CN1408767A - Flame retardant aromatic poly cabonic ester resin composition and finished products - Google Patents

Abstract

The present invention provides a flame-retardant aromatic polycarbonate resin composition and its molded article, and a halogen-free polycarbonate resin composition and its molded article excellent in transparency and anti-dripping properties. In this composition, 0.1-10 weight part of silicone compounds are contained per 100 weight part of resin components. In this siloxane compound, the content of Si-H groups is 0.1-1.2 mol/100g, and the proportion of aryl groups represented by the above-mentioned general formula (1) is 10-70% by weight, wherein each code is as described in the description .

Description

Flame-retardant aromatic polycarbonate resin composition and molded article

technical field

The present invention relates to a flame-retardant aromatic polycarbonate resin composition and its molded article. More specifically, the present invention relates to a flame retardant that does not substantially contain bromide and chloride (halogenated flame retardant) or phosphide as a flame retardant, and is excellent in drip prevention (drip prevention) of the resin when burned. Combustible aromatic polycarbonate resin composition and molded article thereof. The present invention also relates to a flame-retardant aromatic polycarbonate resin composition capable of obtaining a molded article excellent in transparency.

Background technique

Aromatic polycarbonate resins such as aromatic polycarbonate resins, aromatic polycarbonate resin/styrene-based resin alloys, and aromatic polycarbonate resin/aromatic polyester resin alloys can be easily and produced by injection molding, etc. High-efficiency processing methods are used to make various molded products and are widely used in industrial sectors. Specifically, aromatic polycarbonate resins or their alloys are widely used in exterior and interior parts of office automation equipment such as computers, notebook computers, laser printers, inkjet printers, copiers and fax machines, and home appliances. In these applications, the resin composition must reflect the gloss, color tone, vividness and uniformity of the molded product, and sometimes it is important to consider the dyeing performance when a colorant is added to the resin composition. Sometimes it is necessary to use a laser printer with good repeatability, simplicity, and high-speed printing of required text, symbols and graphics to print text and logos on the surface of the molded product. At this time, the clarity of text and symbols must be considered.

On the other hand, moldings of aromatic polycarbonate resins are also widely used in industrial sectors requiring excellent transparency and heat resistance. Give full play to the excellent transparency of aromatic polycarbonate resin, that is, the characteristics of high light transmittance and extremely low haze. In the fields requiring high transparency, such as various lighting lamp covers and protective covers for transparent display, Aromatic polycarbonate resin moldings are widely used. In these applications, due to the high temperature of light sources such as fluorescent lamps and light bulbs, the products are also exposed to high humidity when used in bathrooms or outdoors, so resin materials are required to maintain transparency and color tone in hot and humid environments. and mechanical properties. Therefore, on the basis of considering the transparency of the resin composition, the moisture and heat resistance of the resin composition should also be considered emphatically.

In recent years, among the various applications described above, particular attention has been paid to flame retardancy in the event of a fire. There is a need for a resin composition having high flame retardancy in addition to the above characteristics. As a method for making aromatic polycarbonate resins or their alloys flame retardant, it has been proposed to add halides such as bromide and chloride, and phosphides as flame retardants to obtain flame retardant aromatic polycarbonate resin compositions, It is also used in office automation equipment and home appliances that require high flame retardancy. On the other hand, flame-retardant aromatic polycarbonate resin compositions replacing these flame retardants have also been developed and applied to the above-mentioned articles. The purpose of changing these flame retardants is to suppress the generation of corrosive gases during molding and improve the recycling rate of products.

Examples of flame retardants that can be substituted for the above-mentioned flame retardants include siloxane compounds. In recent years, intensive research has been conducted on flame-retardant resin compositions in which siloxane compounds are incorporated into aromatic polycarbonate resins, and various proposals have been made.

For example, the method of blending perfluoroalkanesulfonic acid alkali (earth) metal salt and organosiloxane with alkoxy, vinyl and phenyl groups in polycarbonate resin (Japanese Patent Laid-Open Publication No. 6-306265) and in Polycarbonate resin blended with perfluoroalkane sulfonic acid alkali metal salt or alkaline earth metal salt and organopolysiloxane containing organosiloxy (olganokysilyl) group bonded to silicon atom through divalent hydrocarbon group method (JP-A-6-336547) and the like.

It has also been proposed to mix specific petroleum-based heavy oils or asphalts and siloxane compounds into resin components (Japanese Patent Laid-Open No. 9-169914) and to mix non-siloxane resins containing aromatic rings containing compounds of the general formula R ₂ The method of a siloxane resin having a unit represented by SiO _1.0 and a unit represented by RSiO _1.5 , and a weight average molecular weight of more than 10,000 and less than 270,000 (JP-A-10-139964).

However, the polycarbonate resin composition of the above-mentioned method cannot be said to be excellent in transparency, heat-and-moisture resistance, and flame retardancy. For example, when the thickness is thinner, dripping occurs, which does not meet the V-0 requirements of UL Standard 94. Moreover, the dispersion of siloxane is insufficient, and the product is cloudy, or after the heat treatment, the siloxane is agglomerated, so that the transparency of the material after the heat treatment is reduced, and so on.

In addition, in the aromatic polycarbonate disclosed in JP-A-60-38419, a resin composition composed of an organic alkali metal salt and poly(methylhydrogensiloxane) is specifically described. However, the resin itself of this resin composition is cloudy, and poor dispersion defects such as peeling occur on the surface of the product, and the dyeability of the resin composition that reflects the luster, tone, clarity and uniformity of the product cannot be said. is good.

Polytetrafluoroethylene with fibril-forming ability is now used more as an anti-dripping agent. However, when polytetrafluoroethylene is blended into aromatic polycarbonate resin, the two are incompatible, so the transparency of the product is reduced.

The problem to be solved by the invention

A first object of the present invention is to provide a flame-retardant aromatic polycarbonate composition substantially free of halides, preferably phosphides. More specifically, it is to provide a flame-retardant aromatic polycarbonate resin composition. The characters and logos printed by laser printing on the molded product of the composition are clear, and the resin has excellent anti-dripping properties when burning, and has excellent dyeability when colored. Also very good.

A second object of the present invention is to provide a transparent flame-retardant aromatic polycarbonate resin composition which is excellent in transparency and heat-and-moisture resistance, and which is also excellent in resin dripping resistance during combustion.

A third object of the present invention is to provide a flame-retardant aromatic polycarbonate composition excellent in tracking resistance (tracking resistance) and antistatic property, and also excellent in resin dripping resistance during combustion.

means of solving problems

In order to achieve the above object, the inventors of the present invention have repeatedly carried out intensive research, and as a result, it has been found that by blending a specific amount of a specific siloxane compound into an aromatic polycarbonate resin, good dyeability during coloring can be obtained, and the printed characters during laser printing can be obtained. Combination with a flame-retardant aromatic polycarbonate resin composition that has clear markings and resin dripping resistance when burning, and can further obtain a flame-retardant aromatic polycarbonate resin composition that is excellent in transparency and heat and humidity resistance material, thus completing the present invention.

