JP2012040724A - Incombustible material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an incombustible material allowing weight and cost reduction, improvement of the degree of freedom of design and prevention of deterioration of the light transmittance.SOLUTION: The incombustible material uses a polycarbonate molding as a support and has at least one layer of a coating film based on an acrylic resin on at least one side of the support. The acrylic resin is one or more of acrylic, acrylic silicone, acrylic urethane and acrylic UV-curable resins, and the support exceeds thickness 1.0 and 3.0 mm or below.

Description

  The present invention relates to a non-combustible material that can be reduced in weight and cost.

  A material used for a railway vehicle has a combustion rank defined according to a use site, and a flammability standard is defined separately for non-flammability, extreme flame retardant, and flame retardant. In particular, ceiling parts, linings, floors, and the like are obliged to satisfy nonflammability standards (see, for example, Non-Patent Document 1 or 2).

  As a material that satisfies the non-flammability standards required for railway vehicle materials, a technique has been proposed in which the base material itself is made non-flammable by impregnating glass cloth with a flame retardant fluororesin. (For example, see Patent Document 1). Further, a polycarbonate sheet for a railway vehicle has been proposed in which a silicone hard coat layer added with a heat ray absorbent such as carbon black is further provided on a polycarbonate sheet mixed with a heat ray absorbent such as carbon black (for example, patent document). 2).

JP 2006-252892 A Japanese Patent Application Laid-Open No. 2004-83753

Ministry of Land, Infrastructure, Transport and Tourism Notification No. 81 "Train Fire Accident Countermeasures" MLIT Ordinance 151 “Ministerial Ordinance Establishing Technical Standards for Railways”

  The technology for making the base material itself incombustible including Patent Document 1 is difficult to reduce the thickness of the base material itself in order to satisfy the incombustibility requirement, and cannot reduce the weight and the cost. . In addition, the degree of freedom in design is poor and it is not suitable for use.

  The technology to make non-flammable by applying paint added with a heat-absorbing agent such as carbon black such as Patent Document 2 is suitable for applications that require light transmission such as in-car advertising covers and parts of ceiling materials. Not suitable.

  Then, this invention aims at providing the nonflammable material which can improve weight reduction, cost reduction, and the freedom degree of design, and can prevent the light transmittance fall.

  The noncombustible material according to the present invention has a polycarbonate molded body as a support, and at least one layer of a coating mainly composed of an acrylic resin is formed on at least one side of the support. The acrylic resin is an acrylic resin. , An acrylic silicon resin, an acrylic urethane resin, and an acrylic ultraviolet curable resin, and the thickness of the support is more than 1.0 mm and not more than 3.0 mm.

  In the incombustible material according to the present invention, the polycarbonate molded body preferably contains no flame retardant. While maintaining the transparency of the support, it is possible to prevent deterioration of physical properties such as heat resistance.

  The present invention can provide a non-combustible material that can be reduced in weight, reduced in cost, improved in design freedom, and prevented from lowering light transmittance.

It is the schematic of the instrument used for the combustion test for railway vehicle materials.

  The non-combustible material according to the present embodiment has a polycarbonate molded body as a support, and at least one layer of a coating mainly composed of an acrylic resin is formed on at least one side of the support. The acrylic resin is an acrylic resin, It is at least one of acrylic silicon resin, acrylic urethane resin, and acrylic ultraviolet curable resin, and the thickness of the support is more than 1.0 mm and not more than 3.0 mm. In the present embodiment, the non-combustible material refers to a material that is determined to be “non-combustible” in the railway vehicle material combustion test of the Ministry of Land, Infrastructure, Transport and Tourism.

  The support is a polycarbonate molded body obtained by molding a polycarbonate resin. The polycarbonate resin is a kind of thermoplastic resin and is usually obtained by reacting a dihydric phenol and a carbonate precursor. However, in the present embodiment, the type and the molecular structure are not limited. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method, and a ring-opening polymerization method. As the divalent phenol, 4,4'-isopropylidenediphenol (bisphenol A) is generally used. Examples of the carbonate precursor include phosgene, diphenyl carbonate, carbonyl chloride, and butyl carbonate. This embodiment is not limited to the reaction method and raw materials.

  The glass transition point (Tg) of the polycarbonate resin is preferably 120 to 160 ° C. More preferably, it is 145-155 degreeC. If it is less than 120 degreeC, heat resistance may be insufficient. If it exceeds 160 ° C., the moldability may be inferior.

