JP2021155693A - Resin composition, molding and resin laminate - Google Patents

Abstract

To provide a resin composition that can give a molding having improved flame retardancy and can also improve the impact resistance of the molding in a low-temperature environment.SOLUTION: A resin composition has a siloxane copolymer polycarbonate resin, a sulfone resin having a structure represented by the formula (1), an inorganic filler, a phosphorus-containing compound, a styrenic resin, and a fluororesin.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin composition containing a siloxane copolymer polycarbonate resin. The present invention also relates to a molded product and a resin laminate containing a siloxane copolymer polycarbonate resin.

Thermoplastic resins such as polycarbonate resins are excellent in durability, light weight, molding processability, and the like. Therefore, the thermoplastic resin is used in various fields such as a construction field, a home appliance field, and a transportation field.

Specific uses of the thermoplastic resin include exterior materials and interior materials of transport aircraft such as railroad vehicles, aircraft, ships and automobiles. Examples of the exterior material and interior material include ceilings, window frames, armrests, backrests, tables, and the like.

In the above applications, it is required that the molded product using the thermoplastic resin has excellent flame retardancy and impact resistance. However, since thermoplastic resins are generally flammable and vulnerable to impact, studies have been widely conducted to improve the flame retardancy and impact resistance of molded articles using thermoplastic resins.

The following Patent Document 1 describes (A) a polycarbonate-based resin, (B) a polycarbonate-polydiorganosiloxane copolymer resin having a specific structure, (C) a styrene-based resin, and (D) a phosphorus-based flame retardant. , (E) A silicate mineral and (F) a flame retardant resin composition containing a drip inhibitor are disclosed.

JP-A-2016-102219

The molded product obtained from the resin composition described in Patent Document 1 can have some degree of flame retardancy. However, the molded product obtained from the resin composition described in Patent Document 1 may have low impact resistance in a low temperature environment. In a molded product obtained from a conventional resin composition, even if the impact resistance in a normal temperature environment can be improved to some extent, the impact resistance in a low temperature environment may not be sufficiently improved, which is difficult. It is particularly difficult to improve both flammability and impact resistance in low temperature environments.

An object of the present invention is to provide a resin composition capable of enhancing the flame retardancy of the obtained molded article and enhancing the impact resistance of the molded article in a low temperature environment. Another object of the present invention is to provide a molded product and a resin laminate using the above resin composition.

According to a broad aspect of the present invention, a siloxane copolymer polycarbonate resin, a salphon resin having a structure represented by the following formula (1), an inorganic filler, a phosphorus-containing compound, a styrene resin, and a fluorine resin. A resin composition comprising the above is provided.

In certain aspects of the resin composition according to the present invention, the salphon resin is a polyphenyl salphon resin.

In a specific aspect of the resin composition according to the present invention, the content of the salphon resin is 5% by weight or more and 30% by weight in the total of 100% by weight of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. It is less than% by weight.

In a specific aspect of the resin composition according to the present invention, the content of the inorganic filler is 5 parts by weight with respect to a total of 100 parts by weight of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. It is 20 parts by weight or less.

In certain aspects of the resin composition according to the invention, the inorganic filler is talc.

In a specific aspect of the resin composition according to the present invention, the content of the phosphorus-containing compound is 5 parts by weight based on 100 parts by weight of the total content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. More than 15 parts by weight or less.

In a specific aspect of the resin composition according to the present invention, the content of the styrene-based resin is 5 parts by weight with respect to a total of 100 parts by weight of the content of the siloxane copolymerized polycarbonate resin and the content of the salphon resin. More than 30 parts and less than 30 parts by weight.

In a specific aspect of the resin composition according to the present invention, the content of the fluororesin is 0. 5 parts by weight or more and 2 parts by weight or less.

According to a broad aspect of the present invention, there is provided a molded body in which the above-mentioned resin composition is molded.

In certain aspects of the molded body according to the present invention, the molded body is in the form of a sheet.

In certain aspects of the article according to the invention, the article has a flame propagation index of 35 or less as measured in accordance with ASTM E162.

In certain aspects of the molded body according to the present invention, the molded body is an exterior material for a transport aircraft.

According to a broad aspect of the present invention, a first layer, which is a molded product obtained by molding the above-mentioned resin composition, an aromatic polycarbonate resin different from the siloxane copolymer polycarbonate resin, and an ultraviolet light stabilizer are contained. Provided is a resin laminate having two layers and having the second layer laminated on the surface of the first layer.

In a specific aspect of the resin laminate according to the present invention, the value of ΔE after the ultraviolet irradiation test in which the resin laminate is irradiated with ultraviolet rays from the second layer side for 200 hours is determined in accordance with JIS K 7350-4. It is 10 or less.

In a specific aspect of the resin laminate according to the present invention, the ratio of the thickness of the first layer to the thickness of the resin laminate is 0.50 or more and 0.90 or less.

The resin composition according to the present invention includes a siloxane copolymer polycarbonate resin, a salphon resin having a structure represented by the above formula (1), an inorganic filler, a phosphorus-containing compound, a styrene resin, and a fluorine resin. including. Since the resin composition according to the present invention has the above-mentioned structure, it is possible to enhance the flame retardancy of the obtained molded product and to enhance the impact resistance of the molded product in a low temperature environment. can.

FIG. 1 is a cross-sectional view schematically showing a resin laminate using the resin composition according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a resin laminate using the resin composition according to the second embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The resin composition according to the present invention includes a siloxane copolymer polycarbonate resin, a salphon resin having a structure represented by the following formula (1), an inorganic filler, a phosphorus-containing compound, a styrene resin, and a fluorine resin. including.

Since the resin composition according to the present invention has the above-mentioned structure, the flame retardancy of the obtained molded product can be enhanced, and the impact resistance of the molded product in a normal temperature environment is maintained. Therefore, the impact resistance of the molded product in a low temperature environment can be improved. In the molded product obtained by the resin composition according to the present invention, for example, the impact resistance at −40 ° C. can be enhanced.

Hereinafter, details of the components contained in the resin composition according to the present invention will be described.

<Siloxane copolymer polycarbonate resin>
The resin composition according to the present invention contains a siloxane copolymer polycarbonate resin. Only one kind of the above-mentioned siloxane copolymer polycarbonate resin may be used, or two or more kinds may be used in combination. The siloxane copolymer polycarbonate resin may be a polysiloxane copolymer polycarbonate resin.

The siloxane copolymer polycarbonate resin is preferably a copolymer of a phenol compound represented by the following formula (2) and a polydiorganosiloxane represented by the following formula (3). The polydiorganosiloxane represented by the following formula (3) has hydroxyaryl groups at both ends. As the phenol compound represented by the following formula (2), only one kind may be used, or two or more kinds may be used in combination. As the polydiorganosiloxane represented by the following formula (3), only one type may be used, or two or more types may be used in combination.

In the above formula (2), R ₁ and R ₂ are hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, and cycloalkyl having 6 to 20 carbon atoms, respectively. Group, cycloalkoxy group with 6 to 20 carbon atoms, alkoxy group with 2 to 10 carbon atoms, aryl group with 3 to 14 carbon atoms, aryloxy group with 3 to 14 carbon atoms, 7 to 20 carbon atoms Represents an alkoxyl group, an alkoxyloxy group having 7 or more and 20 or less carbon atoms, a nitro group, an aldehyde group, a cyano group or a carboxyl group. In the above formula (2), R ₃ represents a group selected from the group consisting of a single bond or a group represented by the following formula (21). In the above equation (2), p and q represent integers of 1 or more and 4 or less, respectively. In the above formula (2), R ₁ and R ₂ may be the same or different from each other. In the above formula (2), p and q may be the same or different, respectively.

