein the inorganic fiber is a glass fiber.

  Moreover, this invention relates to the manufacturing method of a foaming type fireproof sheet-like molded object.

  Moreover, this invention relates to the manufacturing method of a foaming type fireproof sheet-like laminated body.

By using the foam-type fireproofing composition of the present invention, the deterioration of foaming performance due to water absorption and moisture absorption is small, and the moldability can be remarkably improved while having excellent foamability.

More specifically, the foamable curable composition of the present invention contains a phosphorus compound, a polyfunctional alcohol, a metal oxide, and a processability improver as essential components in a thermoplastic resin, and thus expands by heating and / or flame. In order to form a carbonized (ashed) layer with high fire resistance and heat insulation, and because it contains a workability improver, it is heated and kneaded with an extruder or roll. This makes it possible to perform continuous take-up, which has been impossible, and exhibits excellent workability. Furthermore, since it is excellent in moisture resistance and water resistance, it can be used for a long period of time, and there is no need for periodic replacement. Furthermore, the foam-type fireproof sheet-like molded article of the present invention is excellent in flexibility and workability in addition to the above-mentioned composition characteristics. The foam-type fireproof sheet laminate in which the woven fabric or nonwoven fabric made of the inorganic fiber of the present invention is laminated is improved by dripping in a wide temperature range from room temperature to 1000 ° C. Such a foam-type fire-proof composition, foam-type fire-proof sheet-like molded body, and foam-type fire-proof sheet laminate are excellent in that they can be widely applied to places where fire-proof / fire-proof performance is required in general buildings. It is a thing.

  Hereinafter, the present invention will be described in detail. The foam-type fireproof composition of the present invention contains (A) a thermoplastic resin, (B) a phosphorus compound, (C) a polyfunctional alcohol, (D) an inorganic filler, and (E) a processability improver. Become. Although the foaming carbonization mechanism by heating and / or flame of such a foam-type fireproof composition is unclear, it is chemically decomposed and / or reacted, and carbonized with stable and high thermal insulation. A layer can be formed.

  (A) The thermoplastic resin is not particularly limited, and for example, at least one selected from the group consisting of plastics, rubbers, and thermoplastic elastomers can be used. Examples of the plastics include polyolefins such as polypropylene and polyethylene, polystyrene, ABS, MBS, acrylic, polyurethane, polyvinyl chloride, polyester, polyamide, and the like. Examples of rubbers include polyether, polybutadiene, natural rubber, butyl rubber, chloroprene rubber, and ethylene-propylene rubber. Thermoplastic elastomers include, for example, styrene-based block copolymers composed of polystyrene blocks and the like, polybutadiene and polyisoprene blocks, olefins composed of polyolefin components such as polypropylene and rubber components such as ethylene-propylene rubber, and crystals. A vinyl chloride system composed of crystalline and non-crystalline polyvinyl chloride, a urethane system that is a block copolymer composed of a polyurethane block and a polyether block, a polyester system that is a block copolymer composed of a polyester block and a polyether block, In addition, an amide system which is a block copolymer composed of a polyamide block and a polyether block can be used. At least one of these thermoplastic resins can be used regardless of the classification of plastics, rubbers, and thermoplastic elastomers.

  Of the above thermoplastic resins, thermoplastic elastomers are preferable in terms of processability, flexibility, and strength, and block copolymers are more preferable. As the block copolymer, an aromatic vinyl block copolymer composed of a block composed of an aromatic vinyl compound and a block composed of an olefin compound is particularly preferable. When such a thermoplastic elastomer, particularly a block copolymer, is used, the sheet is flexible and easily processed as compared with other thermoplastic resins, and covering with complicated shapes is also easy. The block made of the aromatic vinyl compound means a block in which the aromatic vinyl compound occupies 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more. The block made of the olefin compound means a block in which the olefin compound occupies 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, t-butylstyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, and indene. Among the above compounds, styrene, α-methylstyrene, p-methylstyrene, and indene are preferable from the balance of physical properties and productivity, and two or more types may be selected from them.

Examples of the olefin compound include olefin compounds having 1 to 6 carbon atoms such as ethylene, propylene, 1-butylene, isobutylene, butadiene, and isoprene, and two or more of them may be selected. Furthermore, specific examples of the block comprising an olefin compound obtained from the above compound include a polybutadiene block, a polyisoprene block, and their hydrogenated polyethylene / butylene block, polyethylene / propylene block, and polyisobutylene block. . Of these, a polyisobutylene block containing a large amount of tertiary hydrocarbons necessary for forming a stable and strong carbonized layer, having a high water vapor barrier property and hardly causing a crosslinking reaction during thermal decomposition is particularly preferred.

  The polyisobutylene block refers to a block in which isobutylene occupies 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more.

