WO2016167868A1

WO2016167868A1 - Fire spread prevention member and fire spread suppression method

Info

Publication number: WO2016167868A1
Application number: PCT/US2016/017961
Authority: WO
Inventors: Jun Fujita; Koji Tsuda; Takahiro Kasahara
Original assignee: 3M Innovative Properties Company
Priority date: 2015-04-13
Filing date: 2016-02-15
Publication date: 2016-10-20
Also published as: JP2016199710A

Abstract

To provide a fire spread prevention member having good flexibility while having a high expansion ratio at the time of heating and sufficient mechanical strength after heating, and a method of using this fire spread prevention member to suppress fire spread with a structure used in a fire prevention facility. A fire spread prevention member for suppressing fire spread with a structure used in a fire prevention facility, the fire spread prevention member comprising: (A) 100 parts by mass of a polyurethane binder; and (B) from 30 to 180 parts by mass of expandable graphite; the polyurethane binder (A) comprising a structure derived from a polyol containing a structure with at least ten consecutive carbon atoms.

Description

FIRE SPREAD PREVENTION MEMBER AND FIRE SPREAD

SUPPRESSION METHOD

Technical Field

The present invention relates to a fire spread prevention member for suppressing fire spread installed on a structure used in a fire prevention facility, and a method for suppressing fire spread using a fire spread prevention member installed on a structure used in a fire prevention facility. Here, a structure may include a fireproof door, a fireproof window, or the like.

Background Art

Various fire prevention facilities have been conventionally used to prevent fire in structures such as houses, buildings, railroad cars, and ships. When a structure used in a fire prevention facility has a gap at the time of a fire (for example, a gap between a door and a door frame, a gap between a window and a window frame, a gap between a roof and a wall, a ventilation opening, or the like in a building), this gap may form a pathway for gases (such as air) and/or a

propagation path for flames and heat, which may cause fire spread. Even if the member itself constituting the structure has sufficient fire prevention performance, when such fire spread occurs, it is not possible to realize sufficient fire prevention of the building as a result. Accordingly, there is a demand to suppress fire spread with a structure used in a fire prevention facility. Here, a fire prevention facility may include fire prevention facilities prescribed by various regulations such as the Building Standards Act.

Patent Document 1 describes a fire-resistant resin composition comprising of 100 parts by weight of an epoxy resin, from 10 to 300 parts by weight of

neutralized thermally expandable graphite, and from 50 to 500 parts by weight of an inorganic filler.

Patent Document 2 describes a fire-resistant resin composition in which a thermoplastic resin comprises a phosphorus compound, neutralized thermally expandable graphite, and an inorganic filler, wherein the content of each component is such that the total amount of the phosphorus compound and the neutralized thermally expandable graphite is from 20 to 200 parts by weight and the amount of the inorganic filler is from 50 to 500 parts by weight per 100 parts by weight of the thermoplastic resin, and the weight ratio of the neutralized thermally expandable graphite to the phosphorus compound is from 9: 1 to 1 : 100. Patent Document 3 describes an adhesive fire-resistant sheet comprising a butyl rubber as a resin component, wherein a substrate layer selected from a heat- meltable film, a metal foil laminate film, a metal vapor deposition film, or a metal foil is laminated on one side of a thermally expandable sheet which expands when heated so as to form a fire-resistant insulating layer and has tackiness at room temperature, and the non-laminated side of the substrate layer is subj ected to mold releasing treatment.

Patent Document 4 describes a fire-resistant powder comprising (A) an aluminum hydroxide powder, (B) a titanium oxide powder, (C) a microcapsule in which an ammonium polyphosphate powder is coated with a resin, (D) a melamine compound powder or a pentaerythritol powder, and (E) thermally expandable graphite having a mean particle size of from 50 to 200 micrometers.

Patent Document 5 describes a flame retardant resin composition prepared by incorporating into a polyurethane at least ammonium polyphosphate, aluminum hydroxide or magnesium hydroxide, a polyhydric alcohol-based char layer forming agent, a nitrogen-containing compound having a melamine skeleton, and a flame retardant material containing expandable graphite.

Patent Document 6 describes a fire-resistant powder comprising (A) thermally expandable graphite, (B) a microcapsule in which an ammonium polyphosphate powder is coated with a resin, and (C) an aluminum hydroxide powder, a melamine compound powder, and a pentaerythritol powder.

Citation List

Patent Literatures

Patent Document 1 : Japanese Unexamined Patent Application Publication No. 2000-143941A

Patent Document 2: Japanese Unexamined Patent Application Publication No. H9-227716A

Patent Document 3 : Japanese Unexamined Patent Application Publication No. 2000-38785A

Patent Document 4: Japanese Unexamined Patent Application Publication No. 2014-47251A

Patent Document 5 : Japanese Unexamined Patent Application Publication No. 2012-52092A

Patent Document 6: Japanese Unexamined Patent Application Publication No. 2012-7109A Summary of Invention

Patent Documents 1 to 3 all focus attention on forming an expandable insulating layer using a fire-resistant composition for the coating of building materials and do not focus on the suppression of fire spread from gaps in structures. In addition, the fire-resistant composition described in Patent Document 1 is hard since an epoxy resin is used, and it is difficult to make this composition conform to various shapes of structures or to supply the composition in the form of a rolled sheet, for example. Furthermore, Patent Document 2 describes a polyethylene resin or the like as a thermoplastic resin that can be used, but in this document, there is no focus on the necessity of a member having good flexibility so that it can be made to conform to various shapes of structures or supplied in the form of a rolled sheet, for example. In addition, although the adhesive fire-resistant sheet described in Patent Document 3 can be supplied as a rolled product, it has the drawback that it requires mold releasing treatment of the substrate layer in order to enable unrolling from the rolled product and therefore requires a complicated manufacturing process.

In addition, fire prevention compositions or flame retardant compositions comprising a polyurethane resin are described in Patent Documents 4 to 6, but these documents focus on flame retarding an actual product using a polyurethane resin and do not envision suppressing the fire spread through an already existing structure by applying the composition to the structure. Furthermore, the compositions described in Patent Documents 4 to 6 are thus not designed so as to seal a gap in a structure by means of a high expansion ratio.

The present inventors focused attention on suppressing the flow of gases and the propagation of flames and heat through a gap in a structure so as to suppress the fire spread through a structure by applying a fire spread prevention member to a structure and configuring the fire spread prevention member so as to exhibit a high expansion ratio at the time of heating and sufficient mechanical strength after heating. In addition, the present inventors focused attention on imparting good flexibility to a fire spread prevention member used in this way so as to allow the fire spread prevention member to be applied to structures of various shapes and to provide the fire spread prevention member in a shape with excellent handleability such as a rolled sheet, for example.

Accordingly, the present invention provides a fire spread prevention member that is useful for suppressing fire spread with a structure used in a fire prevention facility, the fire spread prevention member having good flexibility while having a high expansion ratio at the time of heating and sufficient mechanical strength after heating, and a method of using this fire spread prevention member to suppress fire spread with a structure used in a fire prevention facility.

Solution to Problem

One aspect of the present invention provides a fire spread prevention member for suppressing fire spread with a structure used in a fire prevention facility, the fire spread prevention member comprising:

(A) 100 parts by mass of a polyurethane binder; and

(B) from 30 to 180 parts by mass of expandable graphite;

the polyurethane binder (A) comprising a structure derived from a polyol containing a structure with at least ten consecutive carbon atoms.

Another aspect of the present invention is a method for suppressing fire spread with a structure used in a fire prevention facility, the method comprising arranging the fire spread prevention member on at least part of the structure.

Advantageous Effects of Invention

With the present invention, it becomes possible to provide a fire spread prevention member that is useful for suppressing fire spread with a structure used in a fire prevention facility, the fire spread prevention member imparting excellent handleability due to its good flexibility while having a high expansion ratio at the time of heating and sufficient mechanical strength after heating, and a method of using this fire spread prevention member to suppress fire spread with a structure used in a fire prevention facility.

