JPWO2018164095A1 - Multicolor molding material with excellent rigidity and fire resistance - Google Patents

Abstract

  The present invention provides a refractory molded material including a member A having a tensile modulus of 600 MPa or more and a member B having an expansion ratio of 10 times or more.

Description

  The present invention relates to a fireproof molding material.

  One of the performances required for fittings such as windows, shojis, doors (ie doors), doors, brans, and balustrades used in the openings of structures such as houses is to improve fire performance. A fireproof molding material is attached to the joinery. Conventionally, a thermally expansible material is attached to the frame body so that the flame does not penetrate through the frame body of the joinery installed in the opening of the structure.

  Patent Document 1 discloses a fireproof panel using a thermoplastic elastomer. However, since the material is flexible, it is not used for a portion requiring high rigidity.

Japanese Patent No. 3813955

  Conventionally, a fire-resistant molding material having a fire-resistant function often uses a flexible material that easily follows deformation in order to increase the air tightness and water tightness of the opening. However, on the other hand, there is a problem that a portion where rigidity is required cannot be applied with the above-described material.

  An object of the present invention is to provide a fireproof molding material having high rigidity and excellent thermal expansion ratio.

  When manufacturing a fire-resistant molded material in which a member requiring rigidity and a fire-resistant expansion part are integrated, low-cost coextrusion is optimal. However, in general, a member with high rigidity has a high extrusion temperature, and the expansion part starts to expand at that temperature, which causes problems such as shape instability, poor appearance, and deterioration in fire resistance due to inactivated graphite. .

  It has been found that the present invention can solve the above problem by increasing the viscosity of the expanded portion and suppressing the expansion of expanded graphite. That is, by increasing the viscosity of the expanded portion, coextrusion is possible, and a fire-resistant molding material having excellent rigidity can be manufactured. Moreover, by co-extrusion, it became possible to produce a refractory molded material without an adhesive layer / adhesion step.

The present invention provides the following fireproof molding materials.
Item 1. A fireproof molding material comprising a member A having a tensile modulus of 600 MPa or more and a member B having an expansion ratio of 10 times or more.
Item 2. Item 2. The fireproof molding material according to Item 1, wherein the Rockwell hardness of the member A is 70 or more.
Item 3. Item 3. The fireproof molding material according to Item 1 or 2, wherein the member Y has a tensile yield strength of 20 MPa or more.
Item 4. Item 4. The fireproof molding material according to any one of Items 1 to 3, wherein the member A contains a thermoplastic resin.
Item 5. Item 5. The fireproof molding material according to any one of Items 1 to 4, wherein the residual hardness of the member B is 0.3 kgf / cm ² or more.
Item 6. Item 6. The fireproof molding material according to any one of Items 1 to 5, wherein the member B contains 100 parts by mass of a resin component and 3 to 300 parts by mass of thermally expandable graphite.
Item 7. Item 7. The fireproof molding material according to any one of Items 1 to 6, which is produced by coextrusion.

  ADVANTAGE OF THE INVENTION According to this invention, the fireproof molding material with which the part excellent in rigidity and the thermal expansion part were united can be provided.

Sectional drawing of the fireproof molding material which concerns on one embodiment of this invention. The perspective view which shows another example of the molded article of this invention. The fragmentary sectional view which shows the use condition of the molded article of FIG.

  The fireproof molding material of the present invention can be applied to windows (including sliding windows, open windows, raising / lowering windows, etc.), doors (that is, doors), doors and the like that require high rigidity. The high rigidity of the refractory molding is provided by member A, and the fire resistance is provided by member B.

  The fireproof molding material of the present invention includes a member A having a tensile modulus of 600 MPa or more and a member B having an expansion ratio of 10 times or more, and the member A and the member B are integrated.

  The tensile elastic modulus of the member A is 600 MPa or more, preferably 800 MPa or more, more preferably 1000 MPa or more. The upper limit of the tensile modulus of the member A is not particularly limited, but is set to 250,000 MPa or less.

  The Rockwell hardness of the member A is preferably 70 or more, more preferably 75 or more, and further preferably 80 or more. The upper limit of the Rockwell hardness of the member A is not particularly limited, but is 130 or less.

  The tensile yield strength of the member A is preferably 20 MPa or more, more preferably 25 MPa or more, and further preferably 30 MPa or more. The upper limit of the tensile yield strength of the member A is not particularly limited, but is 3000 MPa or less.