  The number average molecular weight of the block copolymer composed of a block composed of an aromatic vinyl compound and a block composed of an olefin compound is not particularly limited, but is preferably 30,000 to 500,000, preferably 40,000 to 400,000. Is particularly preferred. When the number average molecular weight is less than 30,000, mechanical properties and the like are not sufficiently exhibited, and when it exceeds 500,000, the moldability and the like are greatly deteriorated. Although there is no restriction | limiting in particular in the ratio of an olefinic compound and an aromatic vinyl type compound, 95-20 weight part of olefinic compounds and 5-80 weight part of aromatic vinyl type compounds are preferable from the balance of a physical property, Furthermore, an olefinic compound 90 to 60 parts by weight and 10 to 40 parts by weight of an aromatic vinyl compound are more preferable.

  (B) Although there is no restriction | limiting in particular as a phosphorus compound, Red phosphorus; Phosphate esters, such as a triphenyl phosphate and a tricresyl phosphate; Phosphate metal salts, such as a sodium phosphate and a magnesium phosphate Ammonium phosphate; salts or amides of phosphoric acid with organic bases such as melamine; ammonium polyphosphate; salts or amides of polyphosphoric acid with organic bases such as melamine; ammonium polyphosphate; organic bases such as melamine of polyphosphoric acid; Or at least one selected from the group consisting of coated phosphorus compounds obtained by coating these phosphorus compounds with a resin or the like. The polyphosphoric acid is not particularly limited as long as phosphoric acid is condensed, but a 2-5000 mer of phosphoric acid is preferable. The coated phosphorus compound is a phosphorus compound in which the periphery of a phosphorus compound particle that is solid at room temperature is covered with a resin or the like, and the coating material is not particularly limited, but is a thermoplastic resin, a thermosetting resin, an organic material. A compound can be used, and examples thereof include melamine-coated ammonium polyphosphate obtained by coating ammonium polyphosphate with melamine.

  These (B) phosphorus compounds not only act as dehydration and / or carbonization catalysts for organic substances in a heated environment, but also have a function of forming an incombustible inorganic phosphate coating.

  Among the phosphorus compounds, a coated phosphorus compound is preferable from the viewpoints of dispersibility in the thermoplastic resin (A) which is a matrix resin and water resistance.

  (B) Among the phosphorus compounds, as the uncoated phosphorus compound, phosphoric acid or polyphosphoric acid salt, phosphoric acid or polyphosphoric acid amide is preferable. On the other hand, the coated phosphorus compound is not particularly limited, and examples thereof include a coating of a phosphorus compound that is solid at room temperature, such as red phosphorus, phosphoric acid or polyphosphoric acid salt, phosphoric acid or polyphosphoric acid amide. Among the coated phosphorus compounds, a phosphoric acid or polyphosphoric acid salt, or a phosphoric acid or polyphosphoric acid amide coating is preferable in terms of ease of handling.

  Regardless of the presence or absence of coating, the phosphoric acid or polyphosphoric acid salt is preferably phosphoric acid or a salt of polyphosphoric acid with ammonia or an organic base, more preferably ammonium polyphosphate or a derivative thereof. Examples of the amine compound that forms the salt include methylamine, ethylamine, and melamine, and melamine salt of polyphosphoric acid is particularly preferable.

  Regardless of the presence or absence of coating, phosphoric acid or polyphosphoric acid amide is particularly preferably phosphoric acid or polyphosphoric acid melamine amide. When a salt or amide with phosphoric acid, ammonium polyphosphate or amine reaches the decomposition temperature by heating, phosphoric acid and condensed phosphoric acid are produced by deamination such as deammonia. This acid acts as a dehydration catalyst for organic matter and carbonizes the organic matter, resulting in the formation of a carbonized layer. In addition, ammonia gas, nitrogen gas, and the like generated at this time act as a foaming agent to expand the entire composition, and reduce oxygen concentration to suppress combustion. As the phosphorus compound used in the present invention, those having a phosphorus content of 10% by weight or more and a nitrogen content of 9% by weight or more are suitable.

  Such a salt or amide with phosphoric acid or ammonium polyphosphate or amine is not particularly limited. For example, an insolubilized polymer phosphorus compound made of ammonium polyphosphate manufactured by Sumitomo Chemical Co., Ltd. (product “Sumisafe PM”) In addition, there is no particular limitation on the phosphoric acid, ammonium polyphosphate, or a salt or amide coated with an amine, but for example, a coated ammonium polyphosphate (trade name “Terrage C80” manufactured by CBC Corporation). ]) And the like.

  (B) Although the compounding quantity of a phosphorus compound is not necessarily limited, It is preferable to mix | blend 5-200 weight part with respect to 100 weight part of (A) thermoplastic resins. When the compounding amount of the phosphorus compound is less than this range, it cannot be expected to effectively carbonize and foam the entire composition. On the other hand, if the blending amount of the phosphorus compound exceeds this range, the viscosity of the blend increases and the moldability decreases, which is not preferable.

  (C) The polyfunctional alcohol is dehydrated by (B) phosphorus compound to form a carbonized film. Those having a decomposition temperature of carbonization by heating of 180 ° C. or higher, preferably 220 ° C. or higher can be used. Examples of such polyfunctional alcohols include polyhydric alcohols such as mono, di, and tripentaerythritol, polysaccharides such as starch and cellulose, oligosaccharides such as glucose and fructose, and the like. From the viewpoint of foaming characteristics, mono, di, and tripentaerythritol are particularly preferable. These may be used alone or in combination of two or more.

