WO2018198706A1

WO2018198706A1 - Resin composition for thermally expandable fire resistant sheet, thermally expandable fire resistant sheet using same, and method for manufacturing same

Info

Publication number: WO2018198706A1
Application number: PCT/JP2018/014554
Authority: WO
Inventors: 顕士坂本; ティン田
Original assignee: パナソニックＩｐマネジメント株式会社
Priority date: 2017-04-24
Filing date: 2018-04-05
Publication date: 2018-11-01
Also published as: JPWO2018198706A1

Abstract

Provided is a plastisol which comprises a thermoplastic resin powder (A), a plasticizing agent (B), and a nitrogen-containing foaming agent (C), wherein the thermoplastic resin powder (A) and the nitrogen-containing foaming agent (C) are dispersed in the plasticizing agent (B).

Description

Resin composition for heat-expandable fireproof sheet, heat-expandable fireproof sheet using the same, and method for producing the same

The present disclosure generally relates to a resin composition for a heat-expandable refractory sheet, a heat-expandable refractory sheet using the same, and a manufacturing method thereof, and more specifically, a heat-expandable refractory sheet used for forming a heat-expandable refractory resin layer. The present invention relates to a resin composition for heat, a thermally expandable fireproof sheet using the same, and a method for producing the same.

Construction sites such as beams, columns, floors, walls, roofs, and stairs that require fireproof structures in buildings are mainly made of metal such as H steel and steel, or concrete. Conventionally, in these construction sites, steel columns and beams have been covered with a fireproof coating material for the purpose of improving fireproof performance. As such a fireproof covering material, spray rock wool is widely used, and the on-site wet spray method is the mainstream as its construction method. However, on-site spraying of wet rock wool has problems in terms of hygiene and process because dust is generated during work and curing after spraying is necessary.

On the other hand, in construction sites such as indoor walls and ceilings of buildings, inorganic plate-shaped building materials with fire resistance performance, mainly made of calcium silicate board or gypsum board, are used to enhance fire resistance performance. There is also. However, these inorganic plate-like building materials are fragile and heavy, so that they can be broken and cracked during transportation, and it is necessary to secure a place on the construction site. There was a problem.

Various fireproof paints have been proposed as means for solving such problems.

For example, Patent Document 1 discloses (1) a polyhydric alcohol, (2) a nitrogen-containing foaming agent, (3) a synthetic resin, (4) a flame retardant foaming agent, and (5) a foaming composition mainly composed of titanium dioxide. Fire resistant paints have been proposed. This foamable fire-resistant paint is such that (1) the polyhydric alcohol is arbitrarily selected from pentaerythritol, dipentaerythritol, tripentaerythritol and polypentaerythritol, and (4) the flame retardant foaming agent is phosphoric acid Ammonium and / or ammonium polyphosphate. In this foamable fireproof paint, it is said that an excellent fireproof performance that can withstand a fireproof test of 45 minutes or more can be obtained by application of 2 mm thickness.

Further, Patent Document 2 proposes an aqueous foam fire-resistant paint containing (A) a binder, (B) a carbonizing agent, (C) a flame retardant, and (D) a filler. This water-based foam fire-resistant paint comprises: (A) a binder comprising (a-1) an isocyanate compound, (a-2) a compound having an active hydrogen group, (a-3) an acid, and (a-4) a chain extender. And an aqueous resin having an acid value in the range of 3 KOHmg / g or more and 100 KOHmg / g or less. This water-based foam fireproof paint is said to be excellent in both storage stability and fireproof performance.

However, the foamable refractory paint of Patent Document 1 needs to be diluted with water prior to the application work to adjust the viscosity, and further applied to the substrate in order to cure the coating film by dilution with water. He needed to be cured for 21 days. Therefore, there is a problem that it takes too much time to cure the foamed fire-resistant paint film. Moreover, although it is excellent in fire resistance, examination about storage stability and coating workability | operativity was not necessarily enough.

In addition, the water-based foam fire-resistant paint of Patent Document 2 includes (A) one of essential constituents obtained by reacting at least four types of compounds as a binder, and in order to cure the coating film, 7 days after application to the material was required. Further, with this water-based foam fire-resistant paint, fire resistance and storage stability are good, but examination of coating workability is not always sufficient.

As described above, it is known that the fire-resistant paint has a large influence on the fire-resistant performance due to the difference in the film thickness of the coating film. The film thickness control of the coating film to be formed was a big problem on site construction.

So far, instead of on-site construction, fireproof paint or fireproof resin composition is applied to the target substrate in advance in the factory, or a fireproof sheet formed from the fireproof resin composition is prepared in advance. It has been proposed to attach to the surface of the construction site on site. Refractory sheets are easily used according to the shape of the construction site, and are widely used because they are lightweight and stretchable. Above all, in the heat-expandable fireproof sheet in which the heat-expandable fireproof resin is applied to the surface of the substrate, the heat-expandable fire-resistant resin layer burns and expands by heating, and the combustion residue forms a fireproof foam layer. It is preferably used because it can exhibit excellent fire resistance and heat insulation.