Description of Embodiments

Fire spread prevention member

One aspect of the present disclosure provides a fire spread prevention member comprising:

(A) 100 parts by mass of a polyurethane binder; and

(B) from 30 to 180 parts by mass of expandable graphite;

The fire spread prevention member of the present disclosure is useful for suppressing fire spread with a structure used in a fire prevention facility. When applied to a prescribed position of a structure, the fire spread prevention member can suppress fire spread with the structure. Examples of structures used in a fire prevention facility include, but are not limited to, a combination of a door and a door frame, a combination of a window and a window frame, a combination of a roof and a wall, a ventilation opening, and the like in a building, for example. In a typical aspect, when the fire spread prevention member is heated at a high temperature exceeding approximately 250°C, for example, it expands and is maintained without a substantial loss of form, which makes it possible to form a barrier layer for blocking gases, flames, and heat in the structure. Fire spread is suppressed by such a barrier layer.

The fire spread prevention member of the present disclosure may have good flexibility originating from its component composition. The fire spread

prevention member may have various shapes as long as it can be combined with a structure. A fire spread prevention member that is installed so as to follow the shape of a structure (that is, so as to trace the shape of the structure) is

advantageous in that it can demonstrate particularly good fire spread prevention performance. In addition, the fire spread prevention member of the present disclosure can be easily transported in the shape of a rolled sheet, for example, which is advantageous for automation or the like at the time of pasting to a member.

(A) Polyurethane binder

Using a polyurethane binder (A) (that is, using polyurethane as a binder) is advantageous in that it imparts excellent flexibility to the fire spread prevention member. The fire spread prevention member of the present disclosure can demonstrate excellent flexibility in spite of comprising a large amount of at least approximately 30 parts by mass of expandable graphite (B) per 100 parts by mass of the polyurethane binder (A). However, this member must have water resistance since it is used over a long period of time.

Accordingly, from the perspective of water resistance, a polyol containing a structure with at least ten consecutive carbon atoms can be used as the polyurethane binder (A). In the present disclosure, a structure with at least ten consecutive carbon atoms refers to a structure in which at least ten carbon atoms are bonded by carbon-carbon bonds. A structure with consecutive carbon atoms may typically be a carbon chain in a straight-chain or branched-chain, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain and may be a main chain or a side chain in the molecule. From the perspective of stable water resistance over a long period of time, the structure with consecutive carbon atoms is preferably a carbon chain in a saturated hydrocarbon chain. The polyol may further have carbon atoms present in a structure in addition to the structure with consecutive carbon atoms.

A polyurethane polymer may be one type or a blended product of two or more types. A polyurethane polymer can typically be produced from reaction components including one type or two or more types of polyol, one type or two or more types of isocyanate, and a catalyst (also simply called "reaction components" hereafter).

The polyol may be one or more types selected from the group consisting of polyester polyols, polycarbonate polyols, polyacrylate polyols, polyalkylene polyols, and polyether polyols, for example.

In an enbodyment , the hydroxyl value of the polyol is at least approximately 10 mgKOH/g, at least approximately 20 mgKOH/g, or at least approximately 30 mgKOH/g from the perspective of reactivity and at most approximately 500 mgKOH/g, at most approximately 300 mgKOH/g, or at most approximately 200 mgKOH/g from the perspective of flexibility.

In a preferred aspect, the molecular weight of the polyol is at least approximately 200, at least approximately 300, or at least approximately 400 from the perspective of flexibility and at most approximately 10,000, approximately 7,000, or approximately 5,000 from the perspective of the fluidity of the

composition.

In addition, in a preferred aspect, the viscosity of the polyol measured with a rotational viscometer B-type at a temperature of 25°C is preferably at least approximately 10 mPa s, at least approximately 50 mPa s, or at least approximately 100 mPa s from the perspective of inflammability out of consideration of safety at the time of production and at most approximately 50,000 mPa s, at most

approximately 10,000 mPa s, or at most approximately 5,000 mPa s from the perspective of the fluidity of the composition.

Preferred examples of polyols containing a structure with at least ten consecutive carbon atoms include castor oil, modified castor oil, modified cardanol, dimer acid-modified diol, and polybutadiene diol. These polyols are hydrophobic and are therefore impart excellent moisture resistance to the fire spread prevention member, which is advantageous in that it contributes to the weather resistance of the fire spread prevention member. The number of consecutive carbon atoms of the polyol is preferably at least 10 or at least 12 from the perspective of hydrophobicity and, on the other hand, at most 300 or at most 200 from the perspective of viscosity. In addition, the total number of carbon atoms of the polyol may be at least 20 or at least 50 or at most 500 or at most 200.

An example of a particularly preferable polyol is a polyol containing an alkyl group having from 12 to 100 carbon atoms, and even more preferable examples are castor oil, modified castor oil, and dimer acid-modified diol.

The polyol may be a commercially available product. Examples thereof include available under the trade designations ELA-DR (purified castor oil), HS 1- 160, HS 2G- 120, HS 2G-160R, HS KA-001 , HS 2T-1208, and HS 3G-500B (castor oil-modified polyols, commercially available from the Hokoku Corporation (Yao- shi, Osaka)), purified castor oils such as URIC H-30, URIC HF 1300, URIC H- 1830, and URIC Y-403 (the above are castor oil-modified polyols, commercially available from Itoh Oil Chemicals Co., Ltd. (Yokkaichi-shi, Mie)), URIC H-57, URIC AC-009, and URIC H-368 (the above are aromatic modified castor oil- modified polyols, commercially available from Itoh Oil Chemicals Co., Ltd.), Pripol2033 (hydrogenated dimer diol, commercially available from Croda Japan (Inc.) (Chiyoda-ku, Tokyo)), Nikanol Y100 (xylene resin, commercially available from Fudow Co., Ltd. (Yokohama-shi, Kanagawa)), NX-9001LV, GX-9005, GX- 9007, and GX-9201 (the above are cardanol-modified diols, commercially available from Cardolite, Ltd. (Osaka-shi, Osaka)).

In a preferred aspect, the ratio of the polyol containing a structure with at least ten consecutive carbon atoms to the total amount of polyol is at least approximately 60 mass%, at least approximately 80 mass%, or at least

approximately 90 mass% from the perspective of achieving excellent moisture resistance.

Preferred examples of isocyanates are aromatic-containing liquid

polyisocyanates or the like. Of these, aromatic-containing liquid polyisocyanates are advantageous in that they contribute to the good strength of the fire spread prevention member. In the present disclosure, an "aromatic-containing liquid polyisocyanate" refers to a polyisocyanate which has an aromatic ring and is in a liquid form at 25°C.

Preferable examples of aromatic-containing liquid polyisocyanates include TDI (toluene diisocyanate), XDI (xylylene diisocyanate), NDI (1,5-dinaphthalene isocyanate), l,3-bis(2-isocyanate-2-propyl)benzene and polymeric MDI(methylene diphenyl diisocyanate). Of these, polymeric MDI is a preferable example from the perspectives of viscosity and availability. These may also be modified. In a preferred aspect, the ratio of the aromatic-containing liquid

polyisocyanate to the total amount of isocyanate is at least approximately 70 mass%, at least approximately 80 mass%, or at least approximately 90 mass% from the perspective of achieving good flexibility.

The isocyanate may be a commercially available product. Examples of commercially available products include the trade designations Sumidule 44V10, 44V20, and 44V40 (polymeric MDI, commercially available from Sumika Bayer Urethane Co., Ltd. (Osaka-shi, Osaka)), Milionate MTL (MDI carbodiimide, commercially available from Nippon Polyurethane Industry Co., Ltd. (Minato-ku, Tokyo)), Coronate T65, T80, and T 100 (TDI isomer mixture, commercially available from Nippon Polyurethane Industry Co., Ltd. (Minato-ku, Tokyo)), and Takenate 500 (XDI, commercially available from Mitsui Chemical Co., Ltd.

(Minato-ku, Tokyo)).

In a preferred aspect, the polyurethane binder (A) comprises both a structure derived from a polyol containing a structure with at least ten consecutive carbon atoms and a structure derived from an aromatic-containing liquid polyisocyanate.

In a preferred aspect, the quantity ratio of the polyol and the isocyanate in the reaction components is adjusted so that the NCO/OH ratio is at least

approximately 0.85, at least approximately 0.9, or at least approximately 0.95 and at most approximately 1.15, at most approximately 1.1 , or at most approximately 1.05.

In another preferred aspect, the quantity ratio of the polyol and the isocyanate in the reaction components is adjusted so that the NCO/OH ratio is at least approximately 1. 15, at least approximately 1.5, or at least approximately 2.0 from the perspective of imparting particularly good heat resistance and flame retardance to the fire spread prevention member due to the contribution of isocyanurate structures, and is adjusted so that the NCO/OH ratio is approximately at most 5.0, approximately at most 4.0, or approximately at most 3.0 from the perspective of securing good expansibility and flexibility of the fire spread prevention member by avoiding the excessive generation of isocyanurate structures.