  The manufacturing method of a support body is not specifically limited, It can manufacture with the processing method of a normal thermoplastic resin. The normal processing method is, for example, producing a polycarbonate resin composition in which a polycarbonate resin and subcomponents are mixed using a melt kneader such as a single screw extruder or a twin screw extruder, and then the resin composition is variously used. This is a method of forming into various shapes according to the use site by melt molding. The production method of the polycarbonate resin composition is, for example, a method of melting and kneading all of the raw materials at once, or a method of kneading a part of the raw materials in advance and then melt-kneading together with the remaining raw materials. Subcomponents are, for example, pigments, plasticizers, lubricants, antioxidants, heat stabilizers, mold release agents, and hydrolysis inhibitors, and can be added as long as the effects of the present invention are not impaired.

  In the incombustible material according to the present embodiment, the polycarbonate molded body preferably does not contain a flame retardant. Generally, brominated flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, metal hydrate flame retardants such as aluminum hydroxide and magnesium hydroxide, or phosphate esters It is known that a flame-retardant polycarbonate molded body can be obtained by blending and molding various flame retardants such as various phosphorus-based flame retardants such as phosphazene compounds. However, when a flame retardant is blended, there is a problem that the cost increases. Furthermore, brominated flame retardants have a problem of environmental pollution due to bromine gas generated during combustion and a problem that the thermal stability of the resin composition is lowered. The metal hydrate flame retardant has a problem that transparency is deteriorated. Phosphorus flame retardants have the problem of reducing mechanical properties such as impact resistance and heat resistance, and do not completely solve the environmental pollution problem.

  The forming method of the support is, for example, a known forming method such as injection molding, extrusion molding, transfer molding, lamination molding, compression molding, or vacuum molding. In this embodiment, it is not limited to the molding method. Moreover, the polycarbonate molded body marketed can be used for a support body. As a commercial item, it is PC-1600 of Takiron Corporation, for example.

  The thickness of the support is more than 1.0 mm and not more than 3.0 mm. More preferably, they are 1.2 mm or more and 2.5 mm or less, Especially preferably, they are 1.5 mm or more and 2.0 mm or less. When the thickness is 1.0 mm or less, the flame retardancy is determined, but the nonflammability is not determined. If it exceeds 3.0 mm, the weight reduction, cost reduction, and improvement in design flexibility, which are the objects of the present invention, cannot be achieved.

  On at least one side of the support, at least one layer of a coating film mainly composed of an acrylic resin is formed. The acrylic resin is at least one of acrylic resin, acrylic silicon resin, acrylic urethane resin, and acrylic ultraviolet curable resin.

  As the acrylic resin, a known one can be used in the field of paint, and can be obtained by a known method. The acrylic resin is a polymer of acrylic ester or methacrylic ester. Acrylic acid esters include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, Dodecyl acrylate. Methacrylic acid esters are, for example, methyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate. Any of these may be used alone or in appropriate combination of two or more. This embodiment is not limited to the type of monomer and polymerization method.

  The acrylic resin includes a copolymer of an acrylic ester or methacrylic ester and an ethylenically unsaturated monomer. Acrylic acid esters or methacrylic acid esters are those exemplified above, and any one kind can be used alone, or two or more kinds can be used in appropriate combination. This embodiment is not limited to the type of monomer and polymerization method. Examples of ethylenically unsaturated monomers include monomers having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. Ring-opening adduct of γ-butyrolactone to 2-hydroxyethyl methacrylate, ring-opening adduct of ε-caprolactone to 2-hydroxyethyl acrylate, carboxyl group-containing monomers such as acrylic acid and methacrylic acid, styrene, α-methyl Styrene derivatives such as styrene, vinyl toluene, paramethyl styrene and chlorostyrene, vinyl esters such as vinyl acetate and vinyl propionate, halogens such as vinyl chloride and vinylidene chloride Vinyl monomers, acrylamide, diacetone acrylamide, N- methylol acrylamide, acrylonitrile, methacrylamide, a nitrogen-containing vinyl monomers such as methacrylonitrile. Any one ethylenically unsaturated monomer may be used alone, or two or more kinds thereof may be used in appropriate combination. This embodiment is not limited to the type of monomer and polymerization method.

  The acrylic silicon resin is a reaction product of (A) an acrylic resin having basic nitrogen and (B) a compound having an epoxy group and a hydrolyzable silyl group in one molecule. (A) The acrylic resin having basic nitrogen is obtained, for example, by copolymerizing an amino group-containing vinyl monomer and a monomer copolymerizable with this monomer.

  Examples of amino group-containing vinyl monomers include dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. N-dialkylaminoalkyl (meth) acrylamides such as N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-diethylaminopropyl (meth) acrylamide And t-butylaminoethyl (meth) acrylate and t-butylaminopropyl (meth) acrylate.