JP 2001-40290 A JP 2008-144130 A

An object of the present disclosure is to provide a resin composition for a heat-expandable fire-resistant sheet having excellent fire resistance and having good storage stability and coating workability, a heat-expandable fire-resistant sheet using the same, and a method for producing the same It is to be.

A resin composition for a heat-expandable fireproof sheet according to an aspect of the present disclosure includes a powdery thermoplastic resin (A), a plasticizer (B), and a nitrogen-containing foaming agent (C), and the plasticizer (B ) In which the powdery thermoplastic resin (A) and the nitrogen-containing foaming agent (C) are dispersed.

The thermally expandable fireproof sheet of one aspect according to the present disclosure includes a thermally expandable fireproof resin layer obtained by curing the plastisol of the resin composition for a thermally expandable fireproof sheet on one surface of a base material.

In the method for producing a thermally expandable fireproof sheet according to an aspect of the present disclosure, the resin composition for a thermally expandable fireproof sheet is applied to one surface of the substrate, and then cured by heating and cooling, The thermally expandable fireproof resin layer is formed.

The heat-expandable fireproof sheet resin composition of the present embodiment contains a powdery thermoplastic resin (A), a plasticizer (B), and a nitrogen-containing foaming agent (C), and the powder in the plasticizer (B). A plastisol in which a thermoplastic resin (A) and a nitrogen-containing foaming agent (C) are dispersed.

The resin composition for a thermally expandable fireproof sheet of the present embodiment preferably further contains a phosphorus-based flame retardant (D) in addition to the components (A) to (C).

In addition, it is preferable that the resin composition for a heat-expandable fireproof sheet of the present embodiment further contains a carbonizing agent (E) in addition to the components (A) to (D).

Furthermore, it is preferable that the resin composition for a heat-expandable fireproof sheet of this embodiment further contains titanium dioxide (F) in addition to the components (A) to (E).

In such a resin composition for a heat-expandable fireproof sheet, by using plastisol, kneading at the time of preparing a resin composition for a heat-expandable fireproof sheet becomes easy or unnecessary. Loss due to foaming of (C) can be suppressed. Therefore, when the resin composition for a heat-expandable fireproof sheet is applied to the base material and the construction site and heated, the heat-expandable fireproof resin layer is foamed to form the fireproof foam layer, thereby achieving the desired fire resistance. It can be demonstrated. Further, in the resin composition for a heat-expandable fireproof sheet, by using a plastisol, the powdery thermoplastic resin (A) in the resin composition for a heat-expandable fireproof sheet, even when stored for a long time, It is difficult to separate from the plasticizer (B). Therefore, it becomes possible to provide a resin composition for a heat-expandable fireproof sheet that is excellent in storage stability and coating workability.

Hereinafter, each component of the resin composition for a heat-expandable fireproof sheet will be specifically described.

1. Powdered thermoplastic resin (A)
The powdery thermoplastic resin (A) is one of the main components of the resin composition for a thermally expandable fireproof sheet. The powdery thermoplastic resin (A) is not particularly limited as long as it is a thermoplastic resin usually used for fireproof paints, but is preferably a polyvinyl chloride resin or an acrylic resin. About manufacture of these powdery thermoplastic resins (A), if it can be used as a plastisol, it will not restrict | limit in particular, A conventionally well-known thing can be used.

For example, examples of the polyvinyl chloride resin include a homopolymer of vinyl chloride or vinylidene chloride, or a copolymer, that is, a copolymer of vinyl chloride and vinylidene chloride and other vinyl monomers. These can be used individually by 1 type or in combination of 2 or more types.

Examples of vinyl monomers copolymerized with vinyl chloride and vinylidene chloride include vinyl esters such as vinyl acetate, vinyl propionate and vinyl stearate, and vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether. Illustrated. Examples thereof include maleic acid esters such as diethyl maleate, fumaric acid esters such as dibutyl fumarate, and acrylic or methacrylic acid alkyl esters such as methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate. . Further, hydroxyalkyl esters of acrylic acid or methacrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate are exemplified. Examples also include acrylic acid such as N-methylolacrylamide, N-methylolmethacrylamide, N-hydroxyethylacrylamide and N-dihydroxyethylmethacrylamide, hydroxyalkylamides of methacrylic acid, acrylonitrile and the like. Such vinyl monomers can be used singly or in appropriate combination of two or more.

The polyvinyl chloride resin has an average molecular weight in the range of 500 or more and 2500 or less, preferably in the range of 650 or more and 1500 or less, from the viewpoint of exerting desired fire resistance. When the average molecular weight of the polyvinyl chloride resin is within the above range, the fire resistance is good. The average molecular weight is measured by gel permeation chromatography (GPC) and is expressed in terms of standard polystyrene.

Examples of the acrylic resin include particles made of a polymer or copolymer of a monomer such as an alkyl ester of acrylic acid or methacrylic acid. Examples of these monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Moreover, you may use the particle | grains which have a core / shell structure which consists of an acrylic resin core and the acrylic resin shell which coat | covers this. The particles having the core / shell structure are preferably used from the viewpoint of storage stability and coating workability. Moreover, it is used suitably also from the point of low temperature short-time curability.