One type or a combination of two or more types of various catalysts known to be usable for urethane polymerization can be used as a catalyst. For example, a catalyst based on tertiary amine, aluminum, bismuth, tin, titanium, vanadium, zinc, or zirconium can be used. In addition, tertiary amines such as N,N',N" -tris(3- dimethylaminopropyl)hexahydro-s-triazine, carboxylic acid/tertiary amine salts, carboxylic acid/quaternary ammonium salts, carboxylic acid/metal salts, and the like can be used as catalysts having high isocyanuratization performance. Of these, a tin-containing catalyst is preferable in that it is highly active, which makes it possible to increase the reaction rate when added in small amounts. The amount of the catalyst that is used may be, for example, at least approximately 0.001 parts by mass or at least approximately 0.01 parts by mass and at most approximately 5 parts by mass or at most approximately 1 part by mass per total of 100 parts by mass of the polyol and isocyanate.

The reaction components may further comprise one type or two or more types of additives. Examples of additives are chain extension agents such as polyamine. Polyamine typically reacts with polyisocyanate to form polyurea. This is used to control the reaction rate or physical properties such as the hardness. The additive content may be, for example, at least approximately 0.5 parts by mass or at least approximately 1 part by mass and at most approximately 10 parts by mass or at most approximately 5 parts by mass per 100 parts by mass of the amount of the polyol. The timing at which these are added may be selected appropriately in accordance with the objective. For example, a preferable polyamine is a polyamine having an aromatic ring in a liquid state at room temperature, and available under the trade designations ETHACURE 100 (diethyl methyl benzene diamine, DETDA) or ETHACURE 410 (methylene bis secondary butylaniline) (both commercially available from the Albemarle Corporation (Chiyoda-ku, Tokyo)) can be used.

In a preferred aspect, the viscosity of the polyurethane binder (A) measured at 25°C with a rotational viscometer is at most approximately 3,000 mPa s, at most approximately 1 ,500 mPa s, or at most approximately 1,000 mPa s from the perspective of ensuring that the other components (the expandable graphite (B), in particular) are well dispersed in the fire spread prevention member and from the perspective of the ease of production of the fire spread prevention member.

(B) Expandable graphite

In the present disclosure, expandable graphite refers to graphite having the characteristic of expanding at the time of heating. Expandable graphite is typically a substance in which an intercalation compound is inserted between the layers of natural flaky graphite. Such expandable graphite can expand when the intercalation compound generates gas due to heat at the time of combustion. The expanded graphite contributes to the formation of the aforementioned barrier layer and therefore the expression of fire spread prevention performance. The expandable graphite may be one type or a blended product of two or more types.

In a preferred aspect, the onset temperature of the expandable graphite (B) is at least approximately 130°C, at least approximately 150°C, or at least

approximately 180°C from the perspective of the heat resistance of the fire spread prevention member and at most approximately 400°C, at most approximately 300°C, or at most approximately 250°C from the perspective of good expansion at the time of a fire. In the present disclosure, the expansion starting temperature is the value of the temperature at the point when expansion is confirmed visually when heated for 30 minutes at a constant temperature. Measurements were taken in temperature intervals of 10°C.

In a preferred aspect, the particle size of the expandable graphite (B) is at least approximately 30 micrometers, at least approximately 10 micrometers, or at least approximately 50 micrometers from the perspective of expandability and at most approximately 1,000 micrometers, at most approximately 500 micrometers, or at most approximately 300 micrometers from the perspective of the flexibility of the composition. In the present disclosure, the particle size is a value calculated from the average weight distribution when screened with a sieve.

The expandable graphite may be a commercially available product.

Examples of commercially available products include the trade designations GREP- EG (commercially available from Suzuhiro Chemical Co., Ltd. (Moriya-shi, Ibaraki)), SYZR502, SYZR502FP, SYZR503, SYZR802, and SYZR803 (the above are commercially available from Sanyo Trading Co., Ltd. (Chiyoda-ku, Tokyo)), and 9532400A, 9950200, 9550250, 955025L, 9280170, 95100150, and 9510045 (the above are commercially available from Ito Graphite Co., Ltd. (Kuwana-shi, Mie)), EXP-50SB 180, EXP-50S, EXP-50, EXP-50S220 and EXP-50S 150 (the above are commercially available from Fuji Graphite Works Co., Ltd. (Setagaya-ku, Tokyo)), Grafguard multiple grades (commercially available from GrafTech

International Holdings Inc. (Ohio, USA)), Asbury expandable graphite multiple grades (commercially available from Asbury Carbons Inc. (New Jersey, USA)).

The amount of the expandable graphite (B) with respect to 100 parts by mass of the polyurethane binder (A) is at least approximately 30 parts by mass, at least approximately 50 parts by mass, or at least approximately 60 parts by mass from the perspective of achieving good flame retardancy and a high expansion ratio of the fire spread prevention member when heated and at most approximately 180 parts by mass or at most approximately 150 parts by mass from the perspective of good film formability when producing the fire spread prevention member and the perspective of good flexibility.

The fire spread prevention member may also comprise additional

components in addition to the components of (A) and (B) described above.

Preferred examples of additional components are given below.

Additional component (C): phosphorus-containing flame retardant

Examples of phosphorus-containing flame retardants include organic phosphorus compounds, phosphates, and red phosphorus and the like. Organic phosphorus compounds are particularly preferable from the perspective of their flame retarding action and handleability. Examples of preferable organic phosphorus compounds include phosphoric acid esters, aromatic condensed phosphoric acid esters, polyphosphates, or phosphinic acid, phosphonic acid, phosphorous acid, phosphoric acid, and metal salts and amine salts thereof and the like. Specific examples of phosphoric acid esters include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, 2-ethyl hexyl diphenyl phosphate, tri-n-butyl phosphate, trixylenyl phosphate, resorcinol(bis)diphenyl phosphate, and bisphenol A bis(diphenyl phosphate). Specific examples of phosphate esters include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and coated ammonium polyphosphate. In the present disclosure, "coated ammonium polyphosphate" refers to ammonium polyphosphate in which the water resistance is improved by coating or encapsulation with a resin. Specific examples of phosphinic acids include diisooctyl phosphinic acid.

The phosphorus-containing flame retardant may be a commercially available product. Examples of commercially available products include the trade designations Exolit AP422 and AP462 (ammonium polyphosphate), AP750

(melamine-modified ammonium polyphosphate), OP 1200, OP 13 12, and OP930 (phosphinic acid metal salt), OP550 (phosphorus-containing polyol), and RP607 (red phosphorus) (all commercially available from Clariant Co., Ltd. (Bunkyo-ku, Tokyo)), FCP-770 (coated ammonium polyphosphate (commercially available from Suzuhiro Chemical Co., Ltd. (Moriya-shi, Ibaraki)), Apinone 303 (guanidinium phosphate), Apinon 405 (guanylurea phosphate), and MPP-A (melamine

polyphosphate) (all commercially available from Sanwa Chemical (Hiratsuka-shi, Kanagawa)), NcendXP-30 (condensed phosphoric acid ester type), AntiblazeMC (ammonium polyphosphate), AntiblazePI (ammonium polyphosphate),

AntiblazeTMCP (tris(l -chloro-2-propyl)phosphate), Antiblazel95

(tris(dichloropropyl)phosphate), and AntiblazeV-6 (halogen-containing condensed phosphoric acid ester) (all commercially available from the Albemarle Corporation (Chiyoda-ku, Tokyo)).

The amount of the phosphorus-containing flame retardant (C) with respect to 100 parts by mass of the polyurethane binder (A) is at least approximately 5 parts by mass, at least approximately 10 parts by mass, or at least approximately 20 parts by mass from the perspective of achieving good flame retardancy and at most approximately 70 parts by mass, at most approximately 60 parts by mass, or at most approximately 50 parts by mass from the perspective of water resistance.