  “Tensile modulus” is obtained by cutting out a dumbbell-shaped test piece according to JIS K 7161-2 from the member A, and subjecting this dumbbell-shaped test piece to a tensile test according to JIS K 7161-2. A strain curve can be drawn and calculated by the following formula (I) using the first straight line portion of the curve.

（式（１）中、Δσは直線上の２点間の元の平均断面積による応力の差であり、Δεは同じ２点間のひずみの差である。）

(In formula (1), Δσ is the difference in stress due to the original average cross-sectional area between two points on the straight line, and Δε is the difference in strain between the same two points.)

  "Tensile yield strength" can be measured based on JISK7161-2.

  “Rockwell hardness” can be measured based on JIS K7202-2.

  The expansion ratio of the member B of the present invention is 10 times or more, preferably 15 times or more, more preferably 20 times or more. The upper limit of the expansion ratio of member B is not particularly limited, but is 50 times or less.

Residue渣硬of member B of the present invention, 0.3 kgf / cm ² or more, preferably 0.4 kgf / cm ² or more, more preferably 0.5 kgf / cm ² or more. The upper limit of the residual hardness of the member B is not particularly limited, but is set to 3.0 kgf / cm ² or less.

  The material constituting the member A may be, for example, a metal, a non-expandable resin, or a composite material thereof, and a non-expandable resin is preferable. The non-expandable resin is composed of a thermoplastic resin, a thermosetting resin, an elastomer, a rubber, or a combination thereof, and preferably includes a thermoplastic resin. Examples of thermoplastic resins include fluororesin, polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polycarbonate, polyether imide, polyether ether ketone, polyarylate, polyamide, polyamide imide, polybutadiene, polyimide, acrylic resin, polyacetal, polyamide , Polyethylene, polyethylene terephthalate, polycarbonate, polyester, polystyrene, polyphenylene sulfide, polybutylene terephthalate, polypropylene, polyvinyl chloride, ABS resin, AS resin, and the like. Examples of thermosetting resins include epoxy resins, phenol resins, Melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, thermosetting polyimide, etc. Examples of elastomers include olefin elastomers, styrene elastomers, ester elastomers, amide elastomers, and vinyl chloride elastomers. Examples of rubbers include natural rubber, silicone rubber, styrene / butadiene rubber, Examples include isoprene rubber, butadiene rubber, chloroprene rubber, acrylonitrile / butadiene rubber, nitrile butadiene rubber, butyl rubber, ethylene / propylene rubber, ethylene / propylene / diene rubber, urethane rubber, silicone rubber, and fluorine rubber.

  In a preferred embodiment of the present invention, the member B is a resin composition containing thermally expandable graphite as a resin component.

  As the resin component, known resin components can be widely used, and examples thereof include thermoplastic resins, thermosetting resins, rubber substances, and combinations thereof.

  Examples of the thermoplastic resin include polypropylene resins, polyethylene resins, poly (1-) butene resins, polypentene resins and other polyolefin resins, polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, polycarbonate resins, polyphenylene ether resins, ( Examples thereof include synthetic resins such as (meth) acrylic resins, polyamide resins, polyvinyl chloride resins, novolac resins, polyurethane resins, polyisobutylenes, and ethylene vinyl acetate resins.

  Examples of the thermosetting resin include synthetic resins such as polyurethane, polyisocyanate, polyisocyanurate, phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, and polyimide.

  Rubber materials include natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber And rubber materials such as epichlorohydrin rubber, polyvulcanized rubber, non-vulcanized rubber, silicone rubber, fluororubber, urethane rubber, and olefinic thermoplastic elastomer (TPO).

  These synthetic resins and / or rubber substances can be used singly or in combination.

  Among these synthetic resins and / or rubber substances, those which are flexible and have rubber-like properties are preferred. The resin component having such properties can be highly filled with an inorganic filler, and the resulting resin composition is flexible and easy to handle. In order to obtain a resin composition that is more flexible and easy to handle, a non-vulcanized rubber such as butyl and a polyethylene resin are preferably used.

  Instead, an epoxy resin is preferable from the viewpoint of improving the fire resistance by increasing the flame retardancy of the resin itself.

  Thermally expandable graphite is a conventionally known substance. Powders such as natural scaly graphite, pyrolytic graphite, and quiche graphite are mixed with inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, concentrated nitric acid, perchloric acid, and perchlorine. A graphite intercalation compound is produced by treatment with strong oxidants such as acid salts, permanganates, dichromates, dichromates, hydrogen peroxide, etc., while maintaining the layered structure of carbon It is a kind of crystalline compound.