That is, according to the present invention, a kind of flame-retardant aromatic polycarbonate resin composition can be provided, and this composition comprises:

(1) 100 parts by weight of resin components, including 50-100% by weight of aromatic polycarbonate resin (A-1 component), 0-50% by weight of styrene-based resin (A-2 component) and aromatic polyester resin ( A-3 component) 0 to 50% by weight,

(2) 0.1 to 10 parts by weight of at least one siloxane compound (B) per 100 parts by weight of the resin component, the siloxane compound is a siloxane compound containing Si-H groups and aryl groups in the molecule , wherein: ① the Si-H group content (Si-H amount) is 0.1 to 1.2 mol/100g, ② the aryl group content ratio (aryl group amount) represented by the following general formula (1) is 10 to 70% by weight, (In the formula (1), X each independently represents an OH group and a monovalent organic residue with a carbon number of 1 to 20. n represents an integer of 0 to 5. And, in the general formula (1), when n is 2 or more , you can choose different X.)

The flame-retardant aromatic carbonate composition of the present invention will be specifically described below. First, the resin component (component A) constituting the composition and the siloxane compound (component B) of the flame retardant will be described in order.

In the resin component (component A) of the resin composition of the present invention, the aromatic polycarbonate resin used as the component A-1 is not only a conventional polyphenol and a carbonate precursor produced by interfacial polycondensation or melt transesterification In addition to the aromatic polycarbonate resin obtained by the reaction, it can also be an aromatic polycarbonate resin obtained by polymerizing a carbonate prepolymer by a solid-phase transesterification method, or by polymerizing a cyclic carbonate compound by a ring-opening polymerization method. The obtained aromatic polycarbonate resin.

Representative examples of dihydric phenols used here include hydroquinone, resorcinol, 4,4'-dihydroxydiphenylbiphenyl, bis(4-hydroxyphenyl)methane, bis{(4-hydroxy- 3,5-Dimethyl)phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2, 2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis{(4-hydroxy- 3,5-Dimethyl)phenyl}propane, 2,2-bis{(3-isopropyl-4-hydroxy)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl ) phenyl} propane, 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis-(4- hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4 -isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)fluorene, 9, 9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, α,α′-bis(4-hydroxyphenyl-o-diisopropylbenzene, α,α′-bis(4-hydroxybenzene base)-m-dicumene, α,α′-bis(4-hydroxyphenyl)-p-dicumene, 1,3-bis(4-hydroxyphenyl)5,7-dimethyl Adamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenyl Ketones, 4,4'-dihydroxydiphenyl ethers, 4,4'-dihydroxydiphenyl esters, etc. These dihydric phenols may be used alone or in combination of two or more.

Among them, it is preferred to use bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2- Bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydroxyphenyl )-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis{(4-hydroxy-3-methyl ) phenyl}fluorene and a homopolymer or copolymer of at least one bisphenol selected from the group consisting of α,α′-bis(4-hydroxyphenyl)-m-dicumene. Particular preference is given to using homopolymers of bisphenol A as well as 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis{(4- Copolymers of hydroxy-3-methyl)phenyl}propane or α,α'-bis(4-hydroxyphenyl)-m-dicumene.

Carbonyl halides (carbonyl balaid), carbonates or haloformic acid esters (Haroholme-to) can be used as precursors of carbonates, specifically phosgene, diphenyl carbonate or dihalogenated dihydric phenols. Formate and more. Among them, phosgene or diphenyl carbonate is advantageous for industrialization.

When the above-mentioned dihydric phenol and carbonate precursor are reacted to prepare polycarbonate resin by interfacial polycondensation method or melt transesterification method, catalysts, chain terminators, antioxidants for dihydric phenol, etc. can also be used as needed. Moreover, the polycarbonate resin can also be a branched polycarbonate resin copolymerized with a trifunctional or more polyfunctional aromatic compound, or a bifunctional carboxylic acid copolymerized with an aromatic or aliphatic (including alicyclic) polyester polycarbonate, a copolycarbonate resin copolymerized with bifunctional alcohols (including alicyclic), and a polyester polycarbonate copolymerized with the bifunctional carboxylic acid and bifunctional alcohol at the same time. A mixture of two or more of the above polycarbonate resins may also be used.

The multi-functionality aromatic compounds with more than three functions include phloroglucinol, phylloglucol, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris (4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl) base)-4-methylphenol, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, etc. (4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, benzene Tetraacids, benzophenone tetracarboxylic acids and their chlorides, etc. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferably used, particularly preferably 1, 1,1-tris(4-hydroxyphenyl)ethane.

When a polyfunctional compound that forms a branched polycarbonate resin is contained, the ratio thereof is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol%, based on the total amount of aromatic polycarbonate. Especially when the melt transesterification method is used, branched structures may be formed as a side reaction, and the amount of these branched structures is preferably 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, in the total amount of the aromatic polycarbonate, Especially preferably 0.01 to 0.8 mol%. This ratio can be calculated by ¹ H-NMR measurement.

The interfacial polycondensation reaction is usually a reaction between dihydric phenol and phosgene, and it is made to react in the presence of an acid binder and an organic solvent. As the acid binder, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide or amine compounds such as pyridine can be used. As the organic solvent, halogenated hydrocarbons such as dichloromethane and chlorobenzene can be used. At the same time, in order to promote the reaction, catalysts such as triethylammonium, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide and other tertiary amines, quaternary ammonium compounds, and quaternary phosphonium compounds can also be used. In this case, the reaction temperature is generally preferably 0 to 40°C, the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or higher.

(式中，A为氢原子或碳数为1～9的直链或支链烷基或苯基取代烷基，r为1～5，优选1～3的整数。)In interfacial polycondensation reactions, chain terminators are usually used. Monofunctional phenols can be used as chain terminators. Generally, monofunctional phenols are used as chain terminators to adjust the molecular weight. Generally, phenol or lower alcohol-substituted phenols are used as monofunctional phenols, and the monofunctional phenols can be represented by the following general formula (5).

(In the formula, A is a hydrogen atom or a linear or branched alkyl group or a phenyl-substituted alkyl group with a carbon number of 1 to 9, and r is an integer of 1 to 5, preferably 1 to 3.)

Specific examples of the aforementioned monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Other monofunctional phenols can be represented by phenols containing long-chain alkyl or aliphatic polyester groups as substituents, or by benzoic acid chlorides, or by long-chain alkyl carboxylic acid chlorides. Among them, phenols having long-chain alkyl groups represented by the following general formulas (6) and (7) as substituents are preferably used. (In the formula, X is -R-CO-O- or -RO-CO-, R represents a single bond or a divalent aliphatic hydrocarbon group with a carbon number of 1 to 10, preferably 1 to 5, n represents 10 to 50 integer.)

Substituted phenols of general formula (6), preferably n is 10 to 30, particularly preferably 10 to 26, and specific examples include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol Alkylphenols, eicosylphenols, docosylphenols and triacylphenols, etc.

Substituted phenols of general formula (7), preferably X is -R-CO-O-, R is a compound of a single bond, n is 10 to 30, preferably 10 to 26 substituted phenols, specific examples include decyl hydroxybenzoic acid Esters, Lauryl Hydroxybenzoate, Myristyl Hydroxybenzoate, Cetyl Hydroxybenzoate, Eicosyl Hydroxybenzoate, Behenyl Hydroxybenzoate and Hydroxybenzoin triacyl ester and so on. At the same time, the chain terminators may be used alone or in combination of two or more.