The powdery thermoplastic resin (A) is dispersed in the plasticizer (B) in the form of a fine powder having a small average particle diameter when dispersed in the plasticizer (B) described later to form a plastisol. The average particle diameter of the powdery thermoplastic resin (A) at this time is usually in the range of 0.1 μm to 100 μm, preferably in the range of 1 μm to 50 μm. If the average particle size of the powdered thermoplastic resin (A) is within the above range, the powdered thermoplastic resin (A) is uniformly dispersed in the resin composition for a thermally expandable fireproof sheet, And a smooth coating film can be formed on the surface of a base material and a construction site. The average particle size of the powdered thermoplastic resin (A) is measured by a laser diffraction / scattering method.

The blending ratio of the powdery thermoplastic resin (A) is preferably in the range of 15 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition for a thermally expandable fireproof sheet. When the blending ratio is within the above range, the storage stability and the coating workability are good.

2. Plasticizer (B)
The plasticizer (B) is one of the main ingredients of the resin composition for a heat-expandable fireproof sheet, and is a component used for dissolving and dispersing the powdered thermoplastic resin (A). The plasticizer (B) improves the application workability of the resin composition for a heat-expandable fireproof sheet, and is formed by curing the resin composition for a heat-expandable fireproof sheet. Can be softened to contribute to the formation of a fireproof foam layer during heating.

The plasticizer (B) is not particularly limited as long as it is usually used for fireproof paints, but any plasticizer generally used for forming plastisols can be used. For example, phthalate ester plasticizers such as dibutyl phthalate (DBP), dihexyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate (DnOP) and diisooctyl phthalate (DIOP) Is exemplified. Examples include didecyl phthalate (DDP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), dimethyl phthalate (DMP), diethyl phthalate (DEP), and bis-2-ethylhexyl phthalate (DEHP). Further examples include diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), C6-C10 mixed higher alcohol phthalate, butyl benzyl phthalate (BBP), and octyl benzyl phthalate. Moreover, nonyl benzyl phthalate, dimethyl cyclohexyl phthalate (DMCHP), etc. are illustrated. Further, linear dibasic acid esters such as dioctyl adipate (DOA), dioctyl azelate (DOZ), and dioctyl sebacate (DOS) are exemplified. Further, phosphate ester plastics such as tricresyl phosphate (TCP), trioctyl phosphate (TOF), trixylenyl phosphate (TXP), monooctyl diphenyl phosphate and monobutyl-dixylenyl phosphate (BZX) Agents are exemplified. Moreover, benzoate plasticizers such as tri- (2-ethylhexyl) trimellitate (TOTM), tri-n-octyl trimellitate, triisodecyl trimellitate and triisooctyl trimellitate are exemplified. Furthermore, esters such as butyl phthalbutyl glycolate (BPBG), tributyl citrate ester, trioctyl acetyl citrate ester, trimet acid ester, citrate ester, sebacic acid ester and azelaic acid ester are exemplified. Furthermore, esters such as tri- or tetraethylene glycol ester of maleic acid ester C6 to C10 fatty acid, alkylsulfonic acid ester and methylacetylricinoleate are exemplified. Also, epoxidized vegetable oils such as those obtained by epoxidizing double bonds of unsaturated fatty acid glycerides such as soybean oil with hydrogen peroxide or peracetic acid (ESBO), and epoxy compounds such as butyl or octyl alkyl oleates Is exemplified. Furthermore, a viscous low-polymerization degree polyester plasticizer (for example, adipic acid polyester) having a mean molecular weight in the range of 500 to 8000, in which propylene glycol ester units of a dibasic acid such as adipic acid are linearly linked. And phthalic acid polyester). These can be used individually by 1 type or in combination of 2 or more types. Among these, the phthalate ester can uniformly disperse the powdered thermoplastic resin (A) and form a stable plastisol. From the viewpoint of fire resistance, coating workability, and storage stability, it is preferable to use diisononyl phthalate (DINP) and diundecyl phthalate (DUP) among phthalates.

The blending ratio of the plasticizer (B) is preferably within the range of 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition for a thermally expandable fireproof sheet. When the blending ratio is within the above range, the storage stability is improved, and the ejection property during the coating operation by spray coating or the like becomes good. Therefore, a resin composition for a heat-expandable fireproof sheet excellent in application workability can be obtained. In addition, when the mixture ratio of a plasticizer (B) exceeds 40 mass parts, the mixture ratio of the powdery thermoplastic resin (A) in the resin composition for heat-expandable fireproof sheets will fall relatively, and is required. It is difficult to ensure a sufficient coating thickness. Furthermore, there is a possibility that the coating workability is lowered, for example, the viscosity of the paint is lowered and a paint flow occurs during the coating work.