In the above formula (21), R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are hydrogen atoms, alkyl groups having 1 or more carbon atoms and 18 or less carbon atoms, and 3 or more carbon atoms, respectively. It represents an aryl group of 14 or less or an aralkyl group having 7 or more and 20 or less carbon atoms. In the above formula (21), R ₁₉ and R ₂₀ are hydrogen atom, halogen atom, alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 10 carbon atoms, and cycloalkyl group having 6 to 20 carbon atoms, respectively. Group, cycloalkoxy group with 6 or more and 20 or less carbon atoms, alkoxy group with 2 or more and 10 or less carbon atoms, aryl group with 3 or more and 14 or less carbon atoms, aryloxy group with 6 or more and 10 or less carbon atoms, 7 or more and 20 or less carbon atoms Represents an alkoxyl group, an alkoxyloxy group having 7 or more and 20 or less carbon atoms, a nitro group, an aldehyde group, a cyano group or a carboxyl group. In the above equation (21), m represents an integer of 1 or more and 10 or less, and n represents an integer of 4 or more and 7 or less. In the above formula (21), R _{11 to} R ₂₀ may be the same or different.

In the above formula (3), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, or aryl groups having 6 to 12 carbon atoms, respectively. Represents. The aryl group may or may not have a substituent. In the above formula (3), R ₇ and R ₈ represent hydrogen atoms, halogen atoms, alkyl groups having 1 to 10 carbon atoms, or alkoxy groups having 1 to 10 carbon atoms, respectively. In the above formula (3), R ₉ and R ₁₀ each represent a divalent aliphatic group having 2 or more and 8 or less carbon atoms. In the above equation (3), p represents an integer of 1 or more, q represents an integer of 0 or 1 or more, and p + q is an integer of less than 300. In the above formula (3), R _{1 to} R ₆ may be the same or different. In the above formula (3), R ₇ and R ₈ may be the same or different, respectively. In the above formula (3), R ₉ and R ₁₀ may be the same or different, respectively. In the above formula (3), p and q may be the same or different, respectively.

Examples of the phenol compound represented by the above formula (2) include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis ( 4-Hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy) Phenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2, 2-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3) −Bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1- Bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) Fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '-Dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol , 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4 , 4'-dihydroxy-3,3'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1 , 4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydroxyphenyl) ) Cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4'-(1,3) -Adamantane diyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantan and the like can be mentioned.

The phenolic compound represented by the above formula (2) is 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4). -Hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyl Diphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis (2- (4-hydroxyphenyl)) It is preferably propyl) benzene or 1,4-bis (2- (4-hydroxyphenyl) propyl) benzene. The phenol compound represented by the above formula (2) is more preferably 2,2-bis (4-hydroxyphenyl) propane. By using these preferable compounds, flame retardancy and impact resistance (particularly impact resistance in a low temperature environment) can be further effectively enhanced.

The polydiorganosiloxane represented by the above formula (3) can be obtained by subjecting a phenol compound having an olefinically unsaturated carbon-carbon bond to a hydrosilylation reaction at the end of a polysiloxane chain having a predetermined degree of polymerization. Can be done. The phenol compound having an olefinically unsaturated carbon-carbon bond is preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol.

The polydiorganosiloxane represented by the above formula (3) is preferably a polydiorganosiloxane having a 2-allylphenol structure at the terminal or a polydiorganosiloxane having a 2-methoxy-4-allylphenol structure at the terminal. The polydiorganosiloxane represented by the above formula (3) is more preferably a polydimethylsiloxane having a 2-allylphenol structure at the terminal or a polydimethylsiloxane having a 2-methoxy-4-allylphenol structure at the terminal. ..

The siloxane copolymer polycarbonate resin can be produced, for example, as follows. In the following description, the "phenolic compound represented by the above formula (2)" may be referred to as "phenolic compound (2)".

First, a chloroformate compound is produced as follows.

Prepare a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution. In this mixed solution, the phenol compound (2) is reacted with the chloroformate-forming compound. By this reaction, a mixed solution containing the chloroformate compound of the phenol compound (2) and / or the carbonate oligomer of the phenol compound (2) having a chloroformate group at the terminal (mixed solution containing the chloroformate compound) is produced. can get. Examples of the chloroformate-forming compound include phosgene and the chloroformate compound of the phenol compound (2). The chloroformate-forming compound is preferably phosgene.

When producing the chloroformate compound, the entire amount of the phenol compound (2) used for producing the siloxane copolymer polycarbonate resin may be reacted at one time to produce the chloroformate compound, or the phenol compound (2) may be produced. As a post-addition monomer, a part of the above may be added as a reaction raw material to the interfacial polycondensation reaction described later. The post-added monomer is a compound added in order to rapidly proceed with the interfacial polycondensation reaction described later. The post-added monomer may not be added.

The reaction for producing the chloroformate compound is preferably carried out in a solvent in the presence of an acid binder.

Examples of the acid binder include alkali metal hydroxides, alkali metal carbonates, organic bases, and mixtures thereof. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and the like. Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate and the like. Examples of the organic base include pyridine and the like. The content of the acid binder is not particularly limited, but can be appropriately determined in consideration of the stoichiometric ratio of the reaction. The content of the acid binder is 2 with respect to 1 mol of the phenol compound (2) used for forming the chloroformate compound of the phenol compound (2) (1 mol of the phenol compound (2) usually corresponds to 2 equivalents). It is preferably an equivalent amount, or a slightly excess amount than 2 equivalents.

As the solvent, a known solvent used for producing polycarbonate can be used. As the solvent, it is preferable to use a solvent that is inert to various reactions. Examples of the solvent include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. The solvent is preferably a halogenated hydrocarbon solvent, more preferably methylene chloride. Only one type of the solvent may be used, or two or more types may be used in combination.

In the reaction for producing the chloroformate compound, a small amount of the antioxidant may or may not be added. In the reaction for producing the chloroformate compound, it is preferable to add an antioxidant. Examples of the antioxidant include sodium sulfite, hydrosulfide and the like.

By the above method, a mixed solution containing a chloroformate compound (a chloroformate compound of the phenol compound (2) and / or a carbonate oligomer of the phenol compound (2) having a chloroformate group at the terminal) can be obtained.

While stirring the obtained mixed solution, the polydiorganosiloxane represented by the above formula (3) is added to the mixed solution, and the polydiorganosiloxane represented by the above formula (3) and the above chloroformate compound are interfaced with each other. Polycondensate. In this way, a siloxane copolymer polycarbonate resin can be obtained.

By using a branching agent, a siloxane copolymer polycarbonate copolymer having a branched structure can be obtained.

In order to obtain the siloxane copolymer polycarbonate copolymer having the above-mentioned branched structure, the above-mentioned branching agent may be added to the mixed solution at the time of the production reaction of the chloroformate compound, and after the completion reaction of the chloroformate compound is completed. It may be added at the time of the interfacial polycondensation reaction of.