The melt transesterification reaction is usually the transesterification reaction of dihydric phenol and carbonate. In the presence of inert gas, dihydric phenol and carbonate are heated and mixed, and the resulting alcohol or phenol is distilled off. The reaction temperature varies with the boiling point of the formed alcohol or phenol, and the general range is 120-350°C. In the later stage of the reaction, reduce the pressure of the reaction system to about 1.33×10 ³ ~13.3Pa, so that the formed alcohol or phenol can be easily distilled off. The reaction time is usually about 1 to 4 hours.

Carbonates include carbonates such as aryl groups having 6 to 10 carbon atoms, aralkyl groups or alkyl groups having 1 to 4 carbon atoms which may be substituted. Specific examples include diphenyl carbonate, bis(chlorophenyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate or dibutyl carbonate Among them, diphenyl carbonate is preferable.

In order to increase the polymerization rate, a polymerization catalyst can also be used. As the polymerization catalyst, specifically, alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt and potassium salt of dihydric phenol, calcium hydroxide, barium hydroxide, hydrogen Alkaline earth metal compounds such as magnesium chloride, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, triethylamine, alkoxides of alkali metals and alkaline earth metals, alkali metals Common esterification with organic acid salts of alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, etc. Catalysts used in reactions and transesterification reactions. A single catalyst may be used alone, or two or more catalysts may be used in combination. The amount of these polymerization catalysts used is preferably in the range of 1×10 ^-8 to 1×10 ^-3 equivalents, more preferably in the range of 1×10 ^-7 to 5×10 ^-4 equivalents, with respect to 1 mole of the dihydric phenol raw material.

In this polymerization reaction, in order to reduce the phenolic end groups, such as bis(chlorophenyl)carbonate, bis(bromophenyl)carbonate, bis(nitrophenyl)carbonate, etc. Esters, bis(phenylphenyl)carbonate, chlorophenylphenylcarbonate, bromophenylphenylcarbonate, nitrophenylphenylcarbonate, phenylphenylcarbonate, methoxycarbonylphenyl Compounds such as phenyl carbonate and ethoxycarbonylphenyl phenyl carbonate. Among them, preferably use 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate and 2-ethoxycarbonylphenyl phenyl carbonate, particularly preferably use 2-methoxycarbonylphenyl phenyl carbonate.

In this polymerization, it is preferred to use a deactivator which neutralizes the activity of the catalyst. Specific examples of the deactivator include benzenesulfonic acid, p-toluenesulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, p-toluene Methyl sulfonate, p-ethyl toluenesulfonate, p-butyl toluenesulfonate, p-octyl toluenesulfonate, p-phenyl toluenesulfonate and other benzenesulfonate esters; also trifluoromethanesulfonic acid, naphthalenesulfonate acid, sulfonated polystyrene, methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonate-2-phenyl-2-propyl ester, dodecylbenzenesulfonate-2-phenyl- 2-Butyl ester, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, dodecane Tetrabutylphosphonium phenylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate , Lauryl Ammonium Methyl Sulfate, Lauryl Ammonium Ethyl Sulfate, Lauryl Methyl Ammonium Methyl Sulfate, Lauryl Dimethyl Ammonium Tetradecyl Sulfate, Tetradecane Dimethyl ammonium methyl sulfate, tetramethyl ammonium hexyl sulfate, decyl trimethyl ammonium hexadecyl sulfate, tetrabutyl ammonium dodecyl benzyl sulfate, tetraethyl ammonium dodecyl sulfate Compounds such as alkyl benzyl sulfate and tetramethylammonium dodecyl benzyl sulfate, but not limited to this range. Two or more of the above compounds may be used in combination.

Preference is given to using phosphonium or ammonium salts among the deactivators. For 1 mole of residual catalyst, the amount of deactivator is preferably 0.5 to 50 molar ratio, and for polycarbonate resin after polymerization, the amount of deactivator is 0.01 to 500ppm, more preferably 0.01 to 300ppm, especially preferably 0.01 ~100ppm.

The molecular weight of the polycarbonate resin is not particularly limited. However, when the viscosity-average molecular weight is lower than 10,000, the high-temperature characteristics of the resin decrease, and when it exceeds 50,000, the moldability of the resin decreases, so it is preferable that the viscosity-average molecular weight of the polycarbonate resin is 10,000-50,000, more preferably 14,000-30,000 , More preferably 14,000 to 24,000. In addition, two or more polycarbonate resins may be mixed and used, and of course polycarbonate resins having a viscosity-average molecular weight other than the above-mentioned range may be mixed.

It is particularly preferable to mix with a polycarbonate resin having a viscosity average molecular weight exceeding 50,000. Since such a mixture has good anti-dripping performance, the effects of the present invention can be more effectively obtained. More preferably, a mixture with a polycarbonate resin having a viscosity average molecular weight of 80,000 or more is used, and a mixture with a polycarbonate resin having a viscosity average molecular weight of 100,000 or more is more preferably used. That is, it is preferable to use a polycarbonate resin mixture that clearly has a two-peak distribution when measured by a method such as GPC (gel permeation chromatography).

Said viscosity-average molecular weight in the present invention, at first polycarbonate resin 0.7g is dissolved in the dichloromethane 100ml at 20 ℃ to prepare a solution. Test with an Ostwald viscometer and obtain the specific viscosity by the following formula,

Specific viscosity (η _SP )=(tt ₀ )/t ₀

[t ₀ : the number of seconds for methylene chloride to drop, t: the number of seconds for the sample solution to drop] Substituting the obtained specific viscosity into the following formula, the viscosity-average molecular weight M was obtained.

η _SP /c=[η]+0.45×[η] ² c (where [η]: limit viscosity)

[η]=1.23×10 ^-4 M ^0.83

c=0.7

The aromatic polycarbonate of component A-1 of the present invention is the above-mentioned aromatic polycarbonate resin, and is a resin substantially free of halogen atoms. The so-called substantially free of halogen atoms means that the molecule does not contain halogen-substituted dihydric phenols, etc., and does not refer to the trace solvent (halogenated hydrocarbon) and carbonate precursors remaining in the above-mentioned aromatic polycarbonate preparation process.

The aromatic polycarbonate resin of the component A-1 of the present invention, more preferably, has an acid index range of -0.5 to 5.0 (mg equivalent acid/10 kg PC) of the aromatic polycarbonate resin (PC). When the acid index is in the range of -0.5-5.0 (mg equivalent acid/10kgPC), the siloxane compound (component B) of the present invention can effectively function and easily exhibit arc tracking resistance, antistatic properties and Excellent resin drip resistance. An aromatic polycarbonate resin having an acid index in the range of 0.0 to 3.0 (mg equivalent acid/10 kg PC) is more preferable. If the acid index is less than -0.5 (mg equivalent acid/10 kgPC), the aromatic polycarbonate resin itself has a high basicity and the thermal stability of the composition decreases. If it is greater than 5.0 (mg equivalent acid/10kgPC), the free acid or phenolic end group in the aromatic polycarbonate resin is combined with the Si-H group in the siloxane compound (component B), and the arc tracking resistance and antistatic properties are lowered, and it is difficult for the resin to exhibit anti-dripping properties when burned.