3. Nitrogen-containing foaming agent (C)
Nitrogen-containing foaming agent (C) generates flammable gases such as nitrogen and ammonia by decomposition by heating, and carbonizes plastisol and carbonizer (E) described later when carbonized when exposed to heat such as fire. It plays the role of expanding and foaming to form a fireproof foam layer. Further, it is used for the purpose of imparting toughness to the heat-expandable fireproof sheet and exhibiting followability to construction sites such as wall base materials.

Examples of the nitrogen-containing foaming agent (C) include melamine, melamine derivatives, dicyandiamide, azodicarbonamide, urea and guanidine. Among these, from the viewpoint of generation efficiency of nonflammable gas, followability to construction sites, and fire resistance, the nitrogen-containing foaming agent (C) is preferably melamine or dicyandiamide, and more preferably melamine. These can be used alone or in combination of two or more.

The blending ratio of the nitrogen-containing foaming agent (C) is preferably in the range of 5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition for a thermally expandable fireproof sheet. When the blending ratio is less than 5 parts by mass, it is difficult to form a sufficient fire-resistant foamed layer when exposed to heat such as fire, and the toughness of the molded sheet may be significantly impaired. On the other hand, when the blending ratio of the nitrogen-containing foaming agent (C) is more than 25 parts by mass, when exposed to heat such as a fire, the shape maintenance property of the combustion residue in the fireproof foam layer is impaired, and the fire resistance may be lowered. There is. Moreover, there exists a possibility that the storage stability of the resin composition for heat-expandable fireproof sheets may also be impaired.

4). Phosphorus flame retardant (D)
The phosphorus-based flame retardant (D) acts as a catalyst when dehydrating the carbonizer (E) described later by heating and forming a thin film called char. Moreover, when a phosphorus flame retardant (D) is heated at a high temperature of 600 ° C. or higher, it reacts with titanium dioxide (F) described later to form titanium pyrophosphate. Titanium pyrophosphate remains in the fireproof foam layer as an ashing component, thereby improving the shape maintenance of the fireproof foam layer.

Examples of the phosphorus flame retardant (D) include phosphoric esters such as red phosphorus, triphenyl phosphate and tricresyl phosphate, and metal phosphates such as sodium phosphate and magnesium phosphate. . Examples thereof include ammonium phosphate, salts or amides of phosphoric acid with an organic base such as melamine, and ammonium polyphosphates such as ammonium polyphosphate and melamine-modified ammonium polyphosphate. Of these, ammonium polyphosphates such as ammonium polyphosphate and ammonium melamine-modified polyphosphate are preferred from the viewpoints of forming a fireproof foam layer and maintaining shape and long-term durability. These can be used alone or in combination of two or more.

When ammonium polyphosphates reach the decomposition temperature by heating, phosphoric acid and condensed phosphoric acid are generated by deamination such as deammonia. These phosphoric acid and condensed phosphoric acid act as a dehydration catalyst for organic matter, and carbonize the organic matter, resulting in char formation. In addition, ammonia gas, nitrogen gas, and the like generated at that time act as a foaming agent to expand the entire resin composition for a thermally expandable refractory sheet and to suppress combustion by relatively reducing the oxygen concentration. be able to. Furthermore, ammonium polyphosphates decompose when heated at a high temperature of 600 ° C. or more and react with titanium dioxide (F) described later to form titanium pyrophosphate. Titanium pyrophosphate remains in the fireproof foam layer as an ashing component, thereby improving the shape maintenance of the fireproof foam layer.

The blending ratio of the phosphorus-based flame retardant (D) is preferably in the range of 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition for a thermally expandable fireproof sheet. When the blending ratio is less than 20 parts by mass, it becomes difficult to effectively carbonize and foam the thermally expandable resin composition for a refractory sheet, and it is also difficult to ensure the shape retention of the combustion residue in the refractory foam layer. Become. On the other hand, when the blending ratio is more than 50 parts by mass, there is a possibility that the coating workability is lowered.

5). Carbonizer (E)
The carbonizing agent (E) is dehydrated and carbonized by the phosphorus compound contained in the phosphorus-based flame retardant (D) to form a fireproof foam layer.

As the carbonizing agent (E), a carbonizing temperature of 180 ° C. or higher, preferably 220 ° C. or higher can be suitably used. Examples of such a carbonizing agent (E) include polyhydric alcohols such as monopentaerythritol, dipentaerythritol and tripentaerythritol, polysaccharides such as starch and cellulose, and oligosaccharides such as glucose and fructose. Is done. Among these, monopentaerythritol, dipentaerythritol, and tripentaerythritol are particularly preferably used from the viewpoint of foaming characteristics. These can be used alone or in combination of two or more.

The blending ratio of the carbonizing agent (E) is preferably in the range of 5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition for a thermally expandable fireproof sheet. If the blending ratio is less than 5 parts by mass, the formation of the fireproof foam layer becomes insufficient, and it becomes difficult to ensure the shape retention of the combustion residue. When the blending ratio is more than 25 parts by weight, the storage stability of the heat-expandable resin composition for a fireproof sheet may be impaired.