  Monomers copolymerizable with amino group-containing vinyl monomers include, for example, acrylic acid esters, methacrylic acid esters, carboxyl group-containing vinyl monomers, dialkyl esters of unsaturated dibasic acids, acid anhydride groups. A vinyl monomer containing a carboxylic acid amide group, a vinyl monomer containing a sulfonamide group, a vinyl monomer containing a (per) fluoroalkyl group, and an aromatic vinyl monomer. Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso- Butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylexyl (meth) acrylate. Examples of the carboxyl group-containing vinyl monomer include maleic acid, fumaric acid, and itaconic acid. Examples of the dialkyl esters of unsaturated dibasic acid include dimethyl malate and dimethyl fumarate. Examples of the acid anhydride group-containing vinyl monomer include maleic anhydride and itaconic anhydride. Examples of the carboxylic acid amide group-containing vinyl monomer include (meth) acrylamide and N-alkoxy (meth) acrylamide. An example of the sulfonamide group-containing vinyl monomer is p-styrenesulfonamide. An example of the (per) fluoroalkyl group-containing vinyl monomer is perfluorocyclohexyl (meth) acrylate. Examples of the aromatic vinyl monomer include styrene and α-methylstyrene.

  (B) As a compound having an epoxy group and a hydrolyzable silyl group in one molecule, for example, a vinyl copolymer having an epoxy group and a hydrolyzable silyl group, and a silane coupling agent having an epoxy group are typical. It is. The vinyl copolymer having an epoxy group and a hydrolyzable silyl group includes, for example, a vinyl monomer having an epoxy group, a vinyl monomer having a hydrolyzable silyl group, and an amino group-containing vinyl as necessary. It can be obtained by copolymerizing various monomers as described in Vinyl monomers copolymerizable with monomers. Examples of the vinyl monomer having an epoxy group include (β-methyl) glycidyl (meth) acrylate and allyl glycidyl ether. Examples of vinyl monomers having hydrolyzable silyl groups include γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinyltritrimethoxysilane, and vinyltriethoxysilane. is there. Examples of silane coupling agents having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyl. Diethoxysilane. Further, the compounds having hydrolyzable silyl groups include alkoxysilanes, alkenyloxysilanes, acyloxysilanes, halosilanes, for example, partially hydrolyzed condensates of alkoxysilanes, and alkenyloxysilanes. There are hydrolysis condensates. Examples of the alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, and diphenyldiethoxysilane. Examples of alkenylsilanes include tetraisopropenyloxysilane and phenyltriisopropenyloxysilane. Examples of the acyloxysilanes include tetraacetoxysilane and γ-mercaptopropyltriacetoxysilane. Examples of halosilanes are tetrachlorosilane and phenyltrichlorosilane. Any of these may be used alone or in appropriate combination of two or more.

  The blending ratio of (A) an acrylic resin having basic nitrogen and (B) a compound having an epoxy group and a hydrolyzable silyl group in one molecule is such that (B) is 0.5 to 0.5%. It is preferable to be 8 molar equivalents. More preferably, it is 1 to 6 molar equivalents. When it is less than 0.5 molar equivalent, the mechanical strength and water resistance of the coating film may be inferior. If it exceeds 8 molar equivalents, the adhesion to the support may be inferior. Moreover, a coating film may not become uniform and an external appearance may be inferior.

  The acrylic urethane resin is a reaction product of an acrylic polyol and a polyisocyanate compound. The acrylic polyol is an acrylic resin having two or more hydroxyl groups in one molecule, and is, for example, a polymer of a hydroxyl group-containing acrylic monomer. Hydroxyl group-containing acrylic monomers include, for example, monomers having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. A ring-opening adduct of γ-butyrolactone to 2-hydroxyethyl methacrylate, and a ring-opening adduct of ε-caprolactone to 2-hydroxyethyl acrylate. Any one hydroxyl group-containing acrylic monomer can be used alone, or two or more hydroxyl groups can be used in appropriate combination. This embodiment is not limited to the type of monomer and polymerization method.

  In the present embodiment, the acrylic polyol includes a copolymer of a hydroxyl group-containing acrylic monomer and another ethylenically unsaturated monomer. The hydroxyl group-containing acrylic monomers are those exemplified above, and any one of them can be used alone, or two or more of them can be used in appropriate combination. This embodiment is not limited to the type of monomer and polymerization method. Other ethylenically unsaturated monomers are, for example, monomers similar to the acrylic acid esters, methacrylic acid esters, styrene derivatives, vinyl esters, halogenated vinyl monomers, and nitrogen-containing vinyl monomers exemplified above. Other ethylenically unsaturated monomers can be used alone or in appropriate combination of two or more. This embodiment is not limited to the type of monomer and polymerization method.