  (C) Although the compounding quantity of polyfunctional alcohol is not necessarily limited, It is preferable that it is 5-50 weight part with respect to 100 weight part of (A) thermoplastic resins. When the blending amount of the polyfunctional alcohol component (C) is below this range, the expansion becomes insufficient. Conversely, when the blending amount of the polyfunctional alcohol component (C) is above this range, the formation of the foamed carbon film is insufficient. In addition, since it tends to bleed out, a problem arises in formability.

  Since most of the carbonized layer formed from (B) phosphorus compound and (C) polyfunctional alcohol is decomposed and gasified at about 600 ° C., (A) thermoplastic resin, (B) phosphorus compound, and (C) In the composition which consists of polyfunctional alcohol, it is difficult to form the carbonization layer which exhibits fireproof performance at 600 degreeC or more. Therefore, in order to maintain the fire resistance even at 600 ° C. or higher, the foamed fire resistant composition of the present invention must contain the inorganic filler (D) that remains as an ash layer even at a high temperature range of 1000 ° C.

  (D) The inorganic filler is not particularly limited and conventionally known ones can be used. For example, calcium carbonate, gypsum, mica, clay, talc, graphite, asbestos, carbon black cement, antimony oxide, alumina, At least one selected from the group consisting of quartzite, diatomaceous earth, titanium oxide, zinc oxide, aluminum oxide, silicon oxide (silica), calcium oxide, magnesium oxide, iron oxide, copper oxide, lead oxide, and tin oxide is used. As the inorganic filler, titanium oxide is particularly preferable from the viewpoints of expansion ratio and ashing layer strength. Such titanium oxide is not particularly limited. For example, Ishihara Sangyo Co., Ltd.'s rutile titanium oxide (trade name “Taipek R-820”), the company's anatase titanium oxide (trade name “Taipaque A-”). 220 ") and the like.

  (D) It is preferable that the compounding quantity of an inorganic filler is 5-200 weight part with respect to 100 weight part of (A) thermoplastic resins. (D) If the blending amount of the inorganic filler exceeds 200 parts by weight, the foaming ratio of the carbonized layer is lowered, high weatherability is not exhibited, and the flexibility of the composition is lowered, so that the moldability is lowered. It is not preferable. If it is less than 5 parts by weight, when incinerated at 600 ° C. or higher, the density of the incinerated layer becomes sparse and a through part is formed, so that a problem that the contribution as a heat insulating layer is reduced tends to occur.

  (E) In the present invention, the (E) processability improving agent refers to an improving agent that can improve the melt tension during the forming process and improve the formability, and is sometimes called a processing aid. Such an improver that can improve the melt tension of the composition, that is, the processability improver referred to in the present invention, does not impair the physical properties of the resin and suppresses an increase in melt viscosity as much as possible. It greatly improves the melt tension required in processing such as extrusion molding, roll molding, vacuum molding and blow molding with a small amount of addition, and improves molding processability without lowering fluidity. The processability improver is not particularly limited, and inorganic materials and organic polymer materials can be used. Among them, organic polymer materials are preferable, and acrylic polymer materials and polytetrafluoroethylene polymer materials are exemplified. Among them, polytetrafluoroethylene-based modifiers with acrylic modification in particular have a highly rigid molecular structure, low cohesive force, and can take a fibrous network structure in the composition. Is big.

  (E) The compounding quantity of a workability improving agent is not specifically limited, (A) 0.001-20 weight part with respect to 100 weight part of thermoplastic resins, or (F) A plasticizer is mix | blended. In that case, the amount is preferably 0.001 to 20 parts by weight based on 100 parts by weight of the total of components (A) and (F) plasticizer. If the blending amount of the component (E) processability improver is below this range, the processability improving effect will be insufficient. On the other hand, if the blending amount of the component (E) processability improving agent is above this range, the melt tension will increase. Too much, moldability becomes poor. (E) Specific examples of processability improvers include, for example, polytetrafluoroethylene processability improvers such as METABRENE A3000 manufactured by Mitsubishi Rayon Co., Ltd. and Lumiflon manufactured by Asahi Glass Co., Ltd. Can be mentioned. As the processability improver, in particular, from the viewpoint of the processability improvement effect, methabrene A3000 which is a polytetrafluoroethylene-based improver is particularly preferable.

  The foam-type fireproof composition of the present invention contains (A) a thermoplastic resin, (B) a phosphorus compound, (C) a polyfunctional alcohol, (D) an inorganic filler, and (E) a processability improver. However, a composition containing (F) a plasticizer is preferable. (F) By containing a plasticizer, (B) phosphorus compound, (C) polyfunctional alcohol, (D) inorganic filler, and (E) processing which are essential components other than (A) thermoplastic resin composition The foaming type fireproofing composition which can be made to contain a property improvement agent in a larger quantity and was more excellent in fireproof performance can be obtained. Furthermore, (F) the plasticizer moderately lowers the viscosity of the composition to prevent foam breakage and the like, thereby providing a high expansion ratio, and preventing the shape retention (strength) of the carbonized layer from being reduced by moisture or water. He also has a role.