6). Titanium dioxide (F)
When titanium dioxide (F) is heated at a high temperature of 600 ° C. or higher, it reacts with the phosphorus-based flame retardant (D) to form titanium pyrophosphate, and remains as an ashing component in the fireproof foam layer. The shape maintenance property of a fireproof foaming layer can be improved.

Titanium dioxide (F) may be either anatase type or rutile type, and is not particularly limited. As an average particle diameter of titanium dioxide (F), it exists in the range of 0.01 micrometer or more and 200 micrometers or less, for example, More preferably, it exists in the range of 0.1 micrometer or more and 100 micrometers or less.

The blending ratio of titanium dioxide (F) is preferably in the range of 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition for a thermally expandable fireproof sheet. When the blending amount is less than 5 parts by mass, the amount of titanium pyrophosphate remaining in the refractory foam layer as an ashing component when heated at a high temperature of 600 ° C. or more is reduced, and the shape of the combustion residue in the high temperature range is maintained. May become insufficient and fire resistance may be reduced. On the other hand, when the blending ratio is more than 30 parts by weight, the expansion ratio of the fireproof foam layer is lowered, and the fire resistance may be impaired. Moreover, there exists a possibility that the storage stability and coating workability | operativity of the resin composition for heat-expandable fireproof sheets may also fall.

As the other components, a tackifier, an inorganic filler, an antioxidant, a lubricant, and the like are added to the resin composition for a heat-expandable fireproof sheet as necessary, as long as the effects of the present embodiment are not impaired. Can do.

The tackifier is not particularly limited, and examples thereof include rosin resins, rosin derivatives, dammars, polyterpene resins, modified terpenes, aliphatic hydrocarbon resins, and cyclopentadiene resins. Moreover, aromatic petroleum resins, phenol resins, alkylphenol-acetylene resins, styrene resins, xylene resins, coumarone-indene resins, vinyltoluene-α-methylstyrene copolymers and the like are exemplified.

Examples of inorganic fillers include inorganic salts such as calcium carbonate, aluminum hydroxide, magnesium hydroxide, kaolin, clay, bentonite and talc, and oxidized inorganic substances such as glass flakes and wastonite. Examples thereof include inorganic fibers such as rock wool, glass fiber, carbon fiber, ceramic fiber, alumina fiber and silica fiber, and fine inorganic substances such as carbon and fumed silica.

Examples of the antioxidant include an antioxidant containing a phenol compound, an antioxidant containing a sulfur atom, and an antioxidant containing a phosphite compound.

Examples of the lubricant include waxes such as polyethylene, paraffin and montanic acid, waxes such as tall oil, sub-oil, beeswax, carnauba wax and lanolin, ester waxes, and stearic acid, palmitic acid and ricinoleic acid. Examples include organic acids. Examples thereof include organic alcohols such as stearyl alcohol and amide compounds such as dimethylbisamide.

Each of the above components (A) to (C), the components (D) to (F), and other components are uniformly mixed by a conventionally known method, so that the resin for the thermally expandable fireproof sheet of the present embodiment is used. A composition is obtained.

Next, a heat-expandable fireproof sheet using the resin composition for a heat-expandable fireproof sheet of the present embodiment and a manufacturing method thereof will be described.

The heat-expandable refractory sheet includes a heat-expandable refractory resin layer obtained by curing the plastisol of the resin composition for a heat-expandable refractory sheet on one surface of the substrate.

In this heat-expandable fireproof sheet, the substrate is preferably paper or non-woven fabric. Among these, since the base material itself is a flame retardant material, glass fiber chop strands, glass fiber sheets, glass paper, and the like are preferably used. The basis weight is, for example, in the range of 10 g / m ² or more and 100 g / m ² or less, and preferably in the range of 30 g / m ² or more and 60 g / m ² or less. The

The method for producing a heat-expandable fireproof sheet is obtained by applying the plastisol of the resin composition for a heat-expandable fireproof sheet to one surface of the base material, and then heating and cooling the plastisol to cure the heat-expandable material. A refractory resin layer is formed.

Although the coating method of the resin composition for a heat-expandable fireproof sheet is not particularly limited, a conventionally known coating method can be applied. Examples include air spray method, dipping method, curtain coater method, method using brush, method using dispenser, potting method, screen printing, transfer molding and injection molding.

Since the resin composition for a heat-expandable fireproof sheet is in a plastisol state, the resin composition for a heat-expandable fireproof sheet in the resin composition for a heat-expandable fireproof sheet is plasticized even when stored for a long time. The agent (B) is difficult to separate and is uniformly dispersed. Therefore, even if any of the application methods as described above is applied, it is excellent in application workability and can be applied uniformly to the substrate.

When curing the plastisol of the resin composition for a heat-expandable fireproof sheet, the plastisol must be once gelled by heating and then cooled. Examples of the heating condition include heating at a temperature in the range of 70 ° C. to 180 ° C. for 30 seconds to 30 minutes. Such heating can be appropriately performed using, for example, a hot plate or a heat dryer.

It is preferable that the thermally expandable fireproof sheet has at least one layer selected from the group consisting of an inorganic layer, an organic layer, and a metal layer on the other surface of the substrate.