  The thermally expandable graphite obtained by the above acid treatment may be further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like. Examples of commercially available products of thermally expandable graphite include “GREP-EG” manufactured by Tosoh Corporation, “GRAFGUARD” manufactured by GRAFTECH, and the like.

  The member B can contain 3-300 mass parts of thermally expansible graphite with respect to 100 mass parts of resin components, for example. The member B may further contain an inorganic filler.

  When the expanded heat insulating layer is formed, the inorganic filler increases the heat capacity and suppresses heat transfer, and works as an aggregate to improve the strength of the expanded heat insulating layer. The inorganic filler is not particularly limited, and examples thereof include metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrite; calcium hydroxide, magnesium hydroxide, Water-containing inorganic substances such as aluminum hydroxide and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, barium carbonate and the like.

  In addition to these, inorganic fillers include calcium salts such as calcium sulfate, gypsum fiber, calcium silicate; silica, diatomaceous earth, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite. , Imogolite, sericite, glass fiber, glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, Examples include lead zirconate titanate, zinc stearate, calcium stearate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, and dewatered sludge. These inorganic fillers can be used alone or in combination of two or more.

  In the resin composition constituting the member B, the inorganic filler may be included in the range of 1 to 300 parts by mass with respect to 100 parts by mass of the resin component.

  When the member B contains an inorganic filler, the total of the thermally expandable graphite and the inorganic filler is preferably in the range of 3 to 300 parts by mass with respect to 100 parts by mass of the resin component.

  The melt viscosity of the resin composition constituting the member B is preferably 1000 to 2500 Pa · s, more preferably 1200 to 2100 Pa · s at a temperature of 160 ° C. and a shear rate of 120 (1 / s). By increasing the viscosity of the resin composition of member B, expansion of member B can be suppressed when member A and member B are coextruded.

  Such a resin composition expands by heating to form a refractory heat insulating layer. According to this composition, the refractory molding material expands by heating such as a fire, and can obtain a necessary volume expansion rate, and after expansion, forms a residue having a predetermined heat insulation performance and a predetermined strength. It is possible to achieve stable fire prevention performance.

  In addition to the above-mentioned components, the resin composition constituting the fireproof molding material is within a range that does not impair the purpose of the present invention, as necessary, in order to increase the strength of the expansion heat insulating layer and improve the fireproof performance. Various phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate; phosphoric acid such as sodium phosphate, potassium phosphate, magnesium phosphate Metal salt; Ammonium polyphosphate; Phosphorus compounds such as a compound represented by the following chemical formula (1) can be included.

In the chemical formula (1), R ¹ and R ³ are the same or different and each represents hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or carbon. The aryloxy group of Formula 6-16 is shown.

  Furthermore, the resin composition constituting the refractory molding material is within the range that does not impair the object of the present invention, as required, in addition to antioxidants such as phenol-based, amine-based, sulfur-based, metal harm-preventing agent, charging Additives such as inhibitors, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifying resins, molding aids, and tackifiers such as polybutenes and petroleum resins can be included.

  The member B is also available as a commercial product. For example, a fire barrier manufactured by Sumitomo 3M Limited (a fire-resistant molding material comprising a resin composition containing chloroprene rubber and vermiculite, expansion ratio: 3 times, thermal conductivity: 0) .20 kcal / m · h · ° C., Mitsuji Metal Paint Co., Ltd., medium-cut (fireproof molding material comprising a resin composition containing polyurethane resin and thermally expandable graphite, expansion ratio: 4 times, thermal conductivity: 0.21 kcal / M · h · ° C.), Sekisui Chemical Co., Ltd. Fiblock, etc.

The fireproof molding material of the present invention may further include a coating layer. A coating layer may be comprised from the arbitrary materials which accept | permit expansion of the member B accompanying a heating, and can also be a combustible material and can also be a nonflammable material. When the coating layer is a flammable material, the member B is more easily expanded, and a predetermined fire resistance performance is exhibited well.
When a coating layer is provided on the fireproof molding material, the coating layer may be provided in contact with the member B, may be provided in contact with the member A, or may be provided in contact with both the member A and the member B. Absent.