  (F) The plasticizer is not particularly limited, and general ones can be used, but (A) those having good compatibility with the thermoplastic resin are preferable. For example, at least one selected from the group consisting of polybutene, hydrogenated polybutene, liquid polybutadiene, hydrogenated liquid polybutadiene, poly α-olefins, paraffinic oil, naphthenic oil, α-methylstyrene oligomer, atactic polypropylene and the like is used. Is done. Of the plasticizers, at least one selected from polyalphaolefins and polybutenes that do not inhibit foaming carbonization is preferable.

  (F) It is preferable that the compounding quantity of a plasticizer is 1-50 weight part with respect to 100 weight part of (A) thermoplastic resins. (F) When the blending amount of the plasticizer exceeds 50 parts by weight, bleed out is likely to occur, a problem occurs in moldability, and the viscosity of the composition is too low. Problems such as lowering of the foaming ratio are likely to occur.

  Furthermore, in the foam-type fireproof composition of the present invention, in addition to the above components, (G) an amino group-containing compound may be used as a further additive component. (G) The amino group-containing compound acts as a swelling agent, generates non-flammable gases such as nitrogen and ammonia with decomposition by heating, and expands the entire composition to an appropriate size. Specific examples include dicyandiamide, melamine, guanamine, guanidine, urea, azodicarbonamine, amino resins such as melamine resin, guanamine resin, and urea resin, but are not limited thereto. These may be used alone or in combination of two or more.

Although the compounding quantity of this amino group containing compound is not specifically limited, It is preferable that it is 0.1-20 weight part with respect to 100 weight part of (A) thermoplastic resins. If the compounding amount of the amino group-containing compound exceeds this range, the strength of the foamed carbon film to be formed becomes insufficient, such being undesirable.

  In addition to (A) a thermoplastic resin, (B) a phosphorus compound, (C) a polyfunctional alcohol, (D) an inorganic filler, and (E) a workability improver, (F) Plasticizers, (G) Amino group-containing compounds, and in addition to foaming aids, reinforcing agents, lubricants, hindered phenols and hindered amines, depending on the required properties for each application An agent, an ultraviolet absorber, a light stabilizer, a pigment, and the like can be appropriately blended. Examples of the foaming aid include chemical foaming agents such as azodicarbonamide and sodium bicarbonate-citric acid, and inorganic foam particles such as expandable graphite and unexpanded vermiculite.

  As the most preferable composition of the foam-type fireproof resin composition of the present invention, (A) 10 to 50 parts by weight of a phosphorus compound and (C) 5 to 50 polyfunctional alcohols with respect to 100 parts by weight of a thermoplastic resin. Parts by weight, (D) 10 to 50 parts by weight of an inorganic filler, and (E) 0.001 to 20 parts by weight of an improver capable of improving the melt tension of the composition. Furthermore, when (F) a plasticizer is contained, it is preferable to add 1 to 50 parts by weight of (F) plasticizer with respect to 100 parts by weight of the thermoplastic resin (A). F) 10 to 50 parts by weight of a phosphorus compound, (C) 5 to 50 parts by weight of a polyfunctional alcohol, (D) 10 to 50 parts by weight of an inorganic filler, and (E) with respect to 100 parts by weight of the plasticizer. It is preferable that it is 0.001-20 weight part of improvers which can improve the melt tension of a composition.

  The method for preparing the foam-type fireproof composition in the present invention is not particularly limited. For example, the above components are blended and kneaded using a mixer, roll, kneader, extruder, etc. at room temperature or under heating, or an appropriate amount. Ordinary methods such as mixing after dissolving the components in the solvent may be employed. The obtained foam-type fireproof composition can be made into a foam-type fireproof sheet-like molded body by a molding method usually used for thermoplastic resins such as injection molding, extrusion molding, hot press molding, calender molding and the like.

  The point to be noted by using the foam-type fireproofing composition in the present invention is that the take-up property at the time of extrusion or roll processing is remarkably improved. In other words, the preferred blending balance between the improver and the composition that can improve the melt tension of the composition improves the tension at the time of melting of the composition. The handleability of the is improved.

  As a preferable example of the molding method of the composition of the present invention, (A) to (E) (F) and (G) as further preferable components are kneaded with a batch kneader such as a Banbury mixer or a pressure kneader and foamed. A mold fireproofing composition is obtained. The obtained foam-type fireproofing composition is put into a roll or calendar molding machine to produce a sheet or ribbon-shaped molded body. Thereafter, a sheet-like molded body may be obtained by forming to a predetermined thickness using a rolling roll or the like, or a sheet-like or ribbon-like molded body obtained from a roll or a calendering machine is used as a rolling roll on a T die or a head part. The sheet-like molded body having a predetermined thickness may be obtained by continuously feeding it into an extruder provided with the. Also, after the composition kneaded with a batch kneader is pelletized using a kneader, etc., the pellets are put into an extruder or calendar molding machine as described above to obtain a sheet-like molded body having a predetermined thickness. Also good.