The branching agent is preferably a trifunctional phenol compound or a tetrafunctional phenol compound, more preferably triphenol, tetraphenol, or a phenol compound having at least three functional groups having low reactivity. , 1,1,1-Tris- (p-hydroxyphenyl) ethane is more preferred. By using these preferable branching agents, a siloxane copolymer polycarbonate resin having a branched structure can be satisfactorily obtained.

The branching agent may be a phenol compound having an amine group. When the branching agent is a phenol compound having an amine group, the amine group acts as an active functional group, and a siloxane copolymer polycarbonate resin having a branched structure is produced through an amide bond.

The content of the siloxane copolymer polycarbonate resin in 100% by weight of the resin composition is preferably 55% by weight or more, more preferably 60% by weight or more, preferably 75% by weight or less, and more preferably 70% by weight. It is as follows. When the content of the siloxane copolymer polycarbonate resin is at least the above lower limit and at least the above upper limit, flame retardancy and impact resistance (particularly, impact resistance in a low temperature environment) can be further effectively enhanced.

<Salphon resin>
The resin composition according to the present invention contains a salphon resin having a structure represented by the following formula (1). The salphon resin is a thermoplastic resin. By containing the salphon resin in the resin composition, carbides (chars) are satisfactorily formed on the surface of the molded product even when the molded product burns, and the supply amount of oxygen can be suppressed. As a result, the flame retardancy of the molded product can be improved. When the resin composition does not contain the salphon resin, it is difficult to improve the flame retardancy. Further, when the resin composition contains both the salphon resin and the phosphorus-containing compound, formability and flame retardancy can be enhanced. Only one kind of the salphon resin may be used, or two or more kinds may be used in combination.

The salphon resin has a structural unit represented by the above formula (1).

Examples of the sulfone resin include polysulfone resin (PSU), polyethersulfone resin (PESU), polyphenylsulfone resin (PPSU) and the like.

From the viewpoint of further enhancing flame retardancy and impact resistance (particularly impact resistance in a low temperature environment), the salfone resin is preferably a polyether salfone resin or a polyphenyl salfone resin, and polyphenyl. More preferably, it is a salphon resin.

Of the total 100% by weight of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin, the content of the salphon resin is preferably 5% by weight or more, more preferably 10% by weight or more, and is preferable. Is 30% by weight or less, more preferably 20% by weight or less. When the content of the salphon resin is at least the above lower limit and at least the above upper limit, flame retardancy and impact resistance (particularly impact resistance in a low temperature environment) can be further enhanced.

<Inorganic filler>
The resin composition according to the present invention contains an inorganic filler. When the resin composition contains the inorganic filler, the flame retardancy of the molded product can be enhanced. Only one kind of the above-mentioned inorganic filler may be used, or two or more kinds thereof may be used in combination.

Examples of the inorganic filler include talc, mica, montmorillonite, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. , Basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salt, clay mineral, glass fiber, glass beads, silica-based balun, nitride Aluminum, boron nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, metal powder, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, stainless fiber, zinc borate, magnetic powder , Slug fiber, fly ash, silica-alumina fiber, alumina fiber, silica fiber, zirconia fiber and the like.

From the viewpoint of further enhancing flame retardancy and impact resistance (particularly impact resistance in a low temperature environment), the inorganic filler is preferably talc, mica, or montmorillonite, and more preferably talc. ..

The talc may be compressed talc. When the talc is compressed talc, the resin composition can be easily processed.

The inorganic filler may be surface-treated such as silaneization treatment, plasma treatment, and ashing treatment. When the inorganic filler is a surface-treated inorganic filler such as a silaneization treatment, the compatibility with the siloxane copolymer polycarbonate resin becomes even better.

From the viewpoint of further improving flame retardancy and impact resistance (particularly impact resistance in a low temperature environment), the volume average particle size (D50) of the inorganic filler is preferably 1 μm or more, more preferably 1. It is .5 μm or more, preferably 6 μm or less, and more preferably 5 μm or less. When the volume average particle diameter (D50) of the inorganic filler is not more than the above upper limit, a molded product having a small center of gravity distance between adjacent inorganic fillers and a large number of particles of the inorganic filler can be obtained. A molded body having a small distance of the center of gravity between adjacent inorganic fillers and a large number of particles of the inorganic filler is more excellent in flame retardancy and gas barrier property. If the distance of the center of gravity between adjacent inorganic fillers is small and the number of particles of the inorganic filler is large, even if the molded product burns, the amount of oxygen flowing into the gaps between the inorganic fillers can be suppressed, and the flammability generated during combustion can be suppressed. It is possible to suppress the release of sex gas. Further, a molded body having a small distance of the center of gravity between adjacent inorganic fillers and a large number of particles of the inorganic filler tends to have excellent impact resistance.

The volume average particle diameter of the inorganic filler is an average diameter measured on a volume basis, and is a value of a median diameter (D50) at which the cumulative volume calculated from the small diameter side is 50%. The volume average particle diameter (D50) can be measured by a laser diffraction / scattering method, an image analysis method, a Coulter method, a centrifugal sedimentation method, or the like. The volume average particle size (D50) of the inorganic filler is preferably determined by measurement by a laser diffraction / scattering method.

The content of the inorganic filler is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, based on 100 parts by weight in total of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. It is preferably 20 parts by weight or less, more preferably 15 parts by weight or less. When the content of the inorganic filler is at least the above lower limit, the flame retardancy can be further enhanced. When the content of the inorganic filler is not more than the above upper limit, the impact resistance (particularly the impact resistance in a low temperature environment) can be further enhanced.

<Phosphorus-containing compound>
The resin composition according to the present invention contains a phosphorus-containing compound. The phosphorus-containing compound is a compound having a phosphorus atom. When the resin composition contains the phosphorus-containing compound, formability and flame retardancy can be enhanced. When the resin composition does not contain the phosphorus-containing compound, the flame retardancy is lowered. Only one kind of the phosphorus-containing compound may be used, or two or more kinds thereof may be used in combination.

From the viewpoint of further enhancing the flame retardancy, the phosphorus-containing compound is preferably a phosphorus-based flame retardant.

The phosphorus-containing compound may be a phosphorus-containing compound having a halogen atom, a phosphorus-containing compound having no halogen atom, a phosphorus-containing compound having no halogen atom, and a phosphorus-containing compound having a halogen atom. It may be a mixture with a compound.

The phosphorus-containing compound may be any compound containing a phosphorus atom, and may be a compound derived from resorcinol, hydroquinone, bisphenol A, diphenylphenol, or the like.

Examples of the phosphorus-containing compound include a phosphoric acid monomer, a phosphoric acid oligomer, a phosphonic acid ester, an organophosphite, a phosphonate, a phosphonate amine, a phosphate, a phosphazene, and a phosphoric acid ester.

From the viewpoint of further enhancing flame retardancy, the phosphorus-containing compound is preferably a phosphoric acid ester. The phosphoric acid ester is a compound having a phosphoric acid ester structure.

The phosphoric acid ester may be a phosphoric acid monoester, a phosphoric acid diester, or a phosphoric acid triester.

Examples of the phosphoric acid ester include tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl-2-ethyl cresil phosphate, tri- (isopropylphenyl) phosphate, and resorcinol-bridged diphosphate. And bisphenol A cross-linked diphosphate and the like. The phosphoric acid ester is preferably an oligomeric phosphoric acid ester derived from bisphenol A.