  The combustible material is not particularly limited, but it is preferable to use a thermoplastic resin, an elastomer, rubber, or a combination thereof. Examples of thermoplastic resins include fluororesin, polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polycarbonate, polyether imide, polyether ether ketone, polyarylate, polyamide, polyamide imide, polybutadiene, polyimide, acrylic resin, polyacetal, polyamide Polyethylene, polyethylene terephthalate, polycarbonate, polyester, polystyrene, polyphenylene sulfide, polybutylene terephthalate, polypropylene, polyvinyl chloride, ABS resin, and AS resin. Examples of elastomers include olefin elastomers, styrene elastomers, ester elastomers, amide elastomers, and vinyl chloride elastomers. Examples of rubbers include natural rubber, silicone rubber, styrene / butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, acrylonitrile / butadiene rubber, nitrile butadiene rubber, butyl rubber, ethylene / propylene rubber, ethylene / propylene / diene rubber, and urethane rubber. , Silicone rubber, fluorine rubber, and the like. Although the thickness of the coating layer which consists of a thermoplastic resin, an elastomer, rubber | gum, or these combinations is not specifically limited, Usually, it is 0.5-6 mm.

  Moreover, a coating layer may be comprised from the combination of a metal, a metal alloy, or a metal and said combustible material.

  The appearance of the coating layer may be arbitrary, and the color and pattern can be determined according to the purpose. In one embodiment, the color of the covering layer is the same color as the frame of the joinery to which the fireproof molding material is attached. For example, when the fireproof molding material 1 is attached to an aluminum window frame, the color of the coating layer may be aluminum. Similar colors mean three elements represented by color characteristics, that is, hues that are the same or close to each other among hue, brightness, and saturation. Specifically, warm colors, cold colors, white and milky white, transparent and translucent, etc. can be defined as similar colors. In addition, the coating layer can be given a design by giving an arbitrary pattern such as visually producing warmth as a wood grain. Thus, it is possible to improve the designability of the black-gray member B by covering the member B with the coating layer. Furthermore, by covering with the coating layer, the weather resistance of the member B is improved, and the long-term durability of the fireproof molding material is also improved.

  In the case of a kneaded product of the resin composition constituting each of the member A and the member B, in the case of a thermosetting resin such as an extruder, a Banbury mixer, a kneader mixer, a kneading roll, etc. It can be obtained by using a known kneading apparatus such as a reiki machine or a planetary stirrer. In the case of a two-component thermosetting resin, particularly an epoxy resin, a kneaded mixture of each of the two components and the filler is prepared separately by the kneading method, and is used with a plunger pump, a snake pump, a gear pump, etc. Each kneaded product may be supplied and mixed with a static mixer, a dynamic mixer or the like to produce a kneaded product.

  As a molding method of the resin composition constituting each of the member A and the member B, the kneaded material can be molded using a known method such as press molding, calendar molding, extrusion molding, injection molding, or the like. In addition, as a method for molding a two-component thermosetting resin, particularly an epoxy resin, a known method may be used depending on the shape as appropriate, such as roll molding with SMC (Sheet Molding Compound) or the like, or coater molding with a roll coater or blade coater. Can be used.

  Although the manufacturing method of the refractory molding material 1 is not particularly limited, the member A and the member B may be coextrusion molded, or may be integrally bonded to each other by an adhesive means such as an adhesive sheet or an adhesive. You may couple | bond together by fixation. The members A and B are preferably coextruded.

  Although the thickness of the member B is not limited, 0.1-6 mm is preferable. When the thickness is 0.1 mm or more, sufficient fireproof performance can be exhibited by the thickness of the expanded heat insulating layer formed by heating. Moreover, if it is 6 mm or less, the insertion into a cavity may be easy.

  The fireproof molding material of the present invention can be used by being attached to a fitting such as a window, a shoji, a door (that is, a door), a door, a bran, and a rail used for an opening of a structure such as a house or a building. The fireproof molding material of the present invention can also be used as a shoji screen or frame for a resin sash.

  A fireproof molding material according to one embodiment of the present invention will be described with reference to FIG.

  As shown in FIG. 1, the fireproof molding material 1 includes a member A having a tensile elastic modulus of 600 MPa or more and a member B having an expansion ratio of 10 times or more, and the members A and B are integrally molded into a sheet shape. Has been.

  A pair of opposed rail-like ridges 2 a and 2 b extending along the longitudinal direction of the frame body 2 are provided at the upper end portion of the frame body 2. 2a and 2b and the two protrusions 3 have a substantially L-shaped cross section in the longitudinal direction of the refractory molding material 1, and each of the raised portions 2a and 2b engages with the two protrusions 3.

  2 and 3 show still another embodiment of the fireproof molding material of the present invention. FIG. 2 shows an architectural gasket 30 of a glazing channel type mounted on the peripheral edge of the glass panel 38 (see FIG. 3). FIG. 3 is a cross-sectional view for explaining a use state of the gasket 30 of FIG. 2 in the glass panel.