  Further, (A) to (E), preferably (F) and / or (G) are blended in advance with a mixer or the like, and the blended product is put into an extruder or calendar molding machine as described above to have a predetermined thickness. You may obtain a sheet-like molded object. Although only the sheet-like molded body is described here, a molded body having a predetermined shape may be obtained by a modified extrusion using a modified die in the die part instead of the above-described extruder, and other resins and It is also possible to form a laminate by coextrusion.

  Although there is no restriction | limiting in particular in the thickness of the said foaming type fireproof sheet-like molded object, It is preferable that it is 0.2-15 mm. When the thickness is less than 0.2 mm, even if the foamed carbonized layer and / or the incinerated layer is formed, sufficient heat insulation is not exhibited. When the thickness exceeds 15 mm, the sheet weight becomes heavy, and the handleability and workability deteriorate.

  The foam-type fireproof sheet laminate of the present invention is obtained by laminating a woven fabric or a nonwoven fabric made of inorganic fibers on one surface of the foam-type fireproof sheet-like molded body. The inorganic fiber used for the woven or non-woven fabric is not particularly limited, but for example, at least one selected from the group consisting of glass fiber, ceramic fiber, rock wool, carbon fiber, alumina fiber, silicon carbide fiber and the like. Can be used. In particular, glass fiber is preferable because it does not decompose in a high temperature range and is easy to handle.

Although there is no restriction | limiting in particular in the number of driving | running | working of the fiber of the said woven fabric, 10-80 pieces / 25mm is preferable to each length and width. If the number of driving is less than the above range, the sheet is liable to sag, and if it exceeds the above range, the flexibility of the sheet laminate is inferior and problems such as bending occur. Although there is no restriction | limiting in particular in the mass of the said woven fabric, 1-700 g / m < ² > is preferable. When the mass of the woven fabric exceeds the above range, the weight of the sheet laminate increases, and the handleability and workability deteriorate.

There is no particular limitation on the weaving method of the woven fabric, but at least one selected from the group consisting of plain weave, twill weave, satin weave, leopard weave, imitation weave, etc. can be used. A plain weave or twill weave is preferred because of its high handleability, workability and flexibility, and a good balance with strength. Although there is no restriction | limiting in particular in the fabric weight of the said nonwoven fabric, The fabric weight of 1-700 g / m < ² > is preferable. If the basis weight of the nonwoven fabric exceeds the above range, the weight of the sheet laminate increases, and the handleability and workability deteriorate. Although there is no restriction | limiting in particular in the thickness of the said woven fabric or a nonwoven fabric, 0.03-10 mm is preferable.

  When the thickness of the woven fabric or the nonwoven fabric exceeds the above range, the flexibility of the sheet laminate is inferior, and problems such as bending occur. In order to prevent fraying or kinking of the woven fabric or non-woven fabric, it is preferable to apply a binder or a finishing treatment. The binder and the finishing treatment are applied to a woven fabric or a nonwoven fabric by applying a resin or paste such as a phenol resin or a polyester resin or a solution to a woven or non-woven fabric, carrying, prepreg, and dipping, etc. It is to strengthen the entangled part and the overlapping part.

  The surface of the woven or non-woven fabric and the inorganic fibers used for them are subjected to various treatments or used without treatment. When the surface treatment is performed, there is no particular limitation, but it is preferable to perform various silane treatments such as aminosilane, chromium treatment, and the like. By performing the surface treatment, adhesion between the foam-type fireproof composition composed of the thermoplastic resin composition and the sheet-like laminate is further strengthened. Although there is no restriction | limiting in particular in the lamination | stacking method of the said woven fabric or a nonwoven fabric, and a foaming type fireproof sheet-like molded object, The method of heat-seal | fusing by superposing and heat-pressing a woven fabric or a nonwoven fabric, and a sheet-like molded object A method of forming a sheet-like formed body by calendering and simultaneously pressing (heat-sealing) a woven or non-woven fabric with a rolling roll; providing an adhesive / adhesive layer on one side of the woven or woven cloth; A method of adhering and adhering with a press or roll; a method of adhering and adhering to a woven fabric or woven fabric with a press or roll by providing an adhesive / adhesive layer on one side of the sheet-like molded body is preferable.

  Examples of preferred production methods of the foam-type fireproof composition, sheet-like molded product, and sheet laminate of the present invention include the following examples. First, each component (A)-(G) is knead | mixed with batch type kneading apparatuses, such as a Banbury mixer and a pressure kneader, and a foaming type fireproofing composition is obtained. The obtained foam-type fireproofing composition is made into a rolled sheet-like formed body with an extruder having a rolling roll installed in the head part (discharge part), and at the same time, a sheet is formed by crimping a woven or non-woven fabric at the rolling roll part. A laminated state is obtained.