The acid index mentioned here refers to the amount of acid or alkali contained in every 10kg polycarbonate resin (represented by 10kgPC), which is to add methanol 3ml in 100ml of dichloromethane, then add polycarbonate resin sample 10.0g in Dissolve at 20°C to make a solution, add C ₁₅ H ₁₇ CN ₄ -C ₁₆ H ₁₈ CIN ₃ S·nH ₂ O 1ml to the solution as an indicator, and titrate with 0.01mol/l sodium methoxide (CH ₃ ONa), The acid index was obtained by substituting the titration amount when the sample was added and the titration amount when the sample was not added into the following calculation formula.

V=N×k×(X-Y)×10000/W

V: acid index (mg equivalent acid/10kgPC)

N: mol/l of sodium methoxide ( _CH3ONa )

K: Coefficient of 0.01mol/l CH ₃ ONa

X: Titration when adding polycarbonate resin sample (ml)

Y: Titration without adding polycarbonate resin sample (ml)

W: Sample amount (g)

Aromatic polycarbonate resins with an acid index of -0.5 to 5.0 (mg equivalent acid/10kgPC), when preparing aromatic polycarbonate resins by interfacial polycondensation, sometimes remove triethylamine, etc. used to promote the reaction As a catalyst, hydrochloric acid is used, but in order to neutralize the acid components caused by hydrochloric acid, alkali must be added, and the acid index can be controlled at -0.5 to 5.0 (mg Equivalent acid/10kgPC) range. In addition, in the preparation process of the aromatic polycarbonate resin of the interfacial polycondensation method without using a catalyst, in order to neutralize the alkali component produced by the acid binder such as sodium hydroxide, an appropriate acid component should be added, and the acid component can be properly controlled. The amount of ingredients added or the method of strengthening the purification process such as water washing can control the acid value within the range of -0.5 to 5.0 (mg equivalent acid/10kgPC).

In the resin composition of the present invention, the styrene-based resin of A-2 component that can be used as the resin component (component A) is polymerized from styrene monomer or, if necessary, formed from styrene monomer and other vinyl that can be copolymerized with it. A styrene-based resin obtained by copolymerization of one or more selected from monomers and rubbery polymers.

The styrenic monomers used in the aforementioned styrenic resin components include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, di Styrene derivatives such as methylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, etc., especially styrene, these monomers can be used alone or in combination of two or more monomers .

Other vinyl monomers that can be copolymerized with the aforementioned styrene monomers include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; methyl acrylate, ethyl acrylate, etc. Alkyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, dodecyl acrylate, etc.; methyl Aryl methacrylates such as phenyl acrylate and benzyl methacrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, methacrylic acid Alkyl methacrylates such as hexyl ester, 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, etc.; glycidyl methacrylate Epoxy-containing methacrylates; maleic anhydride imide monomers such as maleic anhydride imide, N-methylmaleic anhydride imide, N-phenylmaleic anhydride imide, etc.; Acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, itaconic acid and other α, β-unsaturated carboxylic acids and their anhydrides, etc.

Rubbery polymers that can be copolymerized with the aforementioned styrene-based monomers include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, acrylonitrile-butadiene copolymers Diene-based copolymers such as copolymers of alkyl acrylate or alkyl methacrylate and butadiene, butadiene-isoprene copolymers, random copolymers and block copolymers of ethylene-propylene Copolymers of ethylene and α-olefins such as random copolymers and block copolymers of ethylene and butene, ethylene and unsaturated carboxylic acids such as ethylene and methacrylate copolymers and ethylene and butyl acrylate copolymers Copolymers of esters, copolymers of ethylene and aliphatic vinyl such as ethylene-vinyl acetate copolymers, terpolymers of ethylene, propylene and non-conjugated dienes such as ethylene-propylene-hexadiene copolymers, polyacrylic acid butyl Acrylic rubbers such as esters, and composite rubbers with polyorganosiloxane rubber components and polyalkyl(meth)acrylate rubber components intertwined and inseparable structures (hereinafter referred to as IPN rubbers), etc.

Specific examples of the styrene resin (component A-2) include polystyrene, styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene-styrene copolymer (hydrogenated SBS ), hydrogenated styrene-isoprene-styrene copolymer (SEPS), high-impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-benzene Ethylene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin), propylene Resins such as nitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene-propylene-based rubber-styrene copolymer (AES resin), styrene-IPN type rubber copolymer, and mixtures thereof. These polystyrene resins may be highly stereospecific polystyrenes produced by using catalysts such as metallocene catalysts during their production, and may be styrene-based resins having high stereospecificity. In addition, polymers and copolymers with narrow molecular weight distributions, block copolymers, high stereospecific polymers and copolymers obtained by methods such as anionic living polymerization and radical living polymerization may also be used. Among them, polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin) are preferable , acrylonitrile-butadiene-styrene copolymer (ABS resin), most preferably ABS resin. Two or more types of styrene-based resins may be used in combination.

The so-called ABS resin refers to a thermoplastic graft copolymer of a vinyl cyanide compound and an aromatic vinyl compound grafted on a diene rubber component, and a mixture of a vinyl cyanide compound and an aromatic vinyl compound copolymer. The diene-based rubber component forming the ABS resin can use rubbers such as polybutadiene, polyisoprene, and styrene-butadiene copolymers with a glass transition temperature of 10° C. or less. In 100% by weight of the ABS resin, two The proportion of the ethylenic rubber component used is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight. The vinyl cyanide compound grafted on the diene rubber component includes the above-mentioned compounds, and acrylonitrile is particularly preferably used. As the aromatic vinyl compound grafted on the diene rubber component, the aforementioned compounds can be used in the same way, and styrene and α-methylstyrene are preferably used. The ratio of the grafted component to the diene rubber component is preferably 95 to 20% by weight, particularly preferably 50 to 90% by weight, in 100% by weight of the ABS resin component. For 100% by weight of the total amount of cyanide (sian) vinyl compound and aromatic vinyl compound, the amount of cyanide vinyl compound is preferably 5 to 50% by weight, and the amount of aromatic vinyl compound is preferably 95% by weight. ~50% by weight. Among the components partially grafted onto the diene rubber component, methyl methacrylate, ethyl acrylate, maleic anhydride, N-substituted maleic anhydride imide, and the like may be mixed and used. The content ratio of such compounds is preferably 15% by weight or less in the ABS resin component. Various known additives such as initiators, chain transfer agents, and emulsifiers can be used in the reaction as needed.

In the ABS resin, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.15 to 1.5 μm, particularly preferably 0.2 to 1 μm in terms of weight average particle diameter. The distribution of rubber particle diameters may be a single distribution or a multimodal distribution having two or more peaks, and rubber components having both particle diameter distributions may be used. In terms of morphology, it may be a structure in which the rubber particles form a homogeneous phase, or may be a sea-island structure (Salami structure) formed by including a closed phase (Oculo-d phase) around the rubber particles.

It is well known that ABS resin contains a vinyl cyanide compound and an aromatic vinyl compound that are not grafted onto the diene rubber component. The ABS resin of the present invention may contain free polymer components generated during polymerization. The molecular weight of the copolymer formed from the free vinyl cyanide compound and the aromatic vinyl compound is preferably 0.2 to 1.0, more preferably 0.25 to 0.5 in terms of reduced viscosity (dl/g).