  The hydroxyl value of the acrylic polyol is preferably 5 to 150 mgKOH / g. More preferably, it is 10-100 mgKOH / g. If it is less than 5 mgKOH / g, sufficient crosslinking density of urethane bonds with the polyisocyanate compound cannot be obtained, and the mechanical strength and water resistance of the coating film may be inferior. On the other hand, if it exceeds 150 mgKOH / g, the crosslinking density of the urethane bond becomes excessive, so that excessive curing shrinkage of the coating film occurs, and the adhesion to the support may be lowered.

  A polyisocyanate compound is a compound having two or more isocyanate groups in one molecule, such as 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester. Diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate. Any of these may be used alone or in appropriate combination of two or more.

  The blending ratio of the acrylic polyol and the polyisocyanate compound is preferably such that the isocyanate group of the polyisocyanate compound is 0.5 to 8 molar equivalents relative to the hydroxyl group of the acrylic polyol. More preferably, it is 1 to 6 molar equivalents. When it is less than 0.5 molar equivalent, the mechanical strength and water resistance of the coating film may be inferior. If it exceeds 8 molar equivalents, the adhesion to the support may be inferior. Moreover, a coating film may not become uniform and an external appearance may be inferior.

  The acrylic ultraviolet curable resin is a polymer obtained by blending an ultraviolet curable vinyl compound having one or more double bonds in one molecule and a photopolymerization initiator and irradiating with ultraviolet rays for polymerization.

  Examples of the ultraviolet curable vinyl compound containing one double bond in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc. (Meth) acrylate such as alkyl ester of 1 to 18 carbon atoms, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. 8 hydroxy Hydroxyl-containing (meth) acrylates such as alkyl (meth) acrylate, adduct of 2-hydroxyethyl (meth) acrylate and ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate and γ-butyrolactone, (meth) acrylic In addition to unsaturated dibasic acids such as acid, maleic acid, fumaric acid and itaconic acid, vinyl compounds containing carboxyl or alkoxycarbonyl groups such as dialkyl esters such as dimethyl malate and dimethyl fumarate, maleic anhydride, anhydrous Vinyl compounds containing acid anhydride groups such as itaconic acid, vinyl compounds containing epoxy groups such as glycidyl (meth) acrylate, aromatic vinyl compounds such as styrene, α-methylstyrene and vinylstyrene, dimethylaminomethyl (meth) acrylate, diethylamino Me Le (meth) acrylate is an amino group-containing vinyl compounds such as dimethyl amino propyl acrylamide. In addition to the above compounds, for example, (meth) acrylonitrile, vinyl acetate, vinyl propionate, butadiene, isoprene, and chloroprene can be used.

  Examples of the compound containing two double bonds in one molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol Type A di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate Ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate.

  Examples of the compound containing three or more double bonds in one molecule include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth). ) Acrylate, dipentaerythritol hexa (meth) acrylate. Moreover, an isocyanuric acid derivative can be used. Further, for example, the above-mentioned acrylic acid ester monomer, methacrylic acid ester monomer or ethylenically unsaturated monomer can be used. Any of these may be used alone or in appropriate combination of two or more. In addition to the vinyl compound, urethane-modified (meth) acrylate, polyester-modified (meth) acrylate, and epoxy-modified (meth) acrylate can also be used.

  As the photopolymerization initiator, a known photopolymerization initiator can be used as long as it causes a polymerization reaction of an acrylic oligomer and an acrylic monomer. Examples of the photopolymerization initiator include benzoin, benzoin monomethyl ether, benzoin isopropyl ale, acetoin, benzyl, benzophenone, P-methoxybenzophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxy Rate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-ethylanthraquinone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone .

  It is preferable that the compounding quantity of a photoinitiator shall be 0.1-20 mass parts with respect to 100 mass parts of acrylic oligomers and acrylic monomers. More preferably, it is 1-10 mass parts. If it is less than 0.1 part by mass, polymerization may not start. When it exceeds 20 mass parts, the adhesiveness of a coating film may be inferior.

  The mass average molecular weight of the acrylic resin is preferably 5,000 to 250,000. More preferably, it is 10,000-200,000. If it is less than 5,000, the coating film strength may be insufficient. If it exceeds 250,000, painting workability may be inferior.

  The glass transition point (Tg) of the acrylic resin is preferably 0 to 120 ° C. More preferably, it is 15-100 degreeC. If it is less than 0 degreeC, the intensity | strength of a coating film may be inferior. When it exceeds 120 ° C., the coating film is hard and may be easily broken, and may have poor adhesion.

  The manufacturing method of the coating film which has acrylic resin as a main component changes with kinds of acrylic resin. Next, the specific example of the manufacturing method of a coating film according to the kind of acrylic resin is shown. In addition, this embodiment is not limited to the manufacturing method of a coating film.