The inorganic layer, the organic layer, and the metal layer can be laminated with the base material in advance, and then the thermally expandable fireproof sheet resin composition can be applied to one surface of the base material. Moreover, after apply | coating the resin composition for heat-expandable fireproof sheets to the one surface of a base material, an inorganic layer, an organic layer, and a metal layer can also be laminated | stacked on the other surface of a base material.

The order in which the inorganic layer, the organic layer, and the metal layer are laminated and the thickness of each layer are not limited, and can be appropriately selected according to the construction site and purpose of the building.

In the present embodiment, as the inorganic layer, for example, inorganic fibers such as rock wool, glass wool, ceramic wool, and glass fiber sheet can be used. Among these, it is preferable to use a glass fiber sheet. As the glass fiber sheet, it is preferable to use glass paper, and the weight per unit area is, for example, in the range of 10 g / m ² or more and 100 g / m ² or less, and preferably 30 g / m ² or more. It is exemplified that it is within the range of 60 g / m ² or less.

By providing a glass fiber sheet layer as an inorganic layer on the other side of the substrate, the strength of the thermally expandable refractory sheet itself is improved. The fixing strength when the sheet is fixed using a fixing tool such as a tucker is also improved. Further, when the expandable refractory sheet is fixed using a fixing tool such as a tucker, it can expand and foam by the flame, and the fall-off prevention property of the formed refractory foam layer can be improved.

Examples of the organic layer include polyolefin resins such as polyethylene resin and polypropylene resin, polystyrene resins, and ether resins such as polyester resins, polyurethane resins and polyamide resins. Further, unsaturated ester resins, copolymer resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer and styrene-butadiene copolymer are exemplified.

The shape of such an organic layer is not particularly limited, and examples thereof include shapes such as films and nonwoven fabrics.

Examples of the metal layer include iron, steel, stainless steel, galvanized steel, aluminum zinc alloy plated steel, and aluminum. There is no restriction | limiting in particular as a shape of such a metal layer, For example, shapes, such as a metal plate and metal foil, can be illustrated. Among these, aluminum foil can be suitably used from the viewpoint of handleability.

These inorganic layers, organic layers, and metal layers may be supplied and laminated in a batch manner to the base material, or may be supplied continuously.

As a method of laminating and integrating the inorganic layer, the organic layer and the metal layer with the base material and the resin composition for a heat-expandable refractory sheet, there is a particular limitation as long as it is a normal method and conditions for molding a resin molded body Not. For example, when the plastisol of the resin composition for a heat-expandable fireproof sheet is cured, it is exemplified that it is stacked on top or bottom and simultaneously heated and pressurized.

The thickness of the thermally expandable fireproof resin layer in the thermally expandable fireproof sheet after curing is not particularly limited, but can be appropriately changed according to the type of the substrate, for example, 0.1 mm or more and 5.0 mm or less. Is preferably within the range of 0.3 mm to 3.0 mm.

As a construction site where the thermally expandable fireproof sheet obtained in this way is constructed, a wall base material is preferable, and the wall base material is particularly limited as long as it has a certain strength as a face material itself. It will never be done. Examples include slate plates, ceramic plates, ALC, concrete plates, various cement plates, calcium silicate plates, hydrous inorganic material-containing boards, gypsum boards, and wood chip cement boards. In addition, wood boards such as plywood, OSB, particle board, CLT, and laminated wood are exemplified.

As a method of using the heat-expandable fireproof sheet, it is preferable that the heat-expandable fireproof sheet is used by being fixed to the wall base material with a fixture. Examples of the fixing tool include a tapping screw and a tucker. Moreover, you may use an adhesive, an adhesive agent, etc. as needed. It is also possible to attach a fireproof board such as a calcium silicate plate and a gypsum board to the surface of the thermally expandable fireproof sheet fixed to the wall base material.

As is apparent from the above-described embodiment, the resin composition for a thermally expandable fireproof sheet according to the first aspect of the present disclosure includes a powdery thermoplastic resin (A), a plasticizer (B), and a nitrogen-containing foam. It is a plastisol which contains the agent (C) and in which the powdery thermoplastic resin (A) and the nitrogen-containing foaming agent (C) are dispersed in the plasticizer (B).

According to the first aspect, it is possible to provide a heat-expandable resin composition for a fire-resistant sheet having excellent fire resistance and having good storage stability and coating workability.

The resin composition for a thermally expandable fireproof sheet according to the second aspect of the present disclosure further contains a phosphorus-based flame retardant (D) in the first aspect.

According to the second aspect, it can act as a catalyst when a thin film called char is formed by heating.

The resin composition for a thermally expandable fireproof sheet according to the third aspect of the present disclosure further contains a carbonizing agent (E) in the first or second aspect.

According to the third aspect, dehydration and carbonization can be performed to form a fireproof foam layer.

The resin composition for a thermally expandable fireproof sheet according to the fourth aspect of the present disclosure further contains titanium dioxide (F) in any one of the first to third aspects.

According to the 4th aspect, the shape maintenance property of a fireproof foaming layer can be improved.