For the diene rubber component, the ratio of the grafted vinyl cyanide compound and aromatic vinyl compound is preferably 20 to 200% by weight, more preferably 20 to 70% by weight.

The ABS resin can be prepared by any method of bulk polymerization, suspension polymerization, or emulsion polymerization, and the copolymerization method can also be one-step copolymerization or multi-step copolymerization. Furthermore, it is also possible to use a blended resin obtained by blending a vinyl compound copolymer obtained by copolymerizing an aromatic vinyl compound and a vinyl cyanide compound obtained by another copolymerization route with the ABS resin obtained by the above method.

In the resin composition of the present invention, the aromatic polyester resin of component A-3 that can be used as the resin component (component A) is composed of aromatic dicarboxylic acid or its reactive derivative and dihydric alcohol or its ester derivative It is a polymer or copolymer obtained by polycondensation reaction of the main component.

The aromatic dicarboxylic acid mentioned here can use terephthalic acid, isophthalic acid, phthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-dicarboxylic acid, Phenyldicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 4,4'-biphenylmalonic acid, 4,4'-biphenylsulfonated dicarboxylic acid, 4,4'- Biphenylisopropylidene dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracenyl dicarboxylic acid, 2,6-anthracenyl dicarboxylic acid Aromatic dicarboxylic acids such as carboxylic acid, 4,4'-p-triphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, especially terephthalic acid or 2,6-naphthyl dicarboxylic acid are preferably used acid.

Aromatic dicarboxylic acids may be used in combination of two or more. If the amount is small, you can also combine the dicarboxylic acid with one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and cyclohexanedicarboxylic acid. Cyclic dicarboxylic acids and the like are used in combination.

The glycols of the aromatic polyester component of the present invention include ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, pentylene glycol, hexamethylene glycol, decanediol, 2-methyl -1,3-propanediol, diethylene glycol, triethylene glycol and other aliphatic diols, 1,4-cyclohexanedimethanol and other aliphatic diols, etc., 2,2-linked (β-hydroxyethoxy Aromatic ring-containing diols such as phenyl)propane, etc., and mixtures thereof. If the amount is small, long-chain diols with a molecular weight of 400 to 6,000, that is, long-chain diols that copolymerize more than one kind of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc., can also be used. chain diols.

The aromatic polyester of the present invention can also be branched by introducing a small amount of branching agent. The kind of the branching agent is not limited, and trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, pentaerythritol and the like can be used.

Specific examples of the aromatic polyester resin (component A-3) include polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate (PBT), poly Hexamethylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2-bis(phenoxy)ethane-4 , 4′-dicarboxylates and so on. In addition, copolyesters such as polyethylene isophthalate/terephthalate and polybutylene terephthalate, and mixtures thereof can also be used. In order to obtain a comprehensive performance of better thermal performance and mechanical performance, polyethylene terephthalate and polyethylene naphthalate which use ethylene glycol as the glycol are preferred. In 100% by weight of the aromatic polyester resin, the amount of polyethylene terephthalate and polyethylene naphthalate used is preferably 50% by weight or more. In particular, the amount of polyethylene terephthalate used is preferably 50% by weight or more. In addition, when the overall performance of processability and mechanical properties is required, it is preferred to use polybutylene terephthalate and polybutylene naphthalate with butanediol as the glycol, and by weight ratio, The usage range of polybutylene terephthalate/polyethylene terephthalate is preferably 2-10.

The terminal group structure of the obtained aromatic polyester resin is not particularly limited, and the ratios of hydroxyl groups and carboxyl groups in the terminal groups may be approximately the same, or one of the terminal groups may be more. For these end groups, it is also possible to cap by reacting with reactive compounds.

Regarding the preparation method of these aromatic polyester resins, in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., the dicarboxylic acid and the aforementioned dihydric alcohol components can be polymerized while heating according to the usual method, and the by-product water , lower alcohols or glycols are discharged out of the reaction system to prepare aromatic polyester resins. Examples of germanium-containing polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenoxides, etc. Specific examples include germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. .

In this process, compounds such as manganese, zinc, calcium, and magnesium used in the transesterification reaction of the known pre-condensation stage can also be used in combination. After the transesterification reaction is completed, the catalyst can also be activated by phosphoric acid or phosphorous acid Inactivation for polycondensation.

The molecular weight of the aromatic polyester resin is not particularly limited, and the intrinsic viscosity measured at 35° C. with o-chlorophenol as a solvent is 0.4-1.2, preferably 0.6-1.15.

Regarding the aromatic polycarbonate resin (A-component) and styrene-based resin (A-2 component) and/or aromatic polyester resin (A-3 component) in the aromatic polycarbonate resin composition (A) of the present invention ), the compounding ratio of the aromatic polycarbonate resin is 100 to 50% by weight, preferably 99.5 to 50 wt%, styrene resin and/or aromatic polyester resin is 0 to 50 wt%, preferably 0.5 to 50 wt%. The mixing ratio of the aromatic polycarbonate resin (A-1) is less than 50% by weight, that is, the mixing ratio of the styrene-based resin (A-2) and/or the aromatic polyester resin (A-3) is more than 50% by weight %, the flame retardancy of the resin composition is not enough, so it is not suitable for use.

In the resin composition of the present invention, the siloxane compound (component B) used as a flame retardant is a siloxane compound having a specific Si—H bond. That is, at least one or more siloxane compounds (B) selected from siloxane compounds containing Si-H groups and aryl groups in the molecule, wherein ① the content of Si-H groups (Si-H amount) is 0.1 to 1.2 mol/100g, ②The content ratio (aryl group amount) of the aryl group represented by the following general formula (1) is 10 to 70% by weight, (In the formula (1), X each independently represents an OH group and a monovalent organic residue with a carbon number of 1 to 20. n represents an integer of 0 to 5. In the general formula (1), when n is 2 or more, A different X can be chosen.).

(式(2)和式(3)中，Z¹～Z³表示各自独立氢原子、碳数为1～20的一价有机残基和下述通式(4)所示的化合物。α1～α3是各自独立的，分别表示0或1。m1表示0或1以上的整数。式(3)中，当m1为2以上时，重复单元可以选取各不相同的多种重复单元)，(式(4)中，Z⁴～Z⁸各自独立表示氢原子、碳数为1～20的一价有机残留机。α4～α8是各自独立的，分别表示0或1。m2表示0或1以上的整数。式(4)中，当m2为2以上时的重复单元可以选取各不相同的多种重复单元。)It is preferable to select at least one or more siloxane compounds from siloxane compounds containing at least one structural unit represented by the following general formulas (2) and (3) as a Si—H bond-containing unit.

(In formula (2) and formula (3), Z ¹ to Z ³ represent independent hydrogen atoms, monovalent organic residues with carbon numbers of 1 to 20, and compounds represented by the following general formula (4). α1 to α3 is independent of each other and represents 0 or 1 respectively. m1 represents an integer above 0 or 1. In formula (3), when m1 is more than 2, the repeating unit can be selected from a variety of different repeating units), (In the formula (4), Z ⁴ to Z ⁸ each independently represent a hydrogen atom and a monovalent organic residual machine with a carbon number of 1 to 20. α4 to α8 are independently independent and represent 0 or 1 respectively. m2 represents 0 or 1 Above integer. In formula (4), when m2 is more than 2, the repeating unit can choose different multiple repeating units.)