The content of the phosphorus-containing compound is preferably 5 parts by weight or more, more preferably 9 parts by weight or more, based on 100 parts by weight in total of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. Yes, preferably 15 parts by weight or less, more preferably 12 parts by weight or less. When the content of the phosphorus-containing compound is at least the above lower limit, the flame retardancy can be further enhanced. When the content of the phosphorus-containing compound is not more than the above upper limit, the impact resistance (particularly the impact resistance in a low temperature environment) can be further enhanced.

<Styrene resin>
The resin composition according to the present invention contains a styrene-based resin. By containing the above-mentioned styrene resin, the impact resistance of the molded product can be enhanced. When the resin composition does not contain the styrene resin, the impact resistance of the molded product may be inferior. Only one type of the styrene resin may be used, or two or more types may be used in combination.

The styrene-based resin may be a homopolymer of an aromatic vinyl compound, a copolymer of an aromatic vinyl compound and a vinyl compound, or a copolymer of an aromatic vinyl compound and a rubbery polymer. It may be a polymer, or it may be a copolymer of an aromatic vinyl compound, a vinyl compound, and a rubbery polymer.

The aromatic vinyl compound is preferably styrene.

Examples of the vinyl compound include vinyl cyanide compounds, (meth) acrylic acid ester compounds, epoxy group-containing methacrylate esters such as glycidyl methacrylate, maleimide-based monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide, and acrylics. Examples thereof include α, β-unsaturated carboxylic acids such as acids, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid, and anhydrides thereof. The vinyl compound is preferably a (meth) acrylic acid ester compound, more preferably methyl methacrylate.

Examples of the rubbery polymer include polybutadiene, polyisoprene, diene copolymers (random copolymer and block copolymer of styrene / butadiene, acrylonitrile / butadiene copolymer, (meth) acrylic acid alkyl ester and butadiene. Copolymers, etc.), copolymers of ethylene and α-olefin (ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers, etc.), ethylene and unsaturated Copolymers with carboxylic acid esters (ethylene / methacrylate copolymers, ethylene / butyl acrylate copolymers, etc.), copolymers of ethylene and aliphatic vinyl (ethylene / vinyl acetate copolymers, etc.), ethylene and propylene And non-conjugated dienter polymer (ethylene / propylene / hexadiene copolymer, etc.), acrylic rubber (polybutyl acrylate, poly (2-ethylhexyl acrylate), copolymer of butyl acrylate and 2-ethylhexyl acrylate, etc.), silicone System rubber (IPN type rubber composed of polyorganosiloxane rubber, polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component; that is, it has a structure in which the two rubber components are intertwined with each other so as not to be separated. (IPN type rubber composed of a copolymer rubber, a polyorganosiloxane rubber component and a polyisobutylene rubber component, etc.) and the like.

Examples of the styrene resin include styrene resins such as polystyrene resin, HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and SMA resin, and styrene-butadiene-styrene. Examples thereof include copolymer resins and styrene-isoprene-styrene copolymer resins.

From the viewpoint of further effectively enhancing the impact resistance (particularly the impact resistance in a low temperature environment), the styrene resin is preferably an MBS resin.

The content of the styrene resin is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, based on 100 parts by weight in total of the content of the siloxane copolymerized polycarbonate resin and the content of the salphon resin. It is more preferably 12 parts by weight or more, preferably 30 parts by weight or less, and more preferably 20 parts by weight or less. When the content of the styrene resin is at least the above lower limit, the impact resistance (particularly the impact resistance in a low temperature environment) can be further effectively enhanced. When the content of the styrene resin is not more than the above upper limit, the flame retardancy can be further effectively enhanced.

<Fluorine resin>
The resin composition according to the present invention preferably contains a fluororesin. When the resin composition contains the fluorine-based resin, the flame retardancy of the molded product can be further enhanced. Only one kind of the above-mentioned fluororesin may be used, or two or more kinds may be used in combination.

Examples of the fluororesin include a homopolymer having a fluorinated alpha-olefin monomer as a structural unit, a copolymer containing a fluorinated alpha-olefin monomer as a structural unit, and the like.

The fluorinated alpha-olefin monomer is an alpha-olefin monomer containing a substituent having at least one fluorine atom.

Examples of the fluorinated alpha-olefin monomer include tetrafluoroethylene (CF ₂ = CF ₂ ), CHF = CF ₂ , vinylidene fluoride (CH ₂ = CF ₂ ), CH ₂ = CHF, and chlorotrifluoroethylene (CClF = CF). ₂ ), CCl ₂ = CF ₂ , CClF = CClF, CHF = CCl ₂ , CH ₂ = CClF, CCl ₂ = CClF, Hexafluoropropylene (CF ₂ = CFCF ₃ ), CF ₃ CF = CHF, CF ₃ CH = CF ₂ , CF ₃ CH = CH ₂ , CF ₃ CF = CHF, CHF ₂ CH = CHF, CF ₃ CH = CH _{2, and the} like.

Examples of the fluororesin include poly (tetrafluoroethylene) homopolymer (PTFE), poly (hexafluoroethylene), poly (tetrafluoroethylene-hexafluoroethylene), poly (tetrafluoroethylene-ethylene-propylene) and the like. Can be mentioned. The poly (tetrafluoroethylene) homopolymer (PTFE) may be fibrogenic or non-fibrous.

The content of the fluororesin is preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more, and preferably 2 parts by weight or less, based on 100 parts by weight of the siloxane copolymer polycarbonate resin. More preferably, it is 1.5 parts by weight or less. When the content of the fluororesin is at least the above lower limit, the flame retardancy can be further enhanced. When the content of the fluororesin is not more than the above upper limit, the impact resistance (particularly the impact resistance in a low temperature environment) can be further improved.

The content of the fluororesin is preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight, based on 100 parts by weight in total of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. It is 2 parts by weight or more, preferably 2 parts by weight or less, and more preferably 1.5 parts by weight or less. When the content of the fluororesin is at least the above lower limit, the flame retardancy can be further enhanced. When the content of the fluororesin is not more than the above upper limit, the impact resistance (particularly the impact resistance in a low temperature environment) can be further improved.

<Other ingredients>
The resin composition may contain other components as long as the object of the present invention is not impaired.

Examples of the other components include drip inhibitors, antioxidants, heat stabilizers, light stabilizers, UV absorbers, colorants, plasticizers, lubricants, mold release agents, reinforcing agents and the like. As for each of the above other components, only one kind may be used, or two or more kinds may be used in combination.

When the resin composition contains the other components, the content of the other components is not particularly limited. The content of the other components is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, still more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the siloxane copolymerized polycarbonate resin. It is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less.

Examples of the antioxidant include alkylated monophenols; alkylated polyphenols; tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamete)] methane and other polyphenols and diene alkylation reaction products. Butalization reaction product of para-cresol or dicyclopentadiene; alkylated hydroquinone; hydroxylated thiodiphenyl ether; alkylidene-bisphenol; benzyl compound; beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propion Esters of acids and monovalent or polyhydric alcohols; esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monovalent or polyhydric alcohols; distearylthiopropionates, di Laurylthiopropionate, ditridecylthiodipropionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-) Examples thereof include esters of thioalkyl compounds or thioaryl compounds such as tert-butyl-4-hydroxyphenyl) propionate; and amide compounds of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid.