  There are no particular restrictions on the use of the foam-type fireproofing composition, sheet-like molded product, and sheet laminate of the present invention. For example, for construction purposes, the foam-type fireproofing composition is laminated or laminated on walls, columns, beams, doors, combustibles, etc. It can be used for the purpose of fireproofing and fireproofing an object by forming a heat insulating foam carbonized layer when exposed to a flame. In addition, it is used for parts that require fireproof performance such as fireproof safes, home appliance housings, automobile interior materials, etc., and is used for the purpose of exhibiting fireproof performance.

  Although there is no particular limitation on the method for fixing the foam-type fireproof composition, sheet-like molded body and sheet laminate of the present invention to the surface of the fireproof / fireproof coating target, a thermosetting resin from the viewpoint of long-term use Fixing by at least one of a method of adhering to an object with an adhesive composed of, etc., a method of fixing by heat fusion to the object, and a method of physically fixing to an object with screws, bolts, screws, etc. Is preferred.

  Regarding the method of fixing the foamed fireproof sheet laminate to the surface of the fireproof / fireproof coating object, a method of physically fixing with a screw, bolt, screw or the like is particularly preferable, and further comprising a thermosetting resin. At least one of a method of adhering to an object with an adhesive and a method of fixing by heat fusion to the object can be used in combination.

  Although there is no restriction | limiting in particular in the usage method of the foaming type fireproof sheet | seat laminated body of this invention, It uses so that the surface by the side of the woven fabric which consists of inorganic fiber, or a nonwoven fabric, or a nonwoven fabric side may touch the fireproof / fireproof coating target object Or a method of using the foam-type fireproof sheet surface so as to be positioned on the surface in contact with the object. In particular, the latter method of using the foam-type fireproof sheet surface so as to be located on the surface in contact with the object is preferable because it does not hinder the formation of the foam.

  Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited by these. Prior to the examples, various measurement methods and evaluation methods will be described.

(Foaming ratio)
A 100 mm x 100 mm foam-type fireproof sheet laminate in which a woven fabric or non-woven fabric is laminated on one side of a 2 mm thick sheet-shaped molded product. A woven fabric with 0.8 mm thick steel plates at 80 mm intervals and 4 mm diameter bolts. Or it fixed so that a nonwoven fabric might be located in the steel plate side. Further, a 25 mm-thick ceramic blanket was laminated on the opposite side of the steel sheet foam-type fireproof sheet laminate. The above sample on which the sheet laminate, the steel plate, and the ceramic blanket were superposed was placed vertically and heated in an electric furnace according to Table 1 from the foam-type fireproof sheet side for 2 hours. After heating, the sheet was taken out and the thickness was measured, and the thickness after heating / the original sheet thickness (2 mm) was defined as the expansion ratio.

(Molding processability)
30 kg of foam-type fireproofing composition is heated and mixed with a pressure kneader, then kneaded with a roll for another 10 minutes, the composition is peeled off using a metal spatula, and the end of the composition is brought into a take-up machine and continuously I picked it up. The composition was continuously taken up as a ribbon-like sheet having a thickness of 1 cm and a width of 10 cm, and evaluated according to the following criteria.
Ribbon can be taken continuously; ◎
Can be picked up by slowing the pick-up speed; ○
Can't pick up; x.

(water resistant)
A 100 x 100 mm foam-type fire-proof sheet laminate in which a woven fabric or non-woven fabric is laminated on one side of a 2 mm thick sheet-shaped molded product is placed in a glass container and immersed in warm water at 50 ° C for 0 days and 50 ° C for 7 days. After that, the steel sheet was fixed to a 0.8 mm thick steel plate at intervals of 80 mm with bolts having a diameter of 4 mm so that the woven or non-woven fabric was positioned on the steel plate. Further, a 25 mm-thick ceramic blanket was laminated on the opposite side of the steel sheet foam-type fireproof sheet laminate. The above sample on which the sheet laminate, the steel plate, and the ceramic blanket were superposed was placed vertically and heated in an electric furnace according to Table 1 from the foam-type fireproof sheet side for 2 hours. After heating, the sheet was taken out and the thickness was measured. The thickness after heating / the thickness of the original sheet (2 mm) was taken as the expansion ratio, and the expansion ratio after being immersed in warm water at 50 ° C. for 7 days was 50 ° C. × 0. Dividing by the expansion ratio when immersed in warm water for a day was used as an index of water resistance.