When M is a monofunctional siloxane unit, D is a difunctional siloxane unit, and T is a trifunctional siloxane unit, a siloxane compound composed of MD units or MDT units is preferable.

Z ¹ to Z ⁸ of the structural units represented by the above general formulas (2), (3) and (4), and the monovalent organic residues with carbon numbers of 1 to 20 in X of the general formula (1) include methyl , ethyl, propyl, butyl, hexyl, decyl and other alkyl groups, cyclohexyl and other cycloalkyl groups, vinyl and allyl and other alkenyl groups, phenyl and tolyl and other aryl and aralkyl groups, and These groups may also contain various functional groups such as epoxy groups, carboxyl groups, carboxylic acid anhydride groups, amino groups, and mercapto groups. It preferably contains an alkyl group, alkenyl group, or aryl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group, vinyl group, or phenyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, or a propyl group.

In the siloxane compound containing at least one or more structural units of the structural units represented by the aforementioned general formulas (2) and (3), when there are multiple siloxane bond repeating units, random copolymerization, embedded Any form of interrupted copolymerization or trapezoidal copolymerization (Te-Pa-do co-repetition).

In this invention, in the said siloxane compound which is (B) component, the amount of Si-H in a siloxane compound must exist in the range of 0.1-1.2 mol/100g. The amount of Si-H is in the range of 0.1-1.2mol/100g, and it is easy to form a siloxane structure during combustion. More preferable is a siloxane compound having a Si-H content in the range of 0.2 to 1.0 mol/100 g. When the amount of Si-H is less than 0.1mol/100g, it is difficult to form a siloxane structure, and when it is higher than 1.2mol/100g, the thermal stability of the composition is reduced, and when the heat and humidity treatment is performed, the excess Si-H groups and air The moisture in the mold reacts to generate hydrogen gas, bubbles are generated, and the molded product becomes cloudy. The siloxane structure mentioned here refers to the network structure formed by the reaction of siloxane compounds or the reaction of resin and siloxane.

The amount of Si-H mentioned here means the number of moles of the Si-H structure contained in 100g of siloxane compounds. It can be obtained by measuring the volume of hydrogen gas generated per unit weight of the siloxane compound by an alkali decomposition method. For example, when 1 g of the siloxane compound generates 122 ml of hydrogen gas at 25° C., the amount of Si—H is determined to be 0.5 mol/100 g by the following calculation formula.

122×273/(273+25)÷22400×1000.5

On the other hand, in the resin component (component A), especially the resin composition in which a siloxane compound is mixed with the component A-1, in order to suppress the cloudiness of the molded product or the decrease in transparency caused by the wet heat treatment, silicone The dispersion state of the oxane is very important. This is because if the siloxane is dispersed unevenly, the resin composition itself becomes cloudy, and the surface of the product peels off, or the siloxane compound migrates during the heat-and-moisture treatment, resulting in uneven dispersion and reduced transparency. It is difficult to obtain a molded product with good transparency. Important factors for determining this dispersed state are the amount of aryl groups in the siloxane compound and the average degree of polymerization. Especially in a transparent resin composition, the average degree of polymerization is particularly important.

From this point of view, as the silicone compound of the present invention, the amount of aryl groups therein must be in the range of 10 to 70% by weight. More preferred are siloxane compounds having an aryl group content in the range of 15 to 60% by weight. If the amount of aryl groups is less than 10% by weight, the siloxane compound will be unevenly distributed, resulting in poor dispersion, and it will be difficult to obtain a molded article with good transparency. If the amount of aryl groups exceeds 70% by weight, the molecular rigidity of the siloxane compound itself will increase, and the distribution will still be uneven, resulting in poor dispersion, and it will be difficult to obtain a molded product with good transparency.

The amount of aryl groups referred to here refers to the content ratio of aryl groups represented by the following general formula (1) in the siloxane compound, and can be obtained from the following calculation formula.

Amount of aryl group=[A/M]×100 (% by weight) A and M in the above calculation formula represent the following numerical values, respectively.

A = total molecular weight of all aryl moieties represented by the general formula (1) contained in one siloxane compound molecule

M = molecular weight of the siloxane compound

The silicone compound (component B) of the present invention preferably has a refractive index range of 1.40 to 1.60 at 25°C, more preferably a refractive index range of 1.42 to 1.59, and most preferably a silicone compound of a refractive index range of 1.44 to 1.59. . When the refractive index is within the above range, the siloxane compound is finely dispersed in the aromatic polycarbonate, and a resin composition with less cloudiness and better dyeability can be obtained.

As the siloxane compound (B component) of the present invention, the volatilization amount measured by the heating loss method at 105° C./3 hours is preferably 18% or less. A silicone compound having a volatile amount of 10% or less is more preferable. If the volatilization amount exceeds 18%, the volatilization amount of the siloxane compound increases during the preparation of the resin composition, which may cause trouble in the molding of resin composition molded articles.

As the siloxane compound containing the structural unit represented by the above general formula, as long as the above conditions are satisfied, the structure of the compound may be a linear structure or a branched structure. Various compounds having Si-H groups at any one or more positions of side chains, terminals, and branch points in the molecular structure can also be used.

Generally, the structure of siloxane compound is formed by arbitrarily combining the following four siloxane units. M unit: (CH ₃ ) ₃ SiO _1/2 , H(CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ )SiO _1/2 , (CH ₃ ) ₂ (CH ₂ ＝CH)SiO _1/2 , (CH ₃ ) ₂ (C ₆ H ₆ )SiO _1/2 , (CH ₃ )(C ₆ H ₅ )(CH ₂ =CH)SiO _1/2 and other monofunctional siloxane units D units: (CH ₃ ) ₂ SiO, H(CH ₃ )SiO, H ₂ SiO, H(C ₆ H ₅ )SiO, (CH ₃ )(CH ₂ =CH)SiO, (C ₆ H ₅ ) ₂ SiO and other bifunctional silicon Oxane unit T unit: (CH ₃ )SiO _3/2 , (C ₃ H ₇ )SiO _3/2 , HSiO _3/2 , (CH ₂ =CH)SiO _3/2 , (C ₆ H ₅ )SiO _{3 /2} etc. trifunctional siloxane unit Q unit: tetrafunctional siloxane unit represented by _SiO2

The specific structural formulas of the siloxane compound structure used in the present invention are D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _p , M _m D _n Q _q , M _m T _p Q _q , M _m D _n T _p Q _q , D _n T _p , D _n Q _q , D _n T _p Q _q . Among them, the preferred structure of the siloxane compound is M _m D _n , M _m T _p , M _m D _n T _p , M _m D _n Q _q , and the more preferred structure is M _m D _n or M _m D _n T _p .

(the lower angular coefficients m, n, p, and q in the above-mentioned structural formula are integers representing the degree of polymerization of each siloxane, and the sum of the lower angular coefficients in each structural formula is the average degree of polymerization of the siloxane compound. Among the present invention , the range of the average degree of polymerization is preferably 3 to 150, more preferably in the range of 3 to 80, and further preferably in the range of 3 to 60. When any one of m, n, p, and q is a value of 2 or more, it can be considered that A siloxane unit with a lower angle coefficient is a siloxane unit connected with two or more different hydrogen atoms and organic residues.)