When the resin composition contains the antioxidant, the content of the antioxidant is preferably 0.01 parts by weight or more with respect to 100 parts by weight of the siloxane copolymer polycarbonate resin, preferably 0. It is 1 part by weight or less.

Examples of the photostabilizer include benzotriazoles such as 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) -benzotriazole; and 2-hydroxy-. Examples thereof include 4-n-octoxybenzophenone.

When the resin composition contains the light stabilizer, the content of the light stabilizer is preferably 0.01 part by weight or more, preferably 0.01 parts by weight or more, based on 100 parts by weight of the siloxane copolymer polycarbonate resin. It is 5 parts by weight or less.

Examples of the UV absorber include hydroxybenzophenone; hydroxybenzotriazole; hydroxybenzotriazine; cyanoacrylate; oxanilide; benzoxazineone; 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3). -Tetramethylbutyl) -phenol; 2-hydroxy-4-n-octyloxybenzophenone; 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl]- 5- (octyloxy) -phenol; 2,2'-(1,4-phenylene) bis (4H-3,1-benzoxazine-4-one); 1,3-bis [(2-cyano-3, 3-Diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane; 2,2'-(1,4-phenylene) bis (4H-3) , 1-benzoxazine-4-one); 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl)] ) Oxy] methyl] propane; and inorganic substances having an average particle size of 100 nm or less, such as cerium oxide and zinc oxide.

When the resin composition contains the UV absorber, the content of the UV absorber is preferably 0.01 parts by weight or more, preferably 5 parts by weight, based on 100 parts by weight of the siloxane copolymer polycarbonate resin. It is less than a part.

Examples of the colorant include titanium dioxide, carbon black, and organic dyes.

As the plasticizer, the lubricant, or the mold release agent, only one type may be used, or two or more types may be used in combination. Many of the compounds used as plasticizers also have the properties of lubricants and template agents, and many of the compounds used as lubricants also have the properties of template agents and plasticizers, and are used as template agents. Many of these compounds also have the properties of plasticizers and lubricants.

Examples of the plasticizer, lubricant, or mold release agent include phthalates such as dioctyl-4,5-epoxide-hexahydrophthalate; tris- (octoxycarbonylethyl) isocyanurate; tristearate; poly-alpha-olefin. Epoxidized soybean oil; Esters; Fatty acid esters such as alkyl stearyl esters; Steerates such as methyl stearate, stearyl stearate, pentaerythritol tetrastearate; polyethylene glycol polymers, polypropylene glycol polymers, poly (ethylene glycol-co-propylene) A mixture of a hydrophilic and hydrophobic nonionic surfactant such as a glycol) copolymer and methyl stearate; a mixture of methyl stearate and a polyethylene-polyethylene glycol copolymer; and a wax such as beeswax, montan wax, paraffin wax, etc. And so on.

When the resin composition contains the plasticizer, the lubricant, or the release agent, each of the plasticizer, the lubricant, and the release agent is based on 100 parts by weight of the siloxane copolymer polycarbonate resin. The content is preferably 0.1 part by weight or more, and preferably 1 part by weight or less.

Examples of the reinforcing agent include fibrous reinforcing agents such as glass fiber.

When the resin composition contains the reinforcing agent, the content of the reinforcing agent is preferably 1 part by weight or more, more preferably 10 parts by weight or more, based on 100 parts by weight of the siloxane copolymer polycarbonate resin. It is preferably 25 parts by weight or less, more preferably 20 parts by weight or less.

The relative amount of each component in the other components has an important effect on the mechanical properties such as low smoke concentration, low smoke toxicity, and ductility of the molded product. Even if a large amount of a certain component is blended in order to improve a certain property of the molded product, the other property may be deteriorated.

(Molded body)
The molded product according to the present invention is a molded product on which the above-mentioned resin composition is molded. A molded product can be obtained by molding the resin composition according to the present invention. The molded product is excellent in flame retardancy and impact resistance in a low temperature environment. The molded product is also excellent in impact resistance in a normal temperature environment.

The molded product according to the present invention can be molded by a known method using the above-mentioned resin composition. For example, a molded product can be obtained by heating the resin composition at 230 ° C. to 300 ° C. for molding and curing. Further, by vacuum forming the obtained molded product, a molded product having a predetermined shape can be obtained.

From the resin composition according to the present invention, molded articles having various shapes can be obtained. For example, the molded product according to the present invention may have a rectangular shape, a curved surface shape, an uneven shape, or a sheet shape.

The molded product is preferably in the form of a sheet. The sheet-shaped molded body is a resin sheet. The resin sheet can be produced, for example, by extruding a resin composition into a sheet.

In the above-mentioned molded product, the flame propagation index measured according to ASTM E162 is preferably 80 or less, more preferably 50 or less, and further preferably 35 or less. When the flame propagation index is not more than the above upper limit, the flame retardancy can be further enhanced. The smaller the flame propagation index, the better, in order to further enhance the flame retardancy.

Specifically, the flame propagation index is measured as follows.

The molded body is cut or the like to obtain a test sample having a length of 152 mm, a width of 457 mm and a thickness of 3 mm. The flame propagation index of the obtained test sample is measured using a radiant panel test apparatus according to ASTM E162. Set the sample at an angle of 30 ° with respect to the radiant panel. The sample and the radiant panel are separated by 121 mm at the top of the panel and 367 mm at the bottom of the panel. The radiant panel is heated to 670 ° C. and the sample is ignited using a pilot frame placed on top of the sample. When the thickness of the molded product is less than 3 mm, a test sample having a thickness of 3 mm may be prepared using the material (resin composition) of the molded product.

The flame propagation index is calculated by the following formula from the speed at which the flame propagates on the surface of the sample (propagation velocity: Fs) and the internal temperature rise value (Q) of the exhaust pipe.

Flame propagation index = Fs × Q

The flame propagation index is preferably the average value of the flame propagation indexes of a plurality of test samples, and more preferably the average value of the flame propagation indexes of three or more test samples.

Since the molded product is excellent in flame retardancy and impact resistance in a low temperature environment and a normal temperature environment, it is preferably an exterior material or an interior material of a transport aircraft, and more preferably an exterior material of a transport aircraft. .. Examples of the transport aircraft include railroad vehicles, aircraft, ships, automobiles, and the like. The molded body is preferably an exterior material for a railway vehicle, preferably an exterior material for an aircraft, preferably an exterior material for a ship, and preferably an exterior material for an automobile.

<Resin laminate>
The molded product into which the resin composition is molded is suitably used for laminating with another layer to obtain a resin laminate.

The resin laminate includes, for example, a first layer, which is a molded product on which the resin composition is molded, and a second layer. In the resin laminate, the second layer is laminated on the surface of the first layer.

The second layer preferably contains a thermoplastic resin. The second layer is preferably formed of a thermoplastic resin composition. The second layer preferably contains an aromatic polycarbonate resin different from the siloxane copolymer polycarbonate resin. The second layer preferably contains an ultraviolet light stabilizer. The second layer preferably contains an aromatic polycarbonate resin different from the siloxane copolymer polycarbonate resin and an ultraviolet light stabilizer.

With the above resin laminate, weather resistance can be improved. In the resin laminate, the flame retardancy of the excellent molded product and the impact resistance in an excellent low temperature environment can be maintained for a long period of time. Further, the resin laminate can suppress discoloration. Even if the resin laminate is used in an environment irradiated with ultraviolet rays, the deterioration of the first layer in the resin laminate by ultraviolet rays is less likely to occur. In particular, when the second layer contains an aromatic polycarbonate resin different from the siloxane copolymer polycarbonate resin and an ultraviolet light stabilizer, these effects are exhibited even more effectively.