  The acrylic resin coating film can be obtained, for example, by applying and drying an acrylic resin paint prepared by mixing a liquid solvent in the acrylic resin to a solid content concentration suitable for application on a support.

  A known solvent can be used as the liquid solvent. For example, diethyl ketone (3-pentanone), methyl propyl ketone (2-pentanone), methyl isobutyl ketone (4-methyl-2-pentanone), 2-hexanone, 5 -Methyl-2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, ketones such as cyclopentanone, cyclohexanone, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, acetic acid-3 Esters such as -methoxybutyl, methyl propionate, ethyl propionate, diethyl carbonate, γ-butyrolactone, isophorone, isobutyl butyrate, hydrocarbons such as heptane, hexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene An organic solvent such as can be used. Furthermore, an aqueous medium may be used to further reduce the environmental load. An aqueous medium is a mixture of water and a hydrophilic organic solvent. Examples of hydrophilic organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, Alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, methyl acetate, acetic acid -Esters such as n-propyl, isopropyl acetate, methyl propionate, ethyl propionate, and dimethyl carbonate. In this embodiment, it is not restricted to the kind of liquid solvent, Arbitrary 1 type can be used individually or in combination of 2 or more types as appropriate.

  The acrylic silicon resin coating film is, for example, a mixture of the (A) acrylic resin having basic nitrogen and the (B) compound having an epoxy group and a hydrolyzable silyl group in one molecule at the time of coating film formation. Acrylic silicone resin paint prepared by mixing at a ratio of 1.5% and then adding a liquid solvent to a solid concentration suitable for coating is applied to the support within a predetermined time, dried, and further cured. It is done. As the liquid solvent, any one of the above liquid solvents can be used alone, or two or more of them can be used in appropriate combination.

  The acrylic urethane resin coating film is, for example, an acrylic prepared by mixing the acrylic polyol and the polyisocyanate compound at a certain ratio when forming the coating film, and further mixing a liquid solvent to a solid content concentration suitable for coating. It can be obtained by applying and drying a urethane resin paint on a support within a predetermined time and further performing a curing treatment. As the liquid solvent, any one of the above liquid solvents can be used alone, or two or more of them can be used in appropriate combination.

  The coating film of the acrylic ultraviolet curable resin is, for example, a solid content suitable for coating by mixing the acrylic oligomer, the acrylic monomer, and the photopolymerization initiator and blending the mixture with a liquid solvent. The acrylic ultraviolet curable resin paint prepared in (1) above is applied and dried on a support and then irradiated with ultraviolet rays. At this time, the acrylic oligomer and the acrylic monomer become a polymer by the excitation energy of the photopolymerization initiator. As the liquid solvent, any one of the aforementioned liquid solvents can be used alone, or two or more of them can be used in appropriate combination.

  In the formation of the coating film, a known coating method such as a roll coating method, a spray method, a dip method, or a brush coating method can be selected as the coating method. The thickness of the coating film is preferably 0.2 to 120 μm. More preferably, it is 0.4-70 micrometers, Most preferably, it is 0.8-70 micrometers. If it is less than 0.2 μm, the determination of nonflammability may not be achieved. If it exceeds 120 μm, the coating film may be coherently broken. Moreover, workability | operativity worsens and is not economically preferable. A coating film having a desired thickness may be formed by one application, or a coating film having a desired thickness may be formed by applying a plurality of times.

  As an auxiliary agent added to the paint as necessary, pigments, inorganic fillers, glittering materials, plasticizers, dispersants, emulsifiers, fluidity modifiers, ultraviolet absorbers, light stabilizers, and the like are effective for the present invention. It can be added as long as it is not impaired.

  Next, although an example of the present invention is given and explained, the present invention is not limited to these examples.

Example 1
Acrydic resin A-166 (nonvolatile content 45%, weight average molecular weight 75,000, glass transition point 50 ° C., manufactured by DIC) 100 parts by mass and solvent, methyl ethyl ketone, methyl isobutyl ketone and butyl isobutyrate mixed solvent 150 parts by mass was blended to obtain an acrylic resin paint having a solid content concentration of 18% by mass. The thickness after drying the acrylic resin paint obtained is 0.4 μm on one side of a polycarbonate molded body (glass transition point 150 ° C., PC-1600, manufactured by Takiron Co., Ltd.) having a thickness of 2 mm as a support. After spray-coating and drying at 70 ° C. for 30 minutes, the mixture was further allowed to stand at 25 ° C. for 48 hours to form a coating film to obtain a noncombustible material.

(Example 2)
In Example 1, an incombustible material was obtained according to Example 1 except that the acrylic resin paint was applied so that the thickness after drying was 70 μm.

(Example 3)
In Example 1, an incombustible material was obtained according to Example 1 except that the thickness of the polycarbonate molded body was 3 mm.