Additional component (D): dispersant

A dispersant is added appropriately to secure the viscosity required for coating when the polyurethane binder is filled with a filler such as expandable graphite or a solid phosphorus-based flame retardant. A dispersant having a viscosity-reducing effect can be advantageously used. Dispersants are typically thought to partially adsorb to the surface of particles and to stabilize the particles without coagulating the particles due to 1) electrical repulsion and 2) steric repulsion between the particles. Dispersants are categorized into low-molecular weight compounds such as surfactants and coupling agents and high molecular weight compounds having various functional groups. Examples of functional groups for adsorbing the dispersant to the particle surface include sulfonic acid groups, phosphoric acid groups, carboxylic acid groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, amide groups, ester groups, and ether groups and the like.

Specific examples of surfactant-type dispersants include stearic acid, isostearic acid, dodecyl benzene sulfonic acid, the available under the trade designations Neogen series, the Neocol series, the Plysurf series, and the Solgen series commercially available from Daiichi Kogyo Seiyaku Co., Ltd. (Kyoto-shi, Kyoto), the Leodor series and the Excel series commercially available from the Kao Corporation (Sumida-ku, Tokyo), and the Chirabazol series commercially available from Taiyo Kagaku Co., Ltd. (Yokkaiichi-shi, Mie) and the like. Examples of coupling agent-type dispersants include the silane coupling agent KBM series and KBE series commercially available from Shin-Etsu Chemical Industry Co., Ltd. (Chiyoda-ku, Tokyo), the silane coupling agent SILQUEST Silanes series commercially available from Momentive Performance Materials Japan Inc.

(Minato-ku, Tokyo), the silane coupling agent Dynasilane series commercially available from Evonik Japan Co., Ltd. (Shinjuku-ku, Tokyo), and the titanate and aluminate-based coupling agent Plenact series commercially available from

Ajinomoto Fine Techno Co., Inc. (Kawasaki-shi, Kanagawa) and the like.

Examples of high molecular weight compound-type dispersants include the

DISPERBYK series commercially available from Byk Chemie Japan Co., Ltd. (Shinjuku-ku, Tokyo), the DISPARLON series commercially available from

Kusumoto Chemicals, Ltd. (Chiyoda-ku, Tokyo), the Floren series commercially available from Kyoeisha Chemical Co., Ltd. (Osaka-shi, Osaka), the AgriSperse series commercially available from New Century Coatings Co., Inc. (Arizona, U. S.A.), and the Marialim series commercially available from the NOF Corporation (Shibuya-ku, Tokyo) and the like.

In addition, the dispersant may be used alone, or two or more types may be used in combination.

A phosphorus-containing dispersant is particularly preferable in that it disperses the expandable graphite (B) and the phosphorus-containing flame retardant (C) well in the fire spread prevention member, which makes it possible to reduce the viscosity. Examples of phosphorus-containing dispersants include phosphate ester dispersants and phosphoric acid ester dispersants. Examples of commercially available products include trade designations Disperbykl40 and Disperbykl45 (phosphoric acid ester salt dispersants, commercially available from Byk Chemie Japan Co., Ltd. (Shinjuku-ku, Tokyo)), PhosmerM and PhosmerPE (acid-phosphoxylalkyl-methacrylate, commercially available from Uni Chemical Co., Ltd. (Sango-cho, Ikoma-gun, Nara)), and Plysurf A212C, AL, A208F, A208N, M208F, and DOM (commercially available from Daiichi Kogyo Seiyaku Co., Ltd. (Kyoto-shi, Kyoto)) and the like.

In a preferred aspect, the content of the phosphorus-containing dispersant with respect to 100 parts by mass of the components other than the polyurethane binder (A) in the fire spread prevention member is at least approximately 0.1 parts by mass, at least approximately 0.2 parts by mass, or at least approximately 0.5 parts by mass from the perspective of achieving a good dispersion improving effect of these components and at most approximately 10 parts by mass, at most approximately 5 parts by mass, or at most approximately 3 parts by mass from the perspective of water resistance. Additional component (E): dehydrating agent

Furthermore, a dehydrating agent can be used as a preferable additional component. A dehydrating agent can adjust foaming caused by a reaction between the water content and isocyanate in the composition when producing the fire spread prevention member. Specific examples of dehydrating agents include silica gel, zeolites such as a molecular sieve, and metal oxides such as calcium oxide and magnesium oxide. Zeolites are particularly preferable from the perspective of dispersibility. The content of the dehydrating agent (E) with respect to 100 parts by mass of the polyurethane binder (A) in the fire spread prevention member may be, for example, at least approximately 0 parts by mass or at least approximately 2 parts by mass and at most approximately 20 parts by mass or at most approximately 10 parts by mass.

Additional component (F): inorganic hollow particles

Inorganic hollow particles may be further used as a preferable additional component. Inorganic hollow particles themselves are nonflammable and have a small true specific gravity, so they can reduce the weight of the fire spread prevention member, which yields the advantage that the load at the time of production is small. Examples of inorganic hollow particles include hollow glass and ceramic bubbles and the like, and glass bubbles (3M Japan Co., Ltd.

(Shinagawa-ku, Tokyo)), available under the trade designations Winlite (shirasu balloon, Axyz Chemical Co., Ltd. (Kagoshima-shi, Kagoshima)), Hardlite (perlite balloon, Showa Chemical Industries Co., Ltd. (Meguro-ku, Tokyo)), and the like can be obtained commercially. The content of the inorganic hollow particles (F) with respect to 100 parts by mass of the polyurethane binder (A) in the fire spread prevention member may be, for example, at least approximately 0 parts by mass and at most approximately 50 parts by mass.

Inorganic compounds may be used as other additional components. These may be used for various purposes. For example, hydroxides such as aluminum hydroxide and magnesium hydroxide act as flame retardants utilizing dehydration reactions at high temperatures, and calcium carbonate, magnesium carbonate, and the like are themselves nonflammable, which makes it possible to reduce the cost of the fire spread prevention member. Further examples include non-phosphorus based flame retardants such as zinc borate, melamine compounds, and nanoclay, colorants, and anti-aging agents and the like. Additional component (G): fibers

In a preferred aspect, the fire spread prevention member further contains fibers. In a typical aspect, the fibers in the fire spread prevention member can be dispersed in a state in which the fiber lengthwise direction is aligned in a direction essentially perpendicular to a given direction of the fire spread prevention member (for example, the thickness direction of a sheet-like fire spread prevention member). Such a dispersion state of the fibers is realized, for example, by rolling when a sheet-like fire spread prevention member is formed by rolling a material composition. A fire spread prevention member containing fibers is unlikely to thermally expand in the fiber lengthwise direction but easily expands in a direction perpendicular to the fiber length. When the fire spread prevention member contains fibers, it is possible to thermally expand the fire spread prevention member primarily in a specific direction (that is, to form a fire spread prevention member having an anisotropic thermal expansion ratio). In this case, it is possible to realize good fire spread prevention performance by expanding the fire spread prevention member with a high expansion rate in a specific prescribed direction and to maintain good residue strength by reducing the decrease in density due to the thermal expansion of the fire spread prevention member.

In a preferred aspect, the amount of the fibers with respect to 100 parts by mass of the polyurethane binder (A) is at least approximately 0.1 parts by mass, at least approximately 0.5 parts by mass, or at least approximately 1.0 parts by mass from the perspective of favorably achieving the effect of the fibers, and is at most approximately 20 parts by mass, at most approximately 10.0 parts by mass, or at most approximately 5.0 parts by mass from the perspective of achieving a good thermal expansion ratio.

Examples of materials of the fibers include acrylic fibers (acrylonitrile copolymers), cellulose, polyvinyl alcohol, polyester, polyphenylene sulfide, polyamide, polyimide, and phenol-based fibers. Phenol-based fibers and acrylic fibers are preferable from the perspective that the fibers are dispersed favorably in the fire spread prevention member since the wettability of the fibers with respect to a polyurethane binder is good. The fibers may be a commercially available product. A preferred example of a commercially available product is the trade designations Fiber Kynol (Gunei Chemical Industry (Takasaki-shi, Gunma)).

In a preferred aspect, the fiber diameter of the fibers is at least

approximately 0.1 micrometers, at least approximately 0.5 micrometers, or at least approximately 1.0 micrometers from the perspective of the viscosity, and is at most approximately 200 micrometers, at most approximately 150 micrometers, or at most approximately 100 micrometers from the perspective of dispersibility.

In a preferred aspect, the fiber length of the fibers is at least approximately 0.5 mm, at least approximately 1.0 mm, or at least approximately 2.0 from the perspective of favorably achieving the effect of the fibers, and is at most

approximately 10.0 mm, at most approximately 8.0 mm, or at most approximately 5.0 mm from the perspective of achieving a good thermal expansion ratio.