FIG. 1 is a cross-sectional view schematically showing a resin laminate using the resin composition according to the first embodiment of the present invention.

The resin laminate 10 shown in FIG. 1 includes a first layer 1 and a second layer 2. The second layer 2 is laminated on the surface of the first layer 1. Specifically, the second layer 2 is laminated only on one surface (first surface) of the first layer 1. The second layer 2 is not laminated on the other surface (second surface) of the first layer 1 opposite to the one surface. The first layer 1 is a molded product of the resin composition described above. The second layer 2 preferably contains an aromatic polycarbonate resin different from the siloxane copolymer polycarbonate resin and an ultraviolet light stabilizer.

FIG. 2 is a cross-sectional view schematically showing a resin laminate using the resin composition according to the second embodiment of the present invention.

The resin laminate 10A shown in FIG. 2 includes a first layer 1A and a second layer 2A. The second layer 2A is laminated on the surface of the first layer 1A. Specifically, the second layer 2A is laminated on both one surface (first surface) of the first layer 1A and the other surface (second surface) on the opposite side of the one surface. Has been done. The first layer 1A is a molded product of the above-mentioned resin composition. The second layer 2A preferably contains an aromatic polycarbonate resin different from the siloxane copolymer polycarbonate resin and an ultraviolet light stabilizer.

The second layer may be laminated on at least a part of the surface of the first layer. The second layer may not be laminated on the surfaces on both sides of the first layer. The second layer may not be laminated on the entire surface of the first layer. If the second layer is laminated on at least a part of the surface of the first layer, the weather resistance of the resin laminate can be enhanced from the second layer, and the resin can be improved. Deterioration of the first layer in the laminated body can be suppressed. From the viewpoint of further enhancing the weather resistance of the resin laminate and further suppressing the deterioration of the first layer in the resin laminate, the second layer is formed on both surfaces of the first layer. It is preferable that the first layer is laminated, and it is more preferable that the second layer is laminated on the entire surface of the first layer.

<Second layer>
Aromatic polycarbonate resin:
From the viewpoint of further enhancing the weather resistance, the second layer preferably contains an aromatic polycarbonate resin different from the siloxane copolymer polycarbonate resin. Only one type of the aromatic polycarbonate resin may be used, or two or more types may be used in combination.

From the viewpoint of further enhancing the weather resistance, the aromatic polycarbonate resin is preferably an aromatic polycarbonate resin having a structural unit represented by the following formula (11).

In the above formula (11), R1 and R2 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a group in which a substituent is bonded to an alkyl group having 1 to 20 carbon atoms, or an aryl group, respectively. In the above formula (11), R3 and R4 represent hydrogen atoms or alkyl groups, respectively.

When R3 or R4 in the above formula (11) is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more, preferably 6 or less, more preferably 3 or less, still more preferably 2 or less. be. Preferred alkyl groups include methyl group, ethyl group, propyl group, butyl group, tert-butyl group, pentyl group, heptyl group and the like.

The aromatic polycarbonate resin may have only one type of structural unit represented by the above formula (11), or may have two or more types.

Examples of the compound for introducing the structural unit represented by the above formula (11) in obtaining the aromatic polycarbonate resin include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 2,2-. Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-Methylpentane, 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxy-3- (1-methylethyl) phenyl) propane, 2 , 2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3- (1-methylpropyl) phenyl) propane, 2,2-bis (4-hydroxy-) 3-Cyclohexylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane ( Bisphenol Z), 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1, 1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3) −tert-Butylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, 1,1 -Bis (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dimethyl) Phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) ) -1-Phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-si) Clohexylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-Hydroxyphenyl) cyclooctane, 4,4'-(1,3-phenylenediisopropyridene) bisphenol, 4,4'-(1,4-phenylenediisopropyridene) bisphenol, 9,9-bis (4) -Hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxybiphenyl, 1, Examples thereof include 1-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane and 1,1-bis (4-hydroxy-6-methyl-3-tert-butylphenyl) butane.

From the viewpoint of further enhancing flame retardancy and impact resistance, the compound for introducing the structural unit represented by the above formula (11) when obtaining the above aromatic polycarbonate resin is 2,2-bis (2,2-bis (). With 4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), or 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z) 2,2-Bis (4-hydroxyphenyl) propane (bisphenol A) is more preferable. The aromatic polycarbonate resin preferably has a structural unit derived from such a preferred compound.

Examples of commercially available aromatic polycarbonate resins having a structural unit derived from a bisphenol A type compound include "Iupilon E series" manufactured by Mitsubishi Gas Chemical Company.

Examples of commercially available aromatic polycarbonate resins having a structural unit derived from a bisphenol Z-type compound include "Panlite series" manufactured by Teijin Chemicals Ltd. and "Iupilon Z series" manufactured by Mitsubishi Gas Chemicals Ltd.

The viscosity average molecular weight (Mv) of the aromatic polycarbonate resin is preferably 10,000 or more, more preferably 15,000 or more, preferably 50,000 or less, and more preferably 40,000 or less. When the viscosity average molecular weight is at least the above lower limit and at least the above upper limit, flame retardancy and impact resistance can be further enhanced.

The aromatic polycarbonate resin may or may not have a branched structure.

The aromatic polycarbonate resin can be produced by a conventionally known method. Examples of the method for producing the aromatic polycarbonate resin include a melt polymerization method and a phase interface method.

Examples of the method for producing an aromatic polycarbonate resin by the above-mentioned melt polymerization method include a method in which a diphenol compound and a diphenyl carbonate compound are reacted in a molten state by utilizing a transesterification reaction. In this method, for example, a diphenol compound and a diphenyl carbonate compound are placed in a reactor equipped with a stirrer and a distillate concentrator, and the reactor is heated to a predetermined temperature in a nitrogen gas atmosphere to melt it. Can be in a state. A branching agent, a chain terminator, or the like may be used in the method for producing an aromatic polycarbonate resin by the above-mentioned melt polymerization method.

As a method for producing an aromatic polycarbonate resin by the above-mentioned phase interface method, a diphenol compound, a carbonate halide or an aromatic dicarboxylic acid dihalide, a branching agent if necessary, and a chain terminator if necessary. There is a method of reacting with. In this method, a carbonate halide may be used, an aromatic dicarboxylic acid dihalide may be used, or a carbonate halide and an aromatic dicarboxylic acid dihalide may be used.

The diphenol compound is not particularly limited. As the diphenol compound, a conventionally known diphenol compound can be used. Only one kind of the diphenol compound may be used, or two or more kinds thereof may be used in combination.

The diphenyl carbonate compound is not particularly limited. As the diphenyl carbonate compound, a conventionally known diphenyl carbonate compound can be used. Only one kind of the above diphenyl carbonate compound may be used, or two or more kinds may be used in combination.

The above-mentioned carbonate halide is not particularly limited. As the above-mentioned halide halide, a conventionally known halide-halide can be used. Only one kind of the above-mentioned halide halide may be used, or two or more kinds thereof may be used in combination.

The above-mentioned carbonate halide is preferably phosgene.