  The gasket 30 includes a bottom wall portion 32 that faces the end surface 39 of the glass panel 38, and is provided on both sides of the bottom wall portion 32 so as to be continuous with the bottom wall portion 32, along the longitudinal direction of the glass panel end surface 39. And a side wall portion 33 that covers the portion 40. The bottom wall portion 32 and the side wall portion 33 form the main body portion 31 of the gasket 30. The main body 31 is formed of the member A.

  A protrusion 34 is provided on the upper portion of each side wall 33. Each protrusion 34 has an outer fin portion 35 and an inner fin portion 36 protruding toward the inside, that is, the glass panel 38 side.

Each protrusion 34 has a groove 37 on the outside, that is, on the side opposite to the glass panel. By inserting the end portion of the sash into the groove portion 37, the gasket 30 can be fixed to the sash. The protrusion 34 is made of the member B.
The gasket 30 can be formed by coextrusion of the main body 31 and the protrusion 34.

  Hereinafter, the present invention will be described in detail by way of examples. In addition, this invention is not limited at all by these Examples.

Examples 1-3
The resin composition containing each component is kneaded with the components and blending amounts (parts by mass) of the component A shown in Table 1 and the components and blending amounts (parts by mass) of the member B shown in Table 2, and coextruded to give a sheet-like fire resistance. A molding material was obtained. About the obtained fireproof molding material, melt viscosity, tensile elasticity modulus, Rockwell hardness, tensile yield strength, expansion ratio, and residual hardness were measured under the measurement conditions described in Table 3, Table 4, and Table 5. The measurement conditions of expansion ratio and residue hardness are shown in the following (i) to (ii), and the results are shown in Table 3, Table 4, and Table 5.

(i) Expansion ratio A sample impregnated with a 200 mesh wire net in an electric furnace preheated to 600 ° C. was put into a SUS box frame and heated for 30 minutes. The residue thickness of the sample taken out was measured with calipers, and the expansion ratio was calculated according to the following formula.
Expansion ratio (times) = Thickness of residue after combustion / Initial thickness of refractory rubber composition sheet

(ii) Residual hardness After measuring the expansion ratio, the residue was compressed at a compression rate of 0.1 cm / min with a 0.25 cm ² indenter using a tensile tester (Tensilon RTC, manufactured by Orientec). The maximum point load that appeared was the residue hardness.

Since the member B has a high melt viscosity, the expansion was suppressed and the appearance was good.
The criteria for “determination” in Tables 3, 4, 5, 10, and 11 are shown below.
A: Good B: Bad

Examples 4-5
The resin composition containing each component was kneaded and coextruded with the components and blending amounts (parts by mass) of the components A shown in Tables 6 and 8 and the components and blending amounts (parts by mass) of the members B shown in Tables 7 and 9. A sheet-like fireproof molding material was obtained. About the obtained fireproof molding material, melt viscosity, tensile elastic modulus, Rockwell hardness, tensile yield strength, expansion ratio, and residual hardness were measured under the measurement conditions described in Tables 10 and 11. The measurement conditions of expansion ratio and residue hardness are the same as the above (i) to (ii), and the results are shown in Tables 10 and 11.

DESCRIPTION OF SYMBOLS 1 Refractory molding material 2 Frame 2a Raised part 2b Raised part 3 Projection part 30 Gasket 31 Main body part 32 Bottom wall part 33 Side wall part 34 Projection part 35 External fin part 36 Inner fin part 37 Groove part 38 Glass panel 39 Glass panel end surface 40 Glass Panel edge

Claims (7)

A fireproof molding material comprising a member A having a tensile modulus of 600 MPa or more and a member B having an expansion ratio of 10 times or more. 2. The fireproof molding material according to claim 1, wherein the Rockwell hardness of the member A is 70 or more. 3. The fireproof molding material according to claim 1, wherein the tensile yield strength of the member A is 20 MPa or more. The fireproof molding material according to any one of claims 1 to 3, wherein the member A contains a thermoplastic resin. The fireproof molding material according to any one of claims 1 to 4, wherein the residual hardness of the member B is 0.3 kgf / cm ² or more. 6. The fireproof molding material according to claim 1, wherein the member B contains 3 to 300 parts by mass of thermally expandable graphite with respect to 100 parts by mass of the resin component. The fireproof molding material according to any one of claims 1 to 6, wherein the fireproof molding material is produced by coextrusion.

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