Additional component (H): char former

In a preferred aspect, the fire spread prevention member further contains a char former. In the present disclosure, a char former refers to a component which accelerates carbonization by suppressing the rapid combustion of the fire spread prevention member. A fire spread prevention member containing a char former can exhibit an even better residue residual ratio and residue strength. An example of a char former is a combination of an aromatic compound and the aforementioned flame retardant utilizing a dehydration reaction. An aromatic compound is advantageous in that it favorably generates a carbide.

Using an aromatic compound in combination with a flame retardant utilizing a dehydration reaction is advantageous from the perspective of realizing good carbonization of the aromatic compound and therefore a good residue residual ratio and good residue strength of the fire spread prevention member after thermal expansion. The limiting oxygen index (LOI) of an aromatic compound (in particularly, a compound with a high Tg or high Tm) is typically high. For example, the LOI of a polyether imide (available under the trade designations ULTEM™ 1000 (SABIC Japan Ltd, Chiyoda-ku, Tokyo)) mentioned in the working examples described below is 47. A flame retardant utilizing a dehydration reaction functions as a flame retardant by reducing the ambient temperature by the decomposition of the flame retardant itself and lowering the combustion rate of the fire spread prevention member. At this time, the aromatic compound and other carbon-containing substances in the fire spread prevention member are favorably carbonized, and a residue having good mechanical strength is generated.

Examples of flame retardants utilizing a dehydration reaction include metal hydroxides or metal salt hydrates such as aluminum hydroxide, magnesium hydroxide, or zinc borate, for example. Of these, magnesium hydroxide is preferable in that the decomposition start temperature is relatively high at approximately 300 to approximately 400°C. In a typical aspect, the temperature at the time of thermal expansion presumed when the fire spread prevention member is used is from approximately 200 to approximately 350°C. When a flame retardant having a higher decomposition temperature than the temperature at the time of thermal expansion is used, there is no decrease in temperature due to the

decomposition of the flame retardant at the time of the thermal expansion of the fire spread prevention member, so the fire spread prevention member expands favorably. Moreover, when the fire spread prevention member is exposed to even higher temperatures after thermal expansion, the flame retardant decomposes so as to promote the favorable carbonization of the fire spread prevention member. As a result, it is possible to achieve both a good thermal expansion ratio and good residue strength.

An example of an aromatic compound is an aromatic compound having a glass transition temperature (Tg) of at least approximately 150°C and at most approximately 300°C and/or a melting point (Tm) of at least approximately 150°C and at most approximately 350°C. Examples of such aromatic compounds include crosslinked novolak resins (Tg: at least 300°C), polyphenylene ether (PPE) (Tg: 215°C), polyphenylene sulfide (PPS) (Tm: 278°C), and polyether sulfone (Tg: 225°C). In the present disclosure, the glass transition temperature (Tg) and the melting point (Tm) are values measured with a differential scanning calorimeter at a heating rate of 10°C/min. The aromatic compound may be a commercially available product. Examples of commercially available products include the trade designations PPO Powder (SABIC Japan Ltd, Chiyoda-ku, Tokyo), PEI Powder (SABIC Japan Ltd, Chiyoda-ku, Tokyo), and PPS Powder (Polyplastics Co., Ltd, Minato-ku, Tokyo).

In a particularly preferred aspect, the char former is a combination of magnesium hydroxide and an aromatic compound having a glass transition temperature (Tg) of at least approximately 150°C and at most approximately 300°C and/or a melting point (Tm) of at least approximately 150°C and at most

approximately 350°C.

In an aspect in which the char former is a combination of an aromatic compound and a flame retardant utilizing a dehydration reaction, the amount of the flame retardant with respect to 100 parts by mass of the polyurethane binder is preferably at least approximately 10 parts by mass, at least approximately 15 parts by mass, or at least approximately 20 parts by mass and is preferably at most approximately 60 parts by mass, at most approximately 55 parts by mass, or at most approximately 50 parts by mass. In an aspect in which the char former is a combination of an aromatic compound and a flame retardant utilizing a dehydration reaction, the amount of the aromatic compound with respect to 100 parts by mass of the polyurethane binder is preferably at least approximately 10 parts by mass, at least approximately 15 parts by mass, or at least approximately 20 parts by mass and is preferably at most approximately 60 parts by mass, at most approximately 55 parts by mass, or at most approximately 50 parts by mass.

In an aspect in which the char former is a combination of an aromatic compound and a flame retardant utilizing a dehydration reaction, an example of a preferable composition of the fire spread prevention member comprises 100 parts by mass of a polyurethane binder, from approximately 30 to approximately 100 parts by mass of expandable graphite, from approximately 10 to approximately 100 parts by mass of a phosphorus-containing flame retardant, from approximately 0.1 to approximately 5 parts by mass of a phosphorus-containing dispersant, from approximately 10 to approximately 60 parts by mass of a flame retardant utilizing a dehydration reaction (preferably magnesium hydroxide), and from approximately 30 to approximately 60 parts by mass of an aromatic compound. The

polyurethane binder in this aspect is preferably a polyurethane binder obtained using a castor oil modified polyol and aromatic isocyanate. The polyurethane binder is preferably a polyurethane binder obtained using a polyol and isocyanate at a quantity ratio such that the NCO/OH ratio is at least approximately 1.

Various methods can be used to produce the fire spread prevention member. For example, a fire spread prevention member can be obtained by mixing a polyol serving as the raw material of the polyurethane binder (A) and other components of the fire spread prevention member, further mixing a polyisocyanate serving as a curing component of the polyurethane binder, and then reacting the resulting mixture. As a more preferable production method, a sheet-shaped fire spread prevention member can be obtained, for example, by applying the aforementioned mixture between two mold-releasable film-like substrates, passing the resulting laminate through a gap of a prescribed thickness so as to produce a uniform sheet, then heat-curing the sheet in a heating oven, and then peeling and removing the film-like substrate. Furthermore, when an adhesive tape is used on at least one of the two film-like substrates, it is possible to produce a sheet-shaped fire spread prevention member provided with an adhesive.

Examples of the shape of the fire spread prevention member include a sheet and a block and the like. A sheet is preferable in that it can be applied so as to follow various shapes of the structure and in that it is easy to transport and apply. Of these, a rolled sheet is preferable from the perspective of the ease of

transportation and application.

In order for the fire spread prevention member to function, it is necessary to fill a gap present in the structure at the time of a fire. Accordingly, the initial thickness and expansion ratio of the fire spread prevention member are controlled so that the size of the fire spread prevention member after expansion is sufficiently larger than the gap.

In a preferred aspect, the thickness of the fire spread prevention member is at least approximately 0.3 mm, at least approximately 0.5 mm, or at least approximately 0.8 mm from the perspective of achieving good fire spread prevention performance and at most approximately 10 mm, at most approximately 5 mm, or at most approximately 3 mm from the perspective of favorably achieving the advantages of flexibility and the perspective of the installation location. A fire spread prevention member of such a thickness can be supplied as a sheet and preferably a rolled sheet.

In a preferred aspect, the expansion ratio of the fire spread prevention member at the time of heating is at least approximately 10 times, at least

approximately 15 times, or at least approximately 20 times from the perspective of achieving good fire spread prevention performance and at most approximately 50 times, at most approximately 40 times, or at most approximately 30 times from the perspective of maintaining the shape after expansion.

In a preferred aspect, the glass transition temperature (Tg) of the fire spread prevention member is at most approximately 50°C, at most approximately 40°C, at most approximately 25°C, or at most approximately 20°C from the perspective of achieving good flexibility and at least approximately -40°C, at least approximately -30°C, or at least approximately -20°C from the perspective of achieving good mechanical strength of the fire spread prevention member. When the thickness of the fire spread prevention member is relatively large, it is advantageous from the perspective of the flexibility of the fire spread prevention member for the glass transition temperature to be lower. From this perspective, when the thickness of the fire spread prevention member is at least approximately 0.3 mm, at least approximately 0.5 mm, or at least approximately 0.8 mm, for example, the glass transition temperature may preferably be at most approximately 25°C or at most approximately 20°C. In a preferred aspect, the Shore A hardness of the fire spread prevention member is at least approximately 20, at least approximately 30, or at least approximately 40 from the perspective of achieving good mechanical strength and at most approximately 80, at most approximately 75, or at most approximately 70 from the perspective of achieving good flexibility.