Example 4
In Example 3, an incombustible material was obtained according to Example 3 except that the acrylic resin paint was applied so that the thickness after drying was 100 μm.

(Example 5)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a thermometer, and a nitrogen introduction tube was charged with 420 parts by mass of toluene and 280 parts by mass of iso-butanol and heated to 80 ° C. in a nitrogen atmosphere. Thereafter, (A) 650 parts by mass of methyl methacrylate, 220 parts by mass of n-butyl acrylate and 130 parts by mass of dimethylaminoethyl methacrylate as an acrylic resin having basic nitrogen, and 5 parts by mass of azobisisobutylnitrile (hereinafter referred to as AIBN). Part, 5 parts by mass of tert-butyl peroxyoctoate and 200 parts by mass of toluene were added dropwise for 3 hours. After the completion of dropping, the mixture was kept at the same temperature for 2 hours, and then a mixture of 5 parts by mass of AIBN, 265 parts by mass of toluene, and 20 parts by mass of iso-butanol was added dropwise. Thereafter, the mixture was held at the same temperature for 4 hours to obtain an acrylic resin solution having a tertiary amino group having a nonvolatile content of 50% and a number average molecular weight of 15,000. 60 parts by mass of this resin solution and (B) partial hydrolytic condensation of 10 parts by mass of γ-glycidoxypropyltrimethoxysilane and tetraethoxysilane as a compound having both an epoxy group and a hydrolyzable silyl group in one molecule 15 parts by mass (silicate 40, manufactured by Tama Chemical Co., Ltd.) and 115 parts by mass of a mixed solvent of toluene, ethyl acetate, methyl isobutyl ketone and ethylene glycol monoethyl ether acetate as a solvent were mixed, and the solid content concentration 27. A 5 mass% acrylic silicone resin paint was obtained. On one side of a polycarbonate molded body (PC-1600, manufactured by Takiron Co., Ltd.) having a thickness of 2 mm as a support, the obtained acrylic silicone resin paint is spray-coated so that the thickness after drying is 0.4 μm. After drying at 70 ° C. for 30 minutes, the mixture was further allowed to stand at 25 ° C. for 48 hours and cured to form a coating film to obtain a nonflammable material.

(Example 6)
In Example 5, an incombustible material was obtained according to Example 5 except that the acrylic silicon resin paint was applied so that the thickness after drying was 70 μm.

(Example 7)
In Example 5, an incombustible material was obtained according to Example 5, except that the thickness of the polycarbonate molded body was 3 mm.

(Example 8)
In Example 7, an incombustible material was obtained according to Example 7 except that the acrylic silicon resin paint was applied so that the thickness after drying was 100 μm.

Example 9
Acrydic 57-773 as acrylic polyol (non-volatile content 45%, mass average molecular weight 51,000, glass transition point 55 ° C., hydroxyl value 33 mg KOH / g, manufactured by DIC) 100 parts by mass, and polyisocyanate compound Desmodur N- 3200 (manufactured by Sumika Bayer) 5 parts by mass and 100 parts by mass of a mixed solvent of methyl ethyl ketone, methyl isobutyl ketone and butyl isobutyrate as a solvent are blended to obtain an acrylic urethane resin paint having a solid content concentration of 24.4% by mass. It was. On one side of a polycarbonate molded body (PC-1600, manufactured by Takiron Co., Ltd.) having a thickness of 2 mm as a support, the obtained acrylic urethane resin paint is spray-coated so that the thickness after drying is 0.4 μm. After drying at 70 ° C. for 30 minutes, the mixture was further allowed to stand at 25 ° C. for 48 hours and cured to form a coating film to obtain a nonflammable material.

(Example 10)
In Example 9, an incombustible material was obtained according to Example 9 except that the acrylic urethane resin paint was applied so that the thickness after drying was 70 μm.

(Example 11)
In Example 9, an incombustible material was obtained according to Example 9 except that the thickness of the polycarbonate molded body was 3 mm.

(Example 12)
In Example 11, an incombustible material was obtained according to Example 11 except that the acrylic urethane resin paint was applied so that the thickness after drying was 100 μm.

(Example 13)
50 parts by mass of Unidic C7-164 (manufactured by DIC) as urethane-modified acrylate, and 50 parts by mass of a mixture of dipentaerythritol penta / hexaacrylate (trade name Aronix M-402, manufactured by Toagosei Co., Ltd.) as an acrylic monomer, 5 parts by mass of 1-hydroxycyclohexyl-phenyl ketone (trade name Irgacure 184, manufactured by BASF) as a photopolymerization initiator and 100 parts by mass of a mixed solvent of methyl ethyl ketone, methyl isobutyl ketone and butyl isobutyrate as a solvent are mixed. An acrylic ultraviolet curable resin paint having a partial concentration of 39.5% by mass was obtained. Spray the obtained acrylic UV curable resin paint on one side of a polycarbonate molded body (PC-1600, manufactured by Takiron Co., Ltd.) having a thickness of 2 mm as a support so that the thickness after drying is 0.4 μm. After coating and drying at 70 ° C. for 5 minutes, a high pressure mercury lamp was used to further irradiate with ultraviolet rays (maximum intensity 80 mW / cm ² , integrated light quantity 700 mJcm ² ) to form a coating film, thereby obtaining a noncombustible material.