（実施例１）
［スチレン−イソブチレン−スチレンブロック共重合体（ＳＩＢＳ）の製造］
２００Ｌの耐圧重合反応槽を窒素置換した後、定量ポンプを用いて、ｎ−ヘキサン（モレキュラーシーブスで乾燥したもの）３８．１６Ｌ及び塩化ブチル（モレキュラーシーブスで乾燥したもの）５４Ｌを加え、重合反応槽を−７０℃まで冷却させた後、イソブチレンモノマー２１．７６Ｌを貯槽から送液ポンプで圧送した。次に、貯槽から、ｐ−ジクミルクロライド７１．２ｇ及びＮ,Ｎ−ジメチルアセトアミド４９．６ｇ）を加え、更に四塩化チタン０．６７６Ｌを加えて重合を開始した。重合開始から７５分攪拌を行った後、重合溶液からサンプリング用として重合溶液０．４Ｌを抜き取った。続いて、スチレンモノマー５．５３２ｋｇを重合反応槽に添加した。該混合溶液を添加してから４５分後に、大量の水の入った失活槽に移送し、反応を終了させた。その後、反応溶液を２回水洗し、溶媒を蒸発させ、得られた重合体を６０℃で２４時間脱揮をしながら乾燥することにより目的のブロック共重合体を得た。

(Example 1)
[Production of Styrene-Isobutylene-Styrene Block Copolymer (SIBS)]
After substituting the 200 L pressure-resistant polymerization reactor with nitrogen, 38.16 L of n-hexane (dried with molecular sieves) and 54 L of butyl chloride (dried with molecular sieves) were added using a metering pump. After being cooled to −70 ° C., 21.76 L of isobutylene monomer was pumped from the storage tank with a liquid feed pump. Next, 71.2 g of p-dic milk chloride and 49.6 g of N, N-dimethylacetamide were added from the storage tank, and 0.676 L of titanium tetrachloride was further added to initiate polymerization. After stirring for 75 minutes from the start of polymerization, 0.4 L of the polymerization solution was extracted from the polymerization solution for sampling. Subsequently, 5.532 kg of styrene monomer was added to the polymerization reactor. 45 minutes after adding the mixed solution, the mixture was transferred to an inactivation tank containing a large amount of water to terminate the reaction. Thereafter, the reaction solution was washed twice with water, the solvent was evaporated, and the resulting polymer was dried while devolatilizing at 60 ° C. for 24 hours to obtain the desired block copolymer.

  The molecular weight of the polymer obtained by gel permeation chromatography (GPC) was measured. A block copolymer having a block copolymer Mw of 79000 was obtained.

  The obtained styrene-isobutylene-styrene copolymer 14.814 kg, pentaerythritol 2.964 kg, Taipei R820 4.443 kg (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), polybutene 1.482 kg (manufactured by Idemitsu Petrochemical Co., Ltd.) Terage C80 4.443 kg (flame retardant manufactured by CBC Co., Ltd.), melamine 1.482 kg (manufactured by Nissan Chemical Co., Ltd.), Wax-OP 0.075 kg (lubricant manufactured by Hoechst Co., Ltd.), pigment 0.147 kg (Sanyo) Titanium Yellow (Chemical Co., Ltd.), processability improver 0.147 kg (Metabrene A3000 manufactured by Mitsubishi Rayon Co., Ltd.) was melt kneaded at 150 ° C. using a pressure kneader, and the resin composition was further rolled for 10 minutes. The mixture was kneaded and the molding processability was measured. Further, the obtained resin composition was molded into a sheet having a thickness of 2 mm through an extruder and a T die at a resin temperature of 120 ° C., and the foaming ratio and water resistance of the obtained molded product were evaluated. The results are shown in Table 2.

(Example 2)
14.814 kg of styrene-isobutylene-styrene copolymer obtained by the method described in Example 1, 2.964 kg of pentaerythritol, 4.443 kg of Typek R820 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), 1.482 kg of polybutene (Idemitsu) Petrochemical Co., Ltd.), Terrage C80 4.443 kg (Chisso Co., Ltd. flame retardant), Melamine 1.482 kg (Nissan Chemical Co., Ltd.), Wax-OP 0.075 kg (Hoechst Co., Ltd. lubricant) , Pigment 0.147 kg (Titanium Yellow manufactured by Sanyo Chemical Co., Ltd.), Processability improver 0.147 kg (Mitsubrene A3000 manufactured by Mitsubishi Rayon Co., Ltd.) was melt kneaded at 160 ° C. using a pressure kneader, and the resin composition The product was further kneaded with a roll for 10 minutes, and the molding processability was measured. Further, the obtained resin composition was molded into a sheet having a thickness of 2 mm through an extruder and a T die at a resin temperature of 120 ° C., and the foaming ratio and water resistance of the obtained molded product were evaluated. The results are shown in Table 2.

(Example 3)
14.742 kg of styrene-isobutylene-styrene copolymer obtained by the method described in Example 1, 2.948 kg of pentaerythritol, 4.423 kg of Tyco R820 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), 1.474 kg of polybutene (Idemitsu) Petrochemical Co., Ltd.), Terrage C80 4.423 kg (Chisso Co., Ltd. flame retardant), Melamine 1.474 kg (Nissan Chemical Co., Ltd.), Wax-OP 0.074 kg (Hoechst Co., Ltd. lubricant) , Pigment 0.147 kg (Titanium Yellow manufactured by Sanyo Chemical Co., Ltd.), Processability improver 0.295 kg (Mitsubrene A3000 manufactured by Mitsubishi Rayon Co., Ltd.) was melt kneaded at 160 ° C. using a pressure kneader, and the resin composition The product was further kneaded with a roll for 10 minutes, and the molding processability was measured. Further, the obtained resin composition was molded into a sheet having a thickness of 2 mm through an extruder and a T die at a resin temperature of 120 ° C., and the foaming ratio and water resistance of the obtained molded product were evaluated. The results are shown in Table 2.