In a preferred aspect, the storage modulus of the fire spread prevention member is at least approximately 0.1 MPa(Mega Pascal), at least approximately 0.5 MPa, or at least approximately 1.0 MPa from the perspective of the handleability due to stickiness prevention and the perspective of achieving good mechanical strength and at most approximately 100 MPa, at most approximately 50 MPa, or at most approximately 10 MPa from the perspective of achieving good flexibility.

The residue residual rate of the fire spread prevention member after heating is preferably as high as possible. In a preferred aspect, the residue residual rate is at least approximately 60% or at least approximately 70% from the perspective of exhibiting good fire spread prevention performance.

Each characteristic value described above is a value measured with the method described in the Examples section of the present disclosure or a method that would be understood to be equivalent thereto by a person having ordinary skill in the art.

The fire spread prevention member is arranged at a location where a gap is located or where a gap generates at the time of a high temperature. When exposed to a high temperature, the fire spread prevention member expands so as to fill the gap and prevents fire spread by blocking flames. Methods of arranging the fire spread prevention member include a method of inserting and sealing the fire spread prevention member in a gap part of the structure, a method of directly attaching the fire spread prevention member to a substrate of the structure with a tacker stapler or the like, a method of attaching the fire spread prevention member to the structure with an adhesive.

In the case of a method of inserting and sealing the fire spread prevention member in the gap part and a method of directly attaching the fire spread

prevention member to a substrate with a tacker stapler or the like, it is preferable for a layer of a material with good slippage (also called a "slipping layer" in the present disclosure) to be laminated on at least one side of the fire spread prevention member. A resin film, paper, metal foil, or the like can be used as a material with good slippage. The slipping layer may have colors, a pattern, or the like. For example, a slipping layer formed by applying colors, a pattern, or the like to a vinyl chloride resin sheet is preferable. The thickness of the slipping layer is preferably from approximately 1 micrometers to approximately 150 micrometers.

In the case of a method of adhering the fire spread prevention member with an adhesive, it is preferable for an adhesive layer to be provided on the fire spread prevention member directly or via a substrate. Adhesives such as natural rubber- based adhesives, synthetic rubber-based adhesives, acrylic adhesives, and silicone adhesives, for example, can be used as the adhesive constituting the adhesive layer. Examples of acrylic adhesives include isooctyl acrylate/acrylic acid copolymer adhesives and butyl acrylate/hydroxy ethyl acrylate adhesives.

In a preferred aspect, the peel force of the fire spread prevention member is at least approximately 1 N/cm, at least approximately 3 N/cm, or at least approximately 5 N/cm from the perspective of securely attaching the fire spread prevention member to the structure. In the present disclosure, the peel force is a value measured in accordance with JIS Z 0237 (2009 edition) at a rate of 300 mm/min.

Fire spread suppression method

The present disclosure also provides a method for suppressing fire spread with a structure used in a fire prevention facility, the method comprising arranging the fire spread prevention member according to the present disclosure on at least part of the structure.

The examples listed above can be used as structures. The fire spread prevention member should be arranged at least at a site of the structure which may serve as a pathway for gases and a propagation path for flames and heat. For example, the fire spread prevention member can be arranged at a site of a door opposite a door frame and/or a site of a door frame opposite a door, a site of a window opposite a window frame and/or a site of a window frame opposite a window, in a roof material opposite a ventilation opening, or in a wall material opposite a ventilation opening.

In a preferred aspect, the fire spread prevention member is a sheet. In a preferred aspect, the fire spread prevention member is arranged on at least part of a structure by attaching the fire spread prevention member in the form of a sheet to the structure along the shape of the structure. Methods of attaching the fire spread prevention member to the structure along the shape of the structure include the aforementioned method of inserting and sealing the fire spread prevention member in a gap part, the method of directly attaching the fire spread prevention member to a substrate with a tacker stapler or the like, and the method of adhering the fire spread prevention member with an adhesive. For example, when the surface of the structure where the fire spread prevention member is arranged is a curved surface, the fire spread prevention member can be arranged and attached so as to follow the curved surface.

Examples of adhesive attaching methods include a method of applying an adhesive to the fire spread prevention member and/or the structure and then adhering the fire spread prevention member and the structure to one another and a method of using a fire spread prevention member to which an adhesive (for example, an adhesive agent) is attached in advance and adhering the adhesive to the structure.

Examples

Specific aspects of the present invention will be described further hereinafter using working examples, but the present invention is not limited to these working examples.

Materials

(Polyol)

Nikanol Y100 (xylene resin, hydroxyl value: 25 mgKOH/g, viscosity: 100 mPa s, commercially available from Fudow Co., Ltd. (Yokohama-shi, Kanagawa))

HS 3G-500B (castor oil-modified polyol, hydroxyl value: 50 mgKOH/g, viscosity: 2200 mPa s, commercially available from the Hokoku Corporation)

Pripol2033 (hydrogenated dimer diol, hydroxyl value: 207 mgKOH/g, viscosity: 2500 mPa s, commercially available from Croda Japan (Inc.))

URIC H-30 (castor oil-modified polyol, hydroxyl value: 160 mgKOH/g, viscosity: 690 mPa s, commercially available from Itoh Oil Chemicals Co., Ltd.)

URIC HF 1300 (castor oil-modified polyol, hydroxyl value: 90 mgKOH/g, viscosity: 210 mPa s, commercially available from Itoh Oil Chemicals Co., Ltd.)

URIC Y-403 (castor oil-modified polyol, hydroxyl value: 160 mgKOH/g, viscosity: 220 mPa s, commercially available from Itoh Oil Chemicals Co., Ltd.)

URIC Y-406 (castor oil-modified polyol, hydroxyl value: 160 mgKOH/g, viscosity: 250 mPa s, commercially available from Itoh Oil Chemicals Co., Ltd.)

URIC AC-009 (aromatic modified castor oil-modified polyol, hydroxyl value: 225 mgKOH/g, viscosity: 1550 mPa s, commercially available from Itoh Oil Chemicals Co., Ltd.) P2010 (methyl pentanediol adipic acid polyester polyol, hydroxyl value: 55 mgKOH/g, viscosity: 5700 mPa s, Mw: 2000, commercially available from Kuraray Co., Ltd.)

P510 (methyl pentanediol adipic acid polyester polyol, hydroxyl value: 219 mgKOH/g, viscosity: 510 mPa s, Mw: 500, commercially available from Kuraray Co., Ltd. (Chiyoda-ku, Tokyo))

[0089]

(Isocyanate)

Sumidule 44V10 (polymer MDI, isocyanate (NCO) equivalent: 3 1%, viscosity: 130 mPa s, commercially available from Sumika Bayer Urethane Co., Ltd.)

Milionate MTL (MDI carbodiimide, isocyanate (NCO) equivalent: 29%, viscosity: 50 mPa s, commercially available from Nippon Polyurethane Industry Co., Ltd.)

The viscosity described above is a value measured with a rotational viscometer.

(Expandable graphite)

SYZR502 (particle size: 300 micrometers, expansion starting temperature: 180°C, commercially available from Sanyo Trading Co., Ltd.)

SYZR503 (particle size: 300 micrometers, expansion starting temperature: 300°C, commercially available from Sanyo Trading Co., Ltd.)

SYZR802 (particle size: 180 micrometers, expansion starting temperature: 180°C, commercially available from Sanyo Trading Co., Ltd.)

SYZR803 (particle size: 180 micrometers, expansion starting temperature: 300°C, commercially available from Sanyo Trading Co., Ltd.)

GREP-EG (particle size: 500 micrometers, expansion starting temperature: 300°C, commercially available from Suzuhiro Chemical Co., Ltd. (Moriya-shi, Ibaraki))

9532400A (particle size: 600 micrometers, expansion starting temperature: 180°C, commercially available from Ito Graphite Co., Ltd. (Kuwana-shi, Mie))

953240L (particle size: 500 micrometers, expansion starting temperature: 160°C, commercially available from Ito Graphite Co., Ltd. (Kuwana-shi, Mie)) [0091] (Phosphorus-containing flame retardant)

FCP-770 (coated ammonium polyphosphate, particle size: 10 micrometers, commercially available from Suzuhiro Chemical Co., Ltd. (Moriya-shi, Ibaraki))

Exolit422 (ammonium polyphosphate, particle size: 10 micrometers, commercially available from Clariant Co., Ltd.)