The above-mentioned siloxane compounds may be used alone or in combination of two or more.

The siloxane compound having such a Si-H bond can be prepared by a method known per se. For example, according to the structure of the desired siloxane compound, put the corresponding organochlorosilanes together for hydrolysis, and remove the by-product hydrochloric acid and low boiling point components to obtain the target product. In addition, silicon (oxygen) oils, cyclic siloxanes, and alkoxysilanes containing Si-H bonds, aryl groups represented by general formula (1) and other organic residues in the molecule are used as initial raw materials, and hydrochloric acid is used to , Sulfuric acid, methanesulfonic acid and other acid catalysts, sometimes in order to carry out hydrolysis, but also add water, make it polymerize, remove the acid catalyst and low boiling point components used in the same way, the desired siloxane compound can be obtained.

The siloxane compound of the aforementioned (B) component is compounded in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 7 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the resin component (Component A).

In the resin composition of the present invention, at least one compound selected from radical generators, organic alkali metal salts, and organic alkaline earth metal salts may be blended as the (C) component. By blending the component (C), the flame retardancy can be further improved, and especially the anti-dripping property can be improved. In the present invention, the component (C) is called a flame retardancy improver. (C) The compounding quantity of component (C) is 0.001-0.3 weight part with respect to 100 weight part of resin components (A component), Preferably it is 0.005-0.3 weight part, More preferably, it is 0.005-0.2 weight part share.

The free radical generating agent used as the component (C) of the present invention includes organic peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxy) 3-hexyne, dicumyl peroxide, etc. Substances, 2,3-dimethyl-2,3-diphenylbutane (dicumyl) and the like, these peroxides are available on the market, manufactured by NOF Co., Ltd. under the trade name ofヘキシン 25B, パクミル D, Nofuma BC, etc. are easy to obtain. The most ideal is that little free radicals are generated during melting and kneading, and free radicals with certain stability can be effectively generated during combustion, so 2,3-dimethyl-2,3-diphenylbutadiene is more preferred alkanes (dicumyl) as free radical generators.

As the alkali metal salt and alkaline earth metal salt used in the component (C) of the present invention, various metal salts conventionally used for flame retardancy of polycarbonate resins, especially organic sulfonic acid metal salts or sulfate ester metal salts can be used. These metal salts may be used not only alone but also in combination of two or more. Examples of alkali metals in the present invention include lithium, sodium, potassium, rubidium, and cesium, and alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium, and lithium, sodium, and potassium are particularly preferable.

The aforementioned organic sulfonic acid metal salts include alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, alkaline earth metal salts of aromatic sulfonic acids, and the like. Preferred examples of the aliphatic sulfonic acid metal salts include alkanesulfonic acid alkali (earth) metal salts, sulfonic acid alkali (earth) metal salts in which part of the alkyl group of the alkanesulfonic acid alkali (earth) metal salts is substituted by fluorine atoms. ) metal salts, and alkali (earth) metal salts of perfluoroalkanesulfonic acid, these alkali (earth) metal salts can be used alone, or two or more can be used simultaneously. (The term "alkali (earth) metal salt" here is used in the sense of including alkali metal salts and alkaline earth metal salts.)

Preferable examples of alkanesulfonic acid used in the alkali (earth) metal salt of alkanesulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid , octanesulfonic acid, etc. These sulfonic acids may be used singly or in combination of two or more. There are also metal salts in which part of the alkyl group is replaced by fluorine atoms.

Preferred examples of perfluoroalkanesulfonic acids include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexylsulfonic acid, and perfluoroalkanesulfonic acid. Heptansulfonic acid, perfluorooctylsulfonic acid, etc., particularly preferably perfluoroalkanesulfonic acid having 1 to 8 carbon atoms. These perfluoroalkanesulfonic acids may be used alone or in combination of two or more.

The alkali (earth) metal salt of alkanesulfonic acid is preferably sodium salt of ethanesulfonate, and the alkali (earth) metal salt of perfluoroalkanesulfonate is preferably potassium perfluorobutanesulfonate.

Aromatic sulfonic acids used in aromatic sulfonic acid alkali (earth) metal salts are monomeric or polymeric aromatic sulfide sulfonic acids, aromatic carboxylic acids and ester sulfonic acids, monomeric or polymeric Aromatic ether sulfonic acid, aromatic sulfonic acid ester sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfone sulfonic acid, aromatic ketone sulfonic acid, polycyclic sulfonic acid At least one acid selected from the group consisting of aromatic sulfoxide sulfonic acid, and condensate of aromatic sulfonic acid linked by methylene bonds. These aromatic sulfonic acids may be used singly or in combination of two or more kinds.

Monomer or polymeric sulfonic acid alkali (earth) metal salts of aromatic sulfides are reported in JP-A No. 50-98539, such as diphenylsulfide-4,4'-disulfone Disodium disulfide, dipotassium diphenylsulfide-4,4'-disulfonate, etc.

Sulfonic acid alkali (earth) metal salts of aromatic carboxylic acids and esters are reported in JP-A-50-98540, for example: potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate , Polysodium polyethylene terephthalate polysulfonate and so on.

The sulfonic acid alkali (earth) metal salt of monomeric or polymeric aromatic ethers has been reported in JP-A No. 50-98542, for example: 1-methoxynaphthalene-4-calcium sulfonate, Disodium 4-dodecylphenylene ether disulfonate, polysodium poly(2,6-dimethylphenyleneoxy)polysulfonate, polysodium poly(1,3-phenyleneoxy)polysulfonate , poly(1,4-phenyleneoxy)polysodium polysulfonate, poly(2,6-diphenylphenyleneoxy)polypotassium polysulfonate, poly(2-fluoro-6-butylphenylene Oxygen) lithium polysulfonate and the like.

Alkali (earth) metal sulfonic acid salts of aromatic sulfonic acid esters are reported in JP-A-50-98544, for example, potassium sulfonate of benzenesulfonic acid ester, etc.

Monomer or polymeric aromatic sulfonic acid alkali (earth) metal salts have been reported in JP-A No. 50-98546, for example: sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, p - Dipotassium benzenesulfonate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonate and the like.

Monomer or polymeric aromatic sulfone sulfonic acid alkali (earth) metal salts have been reported in JP-A No. 52-54746, for example: diphenylsulfone-3-sodium sulfonate, diphenylsulfone- 3-Potassium sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, dipotassium diphenylsulfone-3,4'-disulfonate, etc.

Sulfonic acid alkali (earth) metal salts of aromatic ketones have been reported in JP-A-50-98547, for example: α, α, α-trifluoroacetophenone-4-sodium sulfonate, benzophenone-3 , 3′-dipotassium disulfonate, etc.

Polycyclic sulfonic acid alkali (earth) metal salts are reported in JP-A-50-116542, such as thiophene-2,5-disodium disulfonate, thiophene-2,5-dipotassium disulfonate, thiophene - Calcium 2,5-disulfonate, sodium benzothiophene sulfonate, etc.

Sulfonic acid alkali (earth) metal salts of aromatic sulfoxides are reported in JP-A-52-54745, for example: potassium diphenylsulfoxide-4-sulfonate, etc.

The aromatic sulfonic acid base (earth) metal salt condensate condensed with methylene bonds includes formaldehyde condensate of sodium naphthalene sulfonate, formaldehyde condensate of sodium anthracene sulfonate, etc.