The aromatic dicarboxylic acid dihalide is not particularly limited. As the aromatic dicarboxylic acid dihalide, a conventionally known aromatic dicarboxylic acid dihalide can be used. As the aromatic dicarboxylic acid dihalide, only one kind may be used, or two or more kinds may be used in combination.

The aromatic dicarboxylic acid dihalide is preferably a benzenedicarboxylic acid dihalide.

The branching agent is not particularly limited. As the branching agent, a conventionally known branching agent can be used. As the branching agent, only one kind may be used, or two or more kinds may be used in combination.

The branching agent is preferably a trifunctional phenol compound or a tetrafunctional phenol compound, more preferably triphenol, tetraphenol, or a phenol compound having at least three functional groups having low reactivity. , 1,1,1-Tris- (p-hydroxyphenyl) ethane is more preferred. By using these preferable branching agents, an aromatic polycarbonate resin having a branched structure can be satisfactorily obtained.

The branching agent may be a phenol compound having an amine functional group. When the branching agent is a phenol compound having an amine functional group, the amine functional group acts as an active functional group, and branching of the aromatic polycarbonate resin occurs through an amide bond.

The chain terminator is not particularly limited. As the chain terminator, a conventionally known chain terminator can be used. Only one type of the chain terminator may be used, or two or more types may be used in combination.

From the viewpoint of obtaining an aromatic polycarbonate resin satisfactorily, the chain terminator is described in Phenol; p-chlorophenol; p-tert-butylphenol; 2,4,6-tribromophenol; DE-A 2 842 005. Long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) -phenols and monoalkylphenols with 8 to 20 carbon atoms in the alkyl substituents; or 3,5-di-tert-butylphenol, p- Alkylphenols such as isooctylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) -phenol, and 4- (3,5-dimethylheptyl) -phenol are preferable.

From the viewpoint of obtaining an aromatic polycarbonate resin satisfactorily, the content of the chain terminator is preferably 0.5 mol or more, preferably 10 mol or less, with respect to 100 mol of the diphenol compound.

The content of the aromatic polycarbonate resin in 100% by weight of the second layer is preferably 50% by weight or more, more preferably 55% by weight or more, preferably 95% by weight or less, more preferably 90% by weight. Below, it is more preferably 85% by weight or less, and particularly preferably 80% by weight or less. When the content of the aromatic polycarbonate resin is at least the above lower limit and at least the above upper limit, flame retardancy and impact resistance can be further enhanced.

Ultraviolet (UV) stabilizer:
The ultraviolet light stabilizer is a substance that suppresses deterioration due to ultraviolet rays. For example, when polycarbonate and an ultraviolet light stabilizer are used, ultraviolet energy is absorbed and a part of chemical bonds in the polycarbonate is transferred to suppress deterioration of the polycarbonate. By using the above-mentioned ultraviolet light stabilizer, it is possible to satisfactorily absorb ultraviolet rays and suppress deterioration (coloring) of the molded product. Only one kind of the ultraviolet light stabilizer may be used, or two or more kinds thereof may be used in combination.

Examples of the ultraviolet light stabilizer include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -benzotriazole, and 2-hydroxy-4-n-. Benzotriazoles such as octoxybenzophenone and hydroxybenzophenone; hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates; oxanilides; benzoxazines; 2- (2H-benzotriazole-2-yl) -4- (1,1,3) 3-Tetramethylbutyl) -phenol; 2-hydroxy-4-n-octyloxybenzophenone; 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- (octyloxy) -phenol, 2,2'-(1,4-phenylene) bis (4H-3,1-benzoxazine-4-one); 1,3-bis [(2-cyano-3) , 3-Diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane; 2,2'-(1,4-phenylene) bis (4H-) 3,1-benzoxazine-4-one); 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenyl) Acryloyl) oxy] methyl] propane; and inorganic substances such as titanium oxide, cerium oxide, and zinc oxide can be mentioned.

In the resin composition for forming the second layer or the second layer, the content of the ultraviolet light stabilizer is preferably 0.01 weight by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. More than parts, more preferably 0.1 parts by weight or more, still more preferably 0.5 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less.

Other details of the second layer:
The second layer may contain the other components described above as the material of the resin composition.

When the resin composition contains the other components, the content of the other components is not particularly limited. In the resin composition for forming the second layer or the second layer when the second layer or the resin composition for forming the second layer contains the other components, the resin composition for forming the second layer or the second layer. The content of the other components is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, still more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the aromatic polycarbonate resin. Yes, preferably 10 parts by weight or less, more preferably 5 parts by weight or less.

From the viewpoint of effectively maintaining a good appearance, the value of ΔE after the ultraviolet irradiation test in which the resin laminate is irradiated with ultraviolet rays from the second layer side for 200 hours is based on JIS K 7350-4. It is preferably 10 or less, more preferably 8 or less.

From the viewpoint of effectively enhancing weather resistance, flame retardancy, and impact resistance in a low temperature environment, the ratio of the thickness of the first layer to the thickness of the resin laminate is preferably 0.50 or more. , More preferably 0.60 or more, preferably 0.90 or less, and more preferably 0.80 or less.

Since the resin laminate is excellent in flame retardancy and impact resistance in a low temperature environment and a normal temperature environment, it is preferably an exterior material or an interior material of a transport aircraft, and more preferably an exterior material of a transport aircraft. preferable. Examples of the transport aircraft include railroad vehicles, aircraft, ships, automobiles, and the like. The resin laminate is preferably an exterior material for a railway vehicle, preferably an exterior material for an aircraft, preferably an exterior material for a ship, and preferably an exterior material for an automobile.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

The following materials were prepared as materials for the molded product (first layer).

Siloxane copolymer polycarbonate resin:
Siloxane copolymer polycarbonate resin ("EXL1330" manufactured by Sabic)

Salhon resin:
Polyphenyl sulphon resin ("USP1400" manufactured by UNINKO)

Inorganic filler:
Talc (IMI FABI "ULTRA 5C", volume average particle size 0.65 μm)

The volume average particle size (D50) of talc was determined by measuring the particle size distribution using an X-ray transmission type sedimentation method particle size distribution measuring device (“(Sedigraf 5120)” manufactured by Shimadzu Corporation).

Phosphorus-containing compounds:
Phosphoric acid ester ("Fylol Flex Sol DP" manufactured by ICL Japan)

Styrene-based resin:
MBS resin ("CLEAR STRENGH E-950" manufactured by ARKEMA)

Fluorine resin:
Polytetrafluoroethylene ("Teflon CFP6000" manufactured by DuPont)

The following materials were prepared as the materials for the second layer.

Weather-resistant aromatic polycarbonate composition (Teijin's "SS-2525Z")

(Example 1)
Preparation of resin composition:
Using a twin-screw extruder (“TEX30a” manufactured by Japan Steel Works, Ltd.), the mixture blended in the blending amount (part by weight) shown in Table 1 was mixed at a cylinder temperature of 230 ° C., a mold temperature of 230 ° C., and a pressure of 0.7. After melt-kneading under the conditions of a bar (vacuum), a screw diameter of 30 mm, a rotation speed of 400 rpm, and an extrusion rate of 20 kg / hour, melt extrusion was performed. The resin composition obtained by melt extrusion was cooled by a water cooling method, cut into pellets using a pelletizer, and then dried at about 120 ° C. for about 5 hours to obtain a pellet-shaped resin composition.