(Isocyanuratization reaction catalyst)

KAOLIZER No. 14 (N-N'-N"-tris(3-dimethylaminopropyl)hexahydro-s- triazine (commercially available from the Kao Corporation (Chuo-ku, Tokyo))

(Dispersant)

Disperbykl45 (phosphoric acid ester salt dispersant, acid value: 76 mgKOH/g, amine value: 71 mgKOH/g, commercially available from Byk Chemie Japan Co., Ltd. (Shinjuku-ku, Tokyo))

Ply surf A212C (phosphoric acid partial ester, commercially available from Daiichi Kogyo Seiyaku Co., Ltd.)

(Zeolite)

Molecular sieve 4A (powder, commercially available from TOMOE

Engineering Co., Ltd. (Shinagawa-ku, Tokyo))

(Inorganic hollow particles)

GB K17 (glass microscopic hollow spheres, true specific gravity: 0.37 g/ml, particle size: 0.045 mm, commercially available from 3M Japan Co., Ltd.

(Shinagawa-ku, Tokyo))

Winlite MSB-3011 (perlite balloon, true specific gravity: 0.9 g/ml, particle size: 0.1 mm, commercially available from Hayashi-Kasei Co., Ltd. (Osaka-shi, Osaka))

Hard Light B-05S (perlite balloon, true specific gravity: 0.8 g/ml, particle size: 0.06 mm, commercially available from Axyz Chemical Co., Ltd. (Kagoshima- shi, Kagoshima))

(Inorganic filler)

CaC0₃ #1 (calcium carbonate, first grade, commercially available from Sankyo Seifun Co., Ltd. (Niimi-shi, Okayama)

MgC0₃ (magnesium carbonate, commercially available from the Naikai Corporation (Minato-ku, Tokyo)) (Flame retardant utilizing dehydration reaction)

Mg(OH)2 Magseas N-6 (magnesium hydroxide, commercially available from Konoshima Chemical Co., Ltd. (Osaka-shi, Osaka))

Al(OH)₃ B53 (aluminum hydroxide, commercially available from Nippon Light Metal Co., Ltd. (Shinagawa-ku, Tokyo))

(Flame retardant)

Firebrake ZB (zinc borate, commercially available from Hayakawa & Co., Ltd. (Chuo-ku, Tokyo))

(Fibers)

Kynol Fiber (KF-0203 (novoloid fibers, fiber diameter: 14 micrometers, fiber length: 3 mm, commercially available from Gunei Chemical Industry

(Takasaki-shi, Gunma))

(Aromatic compound)

PPE (polyphenylene ether) (PPO™, 300 mesh, Tg: 215°C, commercially available from SABIC Japan Corporation (Chiyoda-ku, Tokyo))

PEI (polyether imide) (ULTEM™ 1000, 50 mesh, Tg: 217°C, commercially available from SABIC Japan Corporation (Chiyoda-ku, Tokyo))

R35 Reclaimed Rubber (250 mesh, Tg: -40°C, commercially available from Global Co., Ltd. (Yokohama- shi, Kanagawa))

Evaluation

Each sample was evaluated as follows.

(1) Expansion ratio

A test piece of 25 mm diameter was cut out from each sample using a punch. The test piece was placed on an alumina plate and covered with a cylindrical steel tube. The plate was placed in an oven and held for 15 minutes at 370°C to thermally expand the test piece. The plate was retrieved from the oven and left to cool. The steel tube was removed, and the height of the expanded test piece was measured with vernier calipers. The expansion ratio was calculated in accordance with the following formula: expansion ratio = height after expansion/initial height. (2) Residue residual rate (a)

A test piece of 25 mm diameter was cut out from each sample using a punch in the same manner as in (1) above. The test piece was placed on an alumina plate and covered with a cylindrical steel tube. The plate was placed in an oven and held for 15 minutes at 370°C to thermally expand the test piece. The plate was retrieved from the oven and left to cool. The steel tube was removed, and the weight of the expanded test piece was measured. The residue residual rate (a) was calculated in accordance with the following formula: residue residual rate (a) = weight after expansion/initial weight.

(3) Expansion volume

A test piece of 25 mm diameter was cut out from each sample using a punch. The test piece was placed in an alumina plate (thickness: 0.3 mm, height: 40 mm, diameter: 100 mm (opening part) and 80 mm (flat base part)). The plate was placed in an oven and held for 10 minutes at 370°C to thermally expand the test piece. The plate was retrieved from the oven and left to cool. The height, maj or axis, minor axis, and weight of the test piece after expansion were measured.

The expansion volume was calculated in accordance with the following formula related to a half-ellipsoid.

Expansion volume = (4/3)*3.14*h*(x/2)(y/2)(l/2)

(x, y, and h are respectively the major axis, the minor axis, and the height of the half-ellipsoid)

In addition, for some examples (Working Examples 22, 24 to 26, 28 to 32, and 34 to 39 and Comparative Example 6), a test piece after expansion was prepared with the same procedure as that described above with the exception of changing the temperature of 370°C to 500°C in addition to the aforementioned test piece, and the height of this test piece was also measured.

(4) Residue residual rate (b)

A test piece after expansion was obtained with the same procedure as described in (3) above. The residue residual rate (b) was calculated in accordance with the following formula: residue residual rate (b) = weight after

expansion/initial weight. (5) Flexibility

A test piece with a length of 100 mm and a width of 25 mm was cut out from each sample. The test piece was rolled around a one-inch core, and it was observed whether cracks or other problems occurred in the test piece.

(6) Moisture resistance

A test piece of 25 mm diameter was cut out from each sample using a punch. The test piece was placed on a steel container and evaluated for 72 hours at 121 °C and 100% humidity using a highly accelerated stress tester (PC-304R8,

manufactured by Hirayama Manufacturing Corporation (Kasukabe-shi, Saitama)). The test piece was removed from the device, and the external appearance after 24 hours was observed visually.

(7) Viscoelasticity characteristics

A test piece with a length of 3.5 cm and a width of 0.5 cm was cut out from each sample. The glass transition temperature (Tg) of the test piece was measured using a dynamic viscoelastic measuring apparatus. Tg was determined by plotting tangent delta of the storage modulus (E')/loss modulus (E") obtained at a frequency of 1 Hz in a tension mode at a heating rate of 5°C/min and using the resulting peak temperature as Tg.

In addition, the storage modulus around room temperature (25°C) was also recorded.

(8) Adhesive force

The sheet sample with an adhesive produced in Working Example 17 was slit to a width of 10 mm and a length of 100 mm, adhered to a SUS304 plate (width: 20 mm, length: 120 mm), and rolled down back and forth with a 2 kg rubber roller once. Next, the peel force when peeled at an angle of 180 degrees was measured at 25°C at a tension speed of 300 mm/min using a Tensilon (Toyo Baldwin Co., Ltd., RTM-100). The average value measured for three samples was 2.9 N/cm.

(9) Compressive stress

The compressive stress was measured by compressing a test piece prepared in accordance with (7) described above with an aluminum sheet (size: 65 mm x 100 mm, thickness: 1 mm) at a compression rate of 100 mm/min using a Tensilon universal testing machine, and the compressive stress up to a compression amount of 10 mm was recorded.

(10) Residue strength

The compressive stress was measured by compressing a test piece prepared in accordance with (7) described above with an aluminum sheet (size: 65 mm x 100 mm, thickness: 1 mm) at a compression rate of 100 mm/min and a compression area of 25 mm in diameter using a Tensilon universal testing machine, and the compressive stress per unit area for a compression amount of 10 mm was recorded.

Production of fire spread prevention member sample

[Working Example 1]

Part A (isocyanate hardening agent)

Sumidule44V10 was used in an amount of 2.0 g.

Part B (base resin)

First, 2.0 g of HS 3G-500B, 3.0 g of Pripol2033, and 3.0 g of Y-100 (as polyols) as well as 0.2 g of Disperbykl45 (as a dispersant) were mixed well in a plastic container. Next, 3.0 g of FCP-770 (as a flame retardant), 4.0 g of GREP- EG and 3.0 g of SYZR802 (as expandable graphite), and 0.3 g of zeolite 4A were added to the container and mixed for 2 minutes at 2000 rpm with a planetary centrifugal mixer.