In the resin composition for a heat-expandable fireproof sheet according to the fifth aspect of the present disclosure, in any one of the first to fourth aspects, the powdery thermoplastic resin (A) is a polyvinyl chloride resin or an acrylic resin. is there.

According to the fifth aspect, fire resistance can be improved.

In the resin composition for a thermally expandable fireproof sheet according to the sixth aspect of the present disclosure, in any one of the first to fifth aspects, the nitrogen-containing foaming agent (C) is melamine.

According to the sixth aspect, it is possible to improve the generation efficiency of nonflammable gas, the followability to the construction site, and the fire resistance.

The heat-expandable fireproof sheet according to the seventh aspect of the present disclosure includes a heat-expandable fireproof resin layer obtained by curing a plastisol of the resin composition for a heat-expandable fireproof sheet according to any one of the first to sixth aspects.

According to the seventh aspect, when heated, the heat-expandable refractory resin layer is foamed to form a refractory foamed layer, thereby exhibiting fire resistance.

In the heat-expandable fireproof sheet according to the eighth aspect of the present disclosure, in the seventh aspect, the base material is paper or non-woven fabric.

According to the eighth aspect, it is easy to form into a sheet shape and easy to attach to the surface of the construction site of the building.

In the thermally expandable fireproof sheet according to the ninth aspect of the present disclosure, in the seventh or eighth aspect, at least one layer selected from the group consisting of an inorganic layer, an organic layer, and a metal layer is provided on the other surface of the base material. Have.

According to the ninth aspect, it is easy to adapt to the construction site and purpose of the building.

In the method for producing a thermally expandable fireproof sheet according to the tenth aspect of the present disclosure, the resin composition for a thermally expandable fireproof sheet according to any one of the first to sixth aspects is applied to one surface of a substrate. Then, it is cured by heating and cooling to form a thermally expandable refractory resin layer.

According to the tenth aspect, it is easy to cure the plastisol.

Hereinafter, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to the examples.

Example 1
As powdered thermoplastic resin (A), 25 parts by mass of acrylic resin (LP-3106, manufactured by Mitsubishi Chemical Corporation) and as plasticizer (B), 25 parts by mass of diisononyl phthalate (DINP, manufactured by Shin Nippon Rika Co., Ltd.) As nitrogen blowing agent (C), 12 parts by mass of melamine (manufactured by Nissan Chemical Industries), as phosphorus-based flame retardant (D), 33 parts by mass of ammonium polyphosphate (AP422, manufactured by Clariant Japan), as carbonizer (E) , 13 parts by mass of pentaerythritol (dipentalit, manufactured by Koei Chemical Co., Ltd.), titanium dioxide (F) as TR92 (average particle size 0.24 μm, manufactured by Huntsman) 14 parts by mass, 0.5 parts by mass of antifoaming agent, A dispersant was blended at a ratio of 2.5 parts by mass, and this was uniformly mixed to obtain a resin composition for a thermally expandable fireproof sheet in a plastisol state.

Next, the obtained resin composition for a heat-expandable fireproof sheet was applied to a glass paper (manufactured by Oji F-Tech Co., Ltd.) having a basis weight of 50 g / m ² with a brush so as to have a predetermined film thickness. It was cured by heating for 5 minutes with the set hot press machine to obtain a thermally expandable fireproof sheet. The thickness of the thermally expandable fireproof resin layer in the thermally expandable fireproof sheet after curing was 1.0 mm.

As a wall base material, on top of two 10 mm thick calcium silicate plates, a thermally expandable refractory sheet is placed so that the glass paper side surface of the thermally expandable refractory sheet is in contact with the calcium silicate plate surface. Fixed with. Furthermore, a stud is installed so that a 20 mm gap is formed between the surface of the thermally expandable refractory sheet fixed to the calcium silicate plate surface and the surface material, and a 12 mm thick calcium silicate plate is attached as the surface material. A test body was prepared.

(Example 2)
Tested in the same manner as in Example 1 except that 25 parts by mass of polyvinyl chloride resin (PSL-675, average molecular weight 900, manufactured by Kaneka Corporation) was used as the powdery thermoplastic resin (A) instead of acrylic resin. The body was made.

(Example 3)
As a powdered thermoplastic resin (A), 25 parts by mass of a polyvinyl chloride resin is used instead of an acrylic resin, and as a plasticizer (B), 25 parts by mass of diundecyl phthalate (DUP, Shin Nippon Rika Co., Ltd.) instead of DINP A test specimen was prepared in the same manner as in Example 1 except that was used.

Example 4
The powdered thermoplastic resin (A) is changed to 18 parts by mass, DUP is used as a plasticizer (B) in place of 10 parts by mass, and the nitrogen-containing foaming agent (C) is changed to 14 parts by mass. Other than using 28 parts by mass of ammonium polyphosphate and 6 parts by mass of aluminum phosphite (APA-100, manufactured by Taihei Chemical Industrial Co., Ltd.) as the flame retardant (D), and changing the carbonizer (E) to 17 parts by mass Were prepared in the same manner as in Example 1.