(Example 14)
In Example 13, an incombustible material was obtained according to Example 13 except that the acrylic ultraviolet curable resin coating was applied so that the thickness after drying was 70 μm.

(Example 15)
In Example 13, an incombustible material was obtained according to Example 13 except that the thickness of the polycarbonate molded body was 3 mm.

(Example 16)
In Example 15, an incombustible material was obtained according to Example 15 except that the acrylic ultraviolet curable resin paint was applied so that the thickness after drying was 100 μm.

(Comparative Example 1)
In Example 1, a coating film was formed on the support according to Example 1 except that the thickness of the polycarbonate molded body was 1 mm.

(Comparative Example 2)
In Example 1, a coating film was formed on the support according to Example 1 except that the thickness of the polycarbonate molded body was 1 mm and the acrylic resin paint was applied so that the thickness after drying was 70 μm. .

(Comparative Example 3)
In Example 5, a coating film was formed on the support according to Example 5 except that the thickness of the polycarbonate molded body was 1 mm.

(Comparative Example 4)
In Example 5, a coating film was formed on the support according to Example 5 except that the thickness of the polycarbonate molded body was 1 mm and the acrylic silicon resin paint was applied so that the thickness after drying was 70 μm. did.

(Comparative Example 5)
In Example 9, an incombustible material was obtained according to Example 9, except that the thickness of the polycarbonate molded body was 1 mm.

(Comparative Example 6)
In Example 9, the thickness of the polycarbonate molded body was 1 mm, and a coating film was formed on the support according to Example 9 except that the acrylic urethane resin paint was applied so that the thickness after drying was 70 μm. did.

(Comparative Example 7)
In Example 13, a coating film was formed on the support according to Example 13 except that the thickness of the polycarbonate molded body was 1 mm.

(Comparative Example 8)
In Example 13, the thickness of the polycarbonate molded body was 1 mm, and the coating film was formed on the support in the same manner as in Example 13 except that the acrylic ultraviolet curable resin coating was applied so that the thickness after drying was 70 μm. Formed.

(Comparative Example 9)
In Example 1, a coating film was formed on a support according to Example 1, except that the coating film was a coating film made of an acrylic nitrocellulose resin that was a mixture of an acrylic polymer and nitrocellulose on a polycarbonate molded body. did. Acrylic nitrocellulose resin coating was prepared by using 100 parts by weight of an acrylic polymer Acrydic A-166 (non-volatile content 45%, mass average molecular weight 75,000, glass transition point 50 ° C., manufactured by DIC) and nitrocellulose (trade name). DLX8-13 (manufactured by NOBEL) (6 parts by mass) and 194 parts by mass of a mixed solvent of methyl ethyl ketone, methyl isobutyl ketone and butyl isobutyrate as a solvent were mixed to prepare a solid concentration of 16.4% by mass.

(Comparative Example 10)
In Comparative Example 9, a coating film was formed on the support according to Comparative Example 9 except that the acrylic nitrocellulose resin coating was applied so that the thickness after drying was 70 μm.

(Comparative Example 11)
In Comparative Example 9, a coating film was formed on the support according to Comparative Example 9 except that the thickness of the polycarbonate molded body was 1 mm.

(Comparative Example 12)
In Comparative Example 9, the thickness of the polycarbonate molded body was 1 mm, and an acrylic nitrocellulose resin coating was applied on the support in accordance with Comparative Example 9 except that the thickness after drying was 70 μm. Formed.

(Comparative Example 13)
In Example 1, no coating film was formed on the support.

(Comparative Example 14)
In Example 4, no coating film was formed on the support.

(Comparative Example 15)
A flame-retardant polycarbonate molded body (N-7S, manufactured by Mitsubishi Gas Chemical Company) having a thickness of 1 mm was used as a support, and no coating film was formed.

(Comparative Example 16)
A flame-retardant polycarbonate molded body (N-7S, manufactured by Mitsubishi Gas Chemical Company) having a thickness of 2 mm was used as a support, and no coating film was formed.

(Comparative Example 17)
A flame-retardant polycarbonate molded body (N-7S, manufactured by Mitsubishi Gas Chemical Company) having a thickness of 3 mm was used as a support, and no coating film was formed.