Preparation of molded product:
After melting the pelletized resin composition using a single-screw extruder (“GT50” manufactured by Plastic Engineering Laboratory Co., Ltd.) under the conditions of a cylinder temperature of 230 ° C., a mold temperature of 230 ° C., and an extrusion rate of 25 kg / hour. , Formed into a sheet. Next, the ratio of the pick-up speed to the roll speed in the pick-up machine (pick-up speed / roll speed) was set to 1.05 and pick-up was performed to obtain a resin sheet (molded product) having a thickness of 3.0 mm.

(Examples 2 to 6 and Comparative Examples 1 to 6)
A resin composition and a molded product were obtained in the same manner as in Example 1 except that the blending amount (part by weight) of each component was changed as shown in Tables 1 and 2 below.

(Example 7)
Preparation of resin laminate:
As the resin composition for forming the first layer (molded article), the same resin composition as in Example 5 was prepared. As a composition for forming the second layer, a weather-resistant aromatic polycarbonate composition (“SS-2525Z” manufactured by Teijin Limited) was prepared.

Using a single-screw extruder, dried pellets are co-extruded into a sheet from a multi-manifold type two-layer mold (width 30 mm x thickness 3 mm) under the condition of melting temperature of 300 ° C. under the condition of extrusion amount of 20 kg / hour. bottom. A resin laminate including the first layer (molded body) and the second layer was produced. The thickness of the resin laminate was adjusted by using three SUS rolls having a width of 40 mm on the downstream side of the multi-manifold type two-layer mold. In the obtained resin laminate, the thickness of the first layer was 2.1 mm, the thickness of the second layer was 0.9 mm, and the thickness of the resin laminate was 3.0 mm.

(evaluation)
(1) Flame retardant (flame propagation index)
The obtained resin sheet was cut into a length of 152 mm, a width of 457 mm, and a thickness of 3 mm to obtain three test samples (samples for measuring the flame propagation index). The flame propagation index of the obtained test sample was determined by the method described above using a radiant panel test device in accordance with ASTM E162.

[Criteria for flame retardancy]
◯: Flame propagation index is 35 or less ×: Flame propagation index exceeds 35

(2) Impact resistance (Izod impact test with notch)
The obtained resin sheet was cut into a length of 63.5 mm, a width of 12.7 mm, and a thickness of 3 mm to obtain 10 test samples (samples for measuring the Izod impact value). With respect to the obtained test sample, the Izod impact value at 23 ° C. and the Izod impact value at −40 ° C. were measured using an “Izod impact tester” manufactured by Toyo Seiki Co., Ltd. in accordance with ASTM D256.

[Criteria for impact resistance (23 ° C)]
○ ○: Izod impact value is 700 J / m or more ○: Izod impact value is 600 J / m or more and less than 700 J / m Δ: Izod impact value is 500 J / m or more and less than 600 J / m ×: Izod impact value is less than 500 J / m

[Criteria for impact resistance (-40 ° C)]
○ ○: Izod impact value is 180 J / m or more ○: Izod impact value is 150 J / m or more and less than 180 J / m Δ: Izod impact value is 120 J / m or more and less than 150 J / m ×: Izod impact value is less than 120 J / m

(3) Weather resistance (ultraviolet irradiation test, weather resistance test (ΔE))
The weather resistance of the molded product of Example 5 and the resin laminate of Example 7 was evaluated. The molded product of Example 5 and the resin laminate of Example 7 were each cut into a size of 150 mm in length × 70 mm in width to obtain a weather resistance test sample having a thickness of 3.0 mm. The obtained test sample was exposed to 200 ultraviolet rays under the conditions of a temperature of 63 ° C. ± 3 ° C. and an irradiation intensity of 255 ± 45 (W / m ^{2) using a sunshine weather meter test device in accordance with JIS K7350-4.} After irradiation for a long time, the change in surface color difference (ΔE) was determined with a color difference meter. Regarding the molded product of Example 5, the molded product was irradiated with ultraviolet rays from one surface side. Regarding the resin laminate of Example 7, the resin laminate was irradiated with ultraviolet rays from the outer surface side of the second layer.

[Criteria for weather resistance]
◯: ΔE10 or less Δ: Exceeds ΔE10, 25 or less ×: Exceeds ΔE25

The composition and results are shown in Tables 1 to 3 below.

The resin sheet (molded body) and the resin laminate obtained in the examples are capable of enhancing flame retardancy, and not only have impact resistance in a normal temperature environment (23 ° C.) but also in a low temperature environment (a low temperature environment (23 ° C.)). The impact resistance at -40 ° C) was also improved. On the other hand, with the resin sheet (molded product) obtained in the comparative example, it was difficult to improve both the flame retardancy and the impact resistance in a low temperature environment (-40 ° C).

Further, in the resin laminate obtained in the examples, the change in surface color difference (ΔE) could be suppressed as compared with the case where only the molded product (first layer) was used.

1,1A ... First layer (molded body)
2,2A ... Second layer 10,10A ... Resin laminate

Claims (15)

A resin composition containing a siloxane copolymer polycarbonate resin, a salphon resin having a structure represented by the following formula (1), an inorganic filler, a phosphorus-containing compound, a styrene resin, and a fluorine resin.

The resin composition according to claim 1, wherein the sulphon resin is a polyphenyl sulphon resin. The first or second claim, wherein the content of the salphon resin is 5% by weight or more and 30% by weight or less in a total of 100% by weight of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. Resin composition. Claims 1 to 3 that the content of the inorganic filler is 5 parts by weight or more and 20 parts by weight or less with respect to a total of 100 parts by weight of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. The resin composition according to any one of the items. The resin composition according to any one of claims 1 to 4, wherein the inorganic filler is talc. Claims 1 to 5 in which the content of the phosphorus-containing compound is 5 parts by weight or more and 15 parts by weight or less with respect to a total of 100 parts by weight of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. The resin composition according to any one of the above. Claims 1 to 6 in which the content of the styrene resin is 5 parts by weight or more and 30 parts by weight or less with respect to a total of 100 parts by weight of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. The resin composition according to any one of the above. Claim 1 in which the content of the fluororesin is 0.5 parts by weight or more and 2 parts by weight or less with respect to a total of 100 parts by weight of the content of the siloxane copolymer polycarbonate resin and the content of the salphon resin. The resin composition according to any one of 7 to 7. A molded product obtained by molding the resin composition according to any one of claims 1 to 8. The molded product according to claim 9, which is in the form of a sheet. The molded article according to claim 9 or 10, wherein the flame propagation index measured according to ASTM E162 is 35 or less. The molded product according to any one of claims 9 to 11, which is an exterior material of a transport aircraft. A first layer, which is a molded product on which the resin composition according to any one of claims 1 to 8 is molded,
A second layer containing an aromatic polycarbonate resin different from the siloxane copolymer polycarbonate resin and an ultraviolet light stabilizer is provided.
A resin laminate in which the second layer is laminated on the surface of the first layer. The resin laminate according to claim 13, wherein the value of ΔE after the ultraviolet irradiation test in which the resin laminate is irradiated with ultraviolet rays from the second layer side for 200 hours in accordance with JIS K 7350-4 is 10 or less. .. The resin laminate according to claim 13 or 14, wherein the ratio of the thickness of the first layer to the thickness of the resin laminate is 0.50 or more and 0.90 or less.

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