(Example 5)
As a powdered thermoplastic resin (A), 20 parts by mass of an acrylic resin and 10 parts by mass of a polyvinyl chloride resin are used in combination. As a plasticizer (B), 40 parts by mass of DUP is used instead of DINP, and a phosphorus flame retardant (D ) Was changed to 30 parts by mass, and titanium dioxide (F) was changed to 12 parts by mass.

(Example 6)
A test specimen was prepared in the same manner as in Example 1 except that 8 parts by mass of melamine and 4 parts by mass of dicyandiamide (DICY7, manufactured by Mitsubishi Chemical Corporation) were used in combination as the nitrogen-containing foaming agent (C).

(Comparative Example 1)
A test specimen was prepared in the same manner as in Example 1 except that 12 parts by mass of P-5 (manufactured by Otsuka Chemical Co., Ltd.) was used as the inorganic foaming agent instead of the nitrogen-containing foaming agent (C).

The test specimens of Examples 1 to 6 and Comparative Example 1 were evaluated for fire resistance, storage stability, and coating workability, respectively. The criteria for evaluation are as follows.

<Fire resistance>
In accordance with the standard heating curve of JIS A1304, one surface of the test body was heated in an electric furnace, and the temperature of the surface opposite to the heating surface after 1 hour of the test was measured with a thermocouple. The evaluation criteria are shown below.

Good: The temperature of the surface opposite to the heating surface of the specimen is within a range of 162 ° C. or less from the initial heating to 1 hour later.

Not good: The temperature of the surface opposite to the heating surface of the specimen is over 162 ° C. from the beginning of heating.

<Storage stability>
About the obtained resin composition for heat-expandable fireproof sheets, the viscosity at a liquid temperature of 20 ° C. was measured with a BL type viscometer, then poured into a glass bottle with a lid, sealed, and stored at 35 ° C. for 24 hours. About the resin composition after storage, the viscosity at a liquid temperature of 20 ° C. was measured with a BL type viscometer, and the rate of increase in viscosity with respect to the viscosity of the resin composition before storage was calculated. The evaluation criteria are shown below.

Good: The resin composition for a heat-expandable fireproof sheet is not solidified, and the rate of increase in viscosity is less than 50%.

Fear: Although the resin composition for a heat-expandable fireproof sheet is not solidified, the viscosity increase rate is 50% or more.

Not good: The resin composition for heat-expandable fireproof sheets was solidified.

<Coating workability>
Using a spray gun (W-101, manufactured by Anest Iwata) as the base material, the distance from the spray gun outlet to the paper is 10 cm, and the discharge pressure is 0.3 MPa. The composition was applied. The evaluation criteria are shown below.

Good: The resin composition for a heat-expandable fireproof sheet is uniformly and sufficiently applied to paper.

Not good: The resin composition for a heat-expandable fireproof sheet is discharged in a dusty manner on paper and is not evenly and sufficiently applied.

The results are shown in Table 1.

As shown in Table 1, it was confirmed that the specimens of Example 1-6 were good in any of fire resistance, storage stability and coating workability.

On the other hand, in Comparative Example 1 in which an inorganic foaming agent was blended instead of the nitrogen-containing foaming agent (C), the storage stability and coating workability were good, but the fire resistance evaluation was not good, and the examples It was confirmed to be inferior.

Claims

A powdery thermoplastic resin (A), a plasticizer (B) and a nitrogen-containing foaming agent (C) are contained, and the powdery thermoplastic resin (A) and the nitrogen-containing foaming are contained in the plasticizer (B). A plastisol in which the agent (C) is dispersed,
A resin composition for a heat-expandable fireproof sheet.
Further containing a phosphorus-based flame retardant (D),
The resin composition for heat-expandable fireproof sheets according to claim 1.
Further containing a carbonizing agent (E),
The resin composition for heat-expandable fireproof sheets according to claim 1 or 2.
Further containing titanium dioxide (F),
The resin composition for heat-expandable fireproof sheets according to any one of claims 1 to 3.
The powdery thermoplastic resin (A) is a polyvinyl chloride resin or an acrylic resin.
The resin composition for thermally expansible fireproof sheets as described in any one of Claim 1 to 4.
The nitrogen-containing blowing agent (C) is melamine,
The resin composition for a heat-expandable fireproof sheet according to any one of claims 1 to 5.
A heat-expandable fire-resistant resin layer obtained by curing the plastisol of the resin composition for a heat-expandable fire-resistant sheet according to any one of claims 1 to 6 is provided on one surface of the substrate.
Thermally expandable fireproof sheet.
The substrate is paper or nonwoven;
The thermally expandable refractory sheet according to claim 7.
On the other surface of the substrate, it has at least one layer selected from the group consisting of an inorganic layer, an organic layer, and a metal layer.
The thermally expandable fireproof sheet according to claim 7 or 8.
After applying the resin composition for a heat-expandable fireproof sheet according to any one of claims 1 to 6 to one surface of a substrate, the heat-expandable fireproof resin is cured by heating and cooling. Forming a layer,
A method for producing a thermally expandable fireproof sheet.