(Reference Example 1)
In Comparative Example 9, a coating film was formed on the support according to Comparative Example 9 except that the thickness of the polycarbonate molded body was 3 mm.

(Reference Example 2)
In Reference Example 1, a coating film was formed on the support according to Reference Example 1 except that the acrylic nitrocellulose resin paint was applied so that the thickness after drying was 100 μm.

  Combustion tests were performed on the incombustible materials, the coating film-forming support and the non-coating-formed support obtained in Examples, Comparative Examples and Reference Examples. Table 1 shows the composition and combustion test categories.

(Combustion test)
A combustion test was conducted in accordance with the method prescribed in “Tetsudo Unyu No. 81“ Train Fire Accident ”” on May 15, 1969. FIG. 1 is a schematic view of an instrument used in a combustion test for railway vehicle materials. As shown in FIG. 1, the test material 1 which cut | disconnected the incombustible material obtained by the Example, the comparative example, and the reference example, the coating-film formation support body, and a coating-film non-formation support body to B5 size (182 mm x 257 mm), The center of the bottom of the fuel container 2 (made of iron, diameter 17.5 mm, depth 7.1 mm, thickness 0.8 mm) is held at an angle of 45 °, and 25.4 mm vertically below the center of the lower surface of the specimen 1 ( 1 inch) was placed on a container cradle 3 made of a low thermal conductive material (cork), 0.5 ml of pure ethanol was put into the fuel container 2 and ignited, and left until the fuel was burned out. The test chamber was maintained at an atmospheric temperature of 15 to 30 ° C. and an atmospheric humidity of 60 to 75% so that there was no air flow. In addition, when the test material of Example 1 was used and the flame side was used as the coating film forming surface and when the flame side was used as the polycarbonate surface (coating film non-forming surface), a preliminary test was performed in advance. Since the test results were the same, the test was held so that the polycarbonate surface of the test material was on the flame side. The determination of combustibility was made separately during and after the combustion of ethanol. During combustion, the ignition, ignition, smoke generation and fire state of the test material were observed with an infrared camera, a video camera and visual observation. After combustion, the state of residual flame, residual dust, carbonization and deformation was observed with an infrared camera, video camera and visual observation. The determination criteria are as shown in Table 2.

  It was confirmed that all of the incombustible materials of Examples 1 to 16 were incombustible. Moreover, all were highly transparent. On the other hand, Comparative Examples 1 to 6 were made of acrylic resin, acrylic silicon resin, or acrylic urethane resin. However, since the thickness of the support was set to 1 mm, it was determined to be flammable. In Comparative Example 7 and Comparative Example 8, although the coating film was formed of an acrylic ultraviolet curable resin, the thickness of the support was set to 1 mm. In Comparative Example 9 and Comparative Example 10, the coating film was formed of an acrylic nitrocellulose resin, and thus the flame retardancy was determined. In Comparative Example 11 and Comparative Example 12, the coating film was formed of an acrylic nitrocellulose resin, and the thickness of the support was 1 mm. Since Comparative Example 13 and Comparative Example 14 did not form a coating film, the determination of flammability was not achieved. Although Comparative Example 15 to Comparative Example 17 used a flame-retardant grade polycarbonate molded article, a coating film was not formed.

  Reference Example 1 and Reference Example 2 are examples in which a polycarbonate molded body having a thickness of 3 mm as a support and a coating film mainly composed of an acrylic nitrocellulose resin was formed on the molded body. Since the thickness was 3 mm, it was judged as nonflammable.

  In all of Comparative Examples 1 to 17, when the support was deformed by the heat of the flame, the fire was further increased in the deformed portion, and the flame retardancy or flammability was determined. On the other hand, since Examples 1 to 16 were able to suppress the deformation of the support by forming a coating film, the fire did not increase, and as a result, the determination of incombustibility was obtained. I was able to.

  The incombustible material according to the present invention is suitable for an interior building material for a railway vehicle because it can reduce the weight, reduce the cost, improve the degree of design freedom, and prevent the light transmittance from decreasing. Furthermore, it is suitable for various interior building materials for stores, offices, aircrafts, vehicles and ships.

1 Test material 2 Fuel container 3 Container stand

Claims (2)

Using a polycarbonate molded body as a support,
At least one layer of a coating composed mainly of an acrylic resin is formed on at least one side of the support,
The acrylic resin is at least one of acrylic resin, acrylic silicon resin, acrylic urethane resin, and acrylic ultraviolet curable resin,
The incombustible material, wherein the support has a thickness of more than 1.0 mm and not more than 3.0 mm. The non-combustible material according to claim 1, wherein the polycarbonate molded body does not contain a flame retardant.

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