(Comparative Example 1)
14.888 kg of styrene-isobutylene-styrene copolymer obtained by the method described in Example 1, 2.978 kg of pentaerythritol, 4.467 kg of Typek R820 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), 1.489 kg of polybutene (Idemitsu) Petrochemical Co., Ltd.), Terrage C80 4.467 kg (Chisso Co., Ltd. flame retardant), Melamine 1.489 kg (Nissan Chemical Co., Ltd.), Wax-OP 0.074 kg (Hoechst Co., Ltd. lubricant) Then, 0.149 kg of pigment (Titanium Yellow manufactured by Sanyo Chemical Co., Ltd.) was melt-kneaded at 160 ° C. using a pressure kneader, and then the resin composition was further kneaded with a roll for 10 minutes to measure molding processability. Further, the obtained resin composition was molded into a sheet having a thickness of 2 mm through an extruder and a T die at a resin temperature of 120 ° C., and the foaming ratio and water resistance of the obtained molded product were evaluated. The results are shown in Table 2.

(Comparative Example 2)
Styrene-isobutylene-styrene copolymer obtained by the method described in Example 1 7.519 kg, pentaerythritol 3.759 kg, Tyco R820 5.639 kg (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), polybutene 1.504 kg (Idemitsu) Petrochemical Co., Ltd.), Terrage C80 5.639 kg (Chisso Co., Ltd. flame retardant), Melamine 5.639 kg (Nissan Chemical Co., Ltd.), Wax-OP 0.075 kg (Hoechst Co., Ltd. lubricant) Then, 0.226 kg of pigment (titanium yellow manufactured by Sanyo Chemical Co., Ltd.) was melt-kneaded at 160 ° C. using a pressure kneader, and then the resin composition was kneaded with a roll for another 10 minutes to measure the molding processability. Further, the obtained resin composition was molded into a sheet having a thickness of 2 mm through an extruder and a T die at a resin temperature of 120 ° C., and the foaming ratio and water resistance of the obtained molded product were evaluated. The results are shown in Table 2.

発泡性硬化組成物中に加工性改良剤を配合した実施例１〜３では、比較例１、２に比べ、成形加工性は著しく改良され、また、発泡倍率、耐水性については、同じレベルであることが確認できた。

In Examples 1 to 3, in which a processability improver was blended in the foamable curable composition, the molding processability was remarkably improved as compared with Comparative Examples 1 and 2, and the foaming ratio and water resistance were at the same level. It was confirmed that there was.

Claims (16)

  A foam-type fireproof composition comprising (A) a thermoplastic resin, (B) a phosphorus compound, (C) a polyfunctional alcohol, (D) an inorganic filler, and (E) a processability improver. Stuff.   2. The foaming fireproofing composition according to claim 1, wherein the processability improving agent is an organic polymer material.   The foamable fireproofing composition according to claim 2, wherein the processability improver is a polytetrafluoroethylene polymer material.   Furthermore, (F) plasticizer is contained, The foaming type fireproofing composition in any one of Claims 1-3 characterized by the above-mentioned.   Furthermore, (G) an amino group containing compound is contained, The foaming type fireproofing composition in any one of Claims 1-4 characterized by the above-mentioned.   (A) The thermoplastic resin is a thermoplastic elastomer, The foaming fireproofing composition according to any one of claims 1 to 5.   7. The foam according to claim 6, wherein the thermoplastic elastomer is a block copolymer comprising a polymer block composed of an aromatic vinyl compound and a polymer block composed of a monomer mainly composed of isobutylene. Mold fireproofing composition.   (B) The foaming fireproof composition according to any one of claims 1 to 7, wherein the phosphorus compound is a polyphosphate and / or a polyphosphoric acid amide.   The foaming fireproofing composition according to claim 8, wherein the polyphosphate and / or polyphosphoric acid amide is a coated phosphorus compound.   (D) An inorganic filler is a titanium oxide, The foaming type fireproofing composition in any one of Claims 1-9 characterized by the above-mentioned.   (F) The foaming type fireproofing composition according to any one of claims 1 to 10, wherein the plasticizer is at least one selected from poly-α-olefin and polybutene.   A foam-type fire-proof sheet-like molded article comprising the foam-type fire-proof composition according to claim 1.   A foam-type fireproof sheet laminate, wherein a woven fabric or a nonwoven fabric made of inorganic fibers is laminated on at least one side of the foam-type fireproof sheet-like molded body according to claim 12.   The foam-type fireproof sheet laminate according to claim 13, wherein the inorganic fibers are glass fibers.   The manufacturing method of the foaming type fireproof sheet-like molded object of Claim 12.   The manufacturing method of the foaming type fireproof sheet laminated body of Claim 13 or 14.