Parts A and B were mixed for 2 minutes at 2000 rpm with a planetary centrifugal mixer and degassed for 1.5 minutes to obtain a material composition.

The material composition obtained above was applied to a silicone-treated polyester film (thickness: 50 micrometers, SP-PET, commercially available from the Panac Corporation (Minato-ku, Tokyo)), and this was covered with a separate silicone-treated polyester film (thickness: 50 micrometers, Tohcello Co., Ltd.

(Chiyoda-ku, Tokyo)). The resulting laminate was passed through a 1.1 mm gap and cured for 24 hours at 25°C to form a layer with a thickness of 1.0 mm derived from the material composition described above. The polyester film described above was peeled and removed from both sides of this layer to obtain the fire spread prevention member sample of Working Example 1.

[Working Examples 2 through 14 and Comparative Examples 1 through 4]

Fire spread prevention member samples were prepared in the same manner as in Working Example 1 with the exception that the material content was changed as shown in Table 1 (Working Examples 2 to 14 and Comparative Examples 1 to 3). In addition, a commercially available product "Fiblock" (epoxy sheet with a thickness of 1.6 mm, commercially available from Sekisui Chemical Co., Ltd.

(Osaka-shi, Osaka)) (Comparative Example 4) was prepared as a fire spread prevention member sample for comparison.

Production of tape having fire spread prevention member layer

[Working Examples 15 through 17]

Using the same material composition as that used in Working Example 12, a tape having the layer structure shown in Table 2 instead of a silicone-treated polyester film was produced. The case of Working Example 15 will be illustrated. The material composition was applied to a silicone-untreated surface of a silicone- treated polyester film (thickness: 38 micrometers, A3 1, commercially available from Teijin Co., Ltd. (Osaka-shi, Osaka)), and this was covered with a silicone- treated surface of a silicone-treated polyester film (thickness: 38 micrometers, A3 1, commercially available from Teijin Co., Ltd.). The resulting laminate was passed through a 1.08 mm gap and cured for 10 minutes at 125°C to form a layer with a thickness of 1.0 mm derived from the material composition described above. The polyester film described above was peeled and removed from one side of this layer, and a tape sample having a fire spread prevention member was formed with the above procedure. In Working Example 17, after a tape with an adhesive was produced, a fire spread prevention member layer was produced on the tape.

Table 1

[Working Example 18]

Part A (isocyanate hardening agent)

Sumidule 44V10 was used in an amount of 2.1 g.

Part B (base resin)

First, 4.0 g of HS 3G-500B, 2.9 g of H-30 and 1.0 g of Y-403 (as polyols) and 0.2 g of Disperbykl45 (as a dispersant) were mixed well in a plastic container. Next, 4.0 g of FCP-770 (as a flame retardant), 3.2 g of GREP-EG and 3.2 g of SYZR502 (as expandable graphite), 3.0 g of calcium carbonate (as an inorganic filler), 2.0 g of KF-0203 (as fibers), and 1.0 g of zeolite 4A were added to the container and mixed for 2 minutes at 2000 rpm with a planetary centrifugal mixer.

Parts A and B were mixed for 1 minutes at 2000 rpm with a planetary centrifugal mixer and degassed to obtain a material composition.

(Chiyoda-ku, Tokyo)). The resulting laminate was passed through a 1.1 mm gap and cured for 7 minutes at 125°C to form a layer with a thickness of 1.3 mm derived from the material composition described above. The polyester film described above was peeled and removed from both sides of this layer to obtain the fire spread prevention member sample of Working Example 18.

[Working Examples 19 to 21 and Comparative Example 5]

Fire spread prevention member samples were prepared in the same manner as in Working Example 3 with the exception that the material content was changed as shown in Table 18 (Working Examples 19 to 21). In addition, a commercially available product "Fiblock" (epoxy sheet with a thickness of 1.6 mm, commercially available from Sekisui Chemical Co., Ltd. (Osaka-shi, Osaka)) (Comparative Example 5), which was the same as that used in Comparative Example 4, was prepared as a fire spread prevention member sample for comparison.

Table 3

[Working Example 22]

Part A (isocyanate hardening agent)

Sumidule 44V10 was used in an amount of 3.0 g.

Part B (base resin)

First, 5.0 g of HS 3G-500B, 2.0 g of Y-403 (as polyols) and 0.02 g of KAOLIZER No. 14 (as catalyst) as well as 0.2 g of Disperbykl45 (as a dispersant) were mixed well in a plastic container. Next, 2.0 g of FCP-770 (as a flame retardant), 7.0 g of 9532400A (as expandable graphite), 11.0 g of CaC0₃ #1 (as an organic filler), 0.3 g of KF-0203 (as fibers), and 1.0 g of zeolite 4A were added to the container and mixed for 2 minutes at 2000 rpm with a planetary centrifugal mixer.

(Chiyoda-ku, Tokyo)). The resulting laminate was passed through a 1.1 mm gap and cured for 7 minutes at 125°C to form a layer with a thickness of 1.7 mm derived from the material composition described above. The polyester film described above was peeled and removed from both sides of this layer to obtain the fire spread prevention member sample of Working Example 22.

[Working Examples 23 to 39 and Comparative Example 6]

Fire spread prevention member samples were prepared in the same manner as in Working Example 4 with the exception that the material content was changed as shown in Table 22 (Working Examples 23 to 39). In addition, a commercially available product "Fiblock" (epoxy sheet with a thickness of 1.6 mm, commercially available from Sekisui Chemical Co., Ltd. (Osaka-shi, Osaka)) (Comparative Example 6), which was the same as that used in Comparative Example 4, was prepared as a fire spread prevention member sample for comparison.

The fire spread prevention member of the present disclosure is often used for long periods of time, and it may also be exposed to wind and rain depending on the installation location. In Comparative Example 1 in which a urethane binder not having a polyol containing a structure with at least ten consecutive carbon atoms was used, the resin dissolved and the moisture resistance was insufficient, so it can be inferred that it cannot withstand sufficient use. In Comparative Example 2 in which the compounding ratio of expandable graphite was too small, the expansion ratio was low, and in Comparative Example 3 in which the compounding ratio of expandable graphite was too large, the viscosity was too high, so it was difficult to produce a uniform sheet. In addition, Comparative Example 4, which is a commercially available product, is hard at room temperature, so it was difficult to bend. Such members are difficult to apply to portions of a structure with high curvature and are also difficult to provide as rolled products.

It can be understood from the results demonstrated in Working Examples 18 to 21 that, when fibers are contained in the fire spread prevention member, the flexibility is maintained favorably so as to impart anisotropy to the thermal expansion of the fire spread prevention member and so as to enhance the residue strength.

It can be understood from the results demonstrated in Working Examples 22 to 39 that, when a char former (specifically, a combination of an aromatic compound having a high Tg or high Tm and a flame retardant utilizing a

dehydration reaction) is contained in the fire spread prevention member, the flexibility is maintained favorably so as to enhance the residue strength.

Industrial Applicability

The fire spread prevention member of the present disclosure is useful for suppressing fire spread with a structure used in a fire prevention facility.

Claims

In the Claims:

1. A fire spread prevention member for suppressing fire spread with a structure used in a fire prevention facility, the fire spread prevention member comprising:

(A) 100 parts by mass of a polyurethane binder; and

(B) from 30 to 180 parts by mass of expandable graphite;

2. The fire spread prevention member according to claim 1, wherein the fire spread prevention member has a glass transition temperature of at most 25°C and further comprises a phosphorus-containing flame retardant.

3. The fire spread prevention member according to claim 1 or 2, further comprising at least 0.1 parts by mass and at most 20 parts by mass of fibers.

4. The fire spread prevention member according to any one of claims 1 to 3, further comprising a char former.

5. The fire spread prevention member according to any one of claims 1 to 4, wherein the fire spread prevention member is a rolled sheet.

6. The fire spread prevention member according to claim 5, wherein the fire spread prevention member has a thickness of from 0.3 mm to 10 mm.

7. A method for suppressing fire spread with a structure used in a fire prevention facility, the method comprising:

arranging the fire spread prevention member described in any one of claims 1 to 6 on at least part of the structure.

8. The method according to claim 7, wherein the fire spread prevention member is a sheet; and

the fire spread prevention member is attached to the structure along the shape of the structure so as to arrange the fire spread prevention member on at least part of the structure.