Alkali (earth) metal salts of sulfates have alkali (earth) metal salts of sulfates of monobasic and/or polyhydric alcohols, and the sulfates of monobasic and/or polyhydric alcohols include methyl sulfate and ethyl sulfate , lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, dodecanoic acid monoglyceride sulfate, Sulfate ester of monoglyceryl palmitate, sulfate ester of monoglyceride stearate, etc. As the alkali (earth) metal salts of these sulfate esters, alkali (earth) metal salts of lauryl sulfate are preferably used.

Other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides, such as o-sulfonyl benzimide, N-(p-toluenesulfonyl)-p-toluenesulfonyl imide, Alkali (earth) metal salts of N-(N'-benzylaminocarbonyl)-p-aminobenzenesulfonimide and N-(phenylcarboxy)-p-aminobenzenesulfonimide, etc.

Among the alkali (earth) metal salts listed above, more preferable components are alkali (earth) metal salts of aromatic sulfonic acids, alkali (earth) metal salts of perfluoroalkane sulfonic acids, and the like.

As mentioned above, the flame retardant resin composition of the present invention is mainly a resin component (A component) of an aromatic polycarbonate resin, and a specific silicone compound (B component) is blended in a specific ratio in this resin component. ) obtained as a flame retardant.

That is, according to the present invention, a flame-retardant aromatic polycarbonate resin composition can be provided, which is obtained by using an aromatic polycarbonate resin as a main resin component (A component), a silicone compound (B component ) and a flame retardant improver (C) component as needed, which does not contain halogen flame retardants such as bromide as a flame retardant excellent in burning drip prevention (hereinafter sometimes referred to as "halogen-free"). In the resin composition of the present invention, other resins, fillers, or various additives may also be blended in the polycarbonate resin composition in the same way as the usual compounding. Details of other resins, fillers, and additives will be described later.

Representative preferred embodiments of the present invention are described below. This preferred embodiment is a halogen-free flame-retardant aromatic polycarbonate resin composition, which is a resin composition capable of obtaining a transparent molded article having good heat-and-moisture resistance.

Conventional halogen-free flame-retardant polycarbonate resin compositions are obtained by simple combination, and practical value in terms of transparency and heat-and-moisture resistance has not yet been seen.

(式(1)中，X各自独立表示OH基、碳数为1～20的一价的有机残基。n表示0～5的整数。通式(1)中，当n为2以上时，可以选取互不相同的X。)。According to the present invention, a transparent flame-retardant aromatic polycarbonate resin composition containing 0.1 to 10 parts by weight of a siloxane compound in 100 parts by weight of an aromatic polycarbonate resin (component A-1) can be provided. (B component). The siloxane compound is selected from siloxane compounds containing Si-H groups and aryl groups in the molecule, wherein ① the content of Si-H groups (Si-H amount) is 0.1 to 1.2 mol/100g, ② the following general formula ( 1) The aryl group content (aryl group amount) shown in 1) is 10 to 70% by weight,

(In the formula (1), X each independently represents an OH group and a monovalent organic residue with a carbon number of 1 to 20. n represents an integer of 0 to 5. In the general formula (1), when n is 2 or more, It is possible to choose mutually different X.).

In the following description, this transparent flame-retardant aromatic polycarbonate resin composition is simply referred to as "transparent resin composition". In this specification, both the transparent composition and the opaque composition are collectively referred to as "resin composition" or "flame-retardant resin composition".

The aforementioned transparent resin composition of the present invention uses aromatic polycarbonate resin (A-1 component) as the resin component, and in 100 parts by weight of the resin component, 0.1 to 10 parts by weight of a siloxane compound is blended, although the composition is simple. , but it is a halogen-free resin composition with flame retardancy, transparency and heat and humidity resistance.

The resin component of the transparent resin composition is basically composed of aromatic polycarbonate resin (A-1 component), but as long as it does not affect the transparency, it may also contain a small amount of other resins (A-2 component, A-3 component) components or other resins). In the transparent resin composition, as the siloxane compound of the B component, it is preferable to use the compound whose structure, average degree of polymerization, Si-H amount, aryl group amount and refractive index are as described above, and it is also preferable to use the aforementioned compound. Preferred example. The average polymerization range is preferably 3-80, preferably 3-60, more preferably 4-40, and particularly preferably 4-20.

The compounding ratio range of the aromatic polycarbonate resin (component A-1) and the siloxane compound (component B) may be the same as the ratio range of the resin component (component A) and the siloxane compound (component B) described above. The aforementioned flame retardancy improver (component C) may also be used in combination with the aforementioned transparent resin composition. The flame retardancy improver (component C), as mentioned above, can exhibit the effect of improving flame retardancy by adding a small amount, so in most cases, there is no problem of lowering transparency due to the addition of the flame retardancy improver .

In the transparent resin composition of the present invention, other resins and fillers may be blended as long as the transparency is not impaired. Most other resins and fillers will affect transparency, so this should be fully considered when choosing their type and amount.

With the transparent resin composition of the present invention, a molded article excellent in transparency and heat-and-moisture resistance can be obtained. As will be described later, the haze of a molded product having a thickness of 2 mm is 0.3 to 20%, preferably 0.5 to 15%. At the same _time , as described later, the difference _ΔH (H ₁ -H _O ) is 0.01 to 10%, preferably 0.02 to 7%. In this way, the transparent resin composition of the present invention is suitable for preparing molded articles with good transparency and heat and humidity resistance.

Since the transparent resin composition of the present invention is also a halogen-free flame-retardant composition, it can also be effectively used in various molded articles requiring transparency and heat-and-moisture resistance.

Since the transparent resin composition of the present invention is excellent in transparency, by blending pigments and dyes, it is possible to obtain molded articles with good transparency and bright colors.

The A component, B component, and C component in the resin composition of this invention were demonstrated above. Fillers, other resins and various additives that can be blended in this composition are further described below.

In the resin composition of this invention, you may further mix|blend a filler as (D)component. By blending the filler (D) component, the mechanical strength of the molded article can be improved. As the filler, a filler compounded to improve the strength of a resin molded product can be used. The compounding quantity of D component is 1-100 weight part with respect to 100 weight part of resin components (A component), Preferably it is 3-80 weight part, More preferably, it is 5-60 weight part.

Component D includes talc, mica, white clay, wollastonite, calcium carbonate, glass fiber, glass microspheres, hollow glass microspheres, flexible fibers, glass flakes, carbon fibers, carbon flakes, carbon microbeads, flexible carbon fibers, Metal flakes, metal fibers, metal-coated glass fibers, metal-coated carbon fibers, metal-coated glass flakes, silica, ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, Materials such as graphite, conductive carbon black and various whiskers.

In the resin composition of the present invention, a thermoplastic resin other than component A may be blended in order to improve the physical and mechanical properties, chemical properties, and electrical properties of the molded article. The blending amount of the thermoplastic resin varies depending on the type and purpose, but usually the blending amount of other thermoplastic resins is 1 to 30 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the resin component (component A).

Other thermoplastic resins include general-purpose plastics represented by polyethylene resins, polypropylene resins, and polyalkylmethacrylate resins, polyphenylene ether resins, polyoxymethylene resins, polyamide resins, and cyclic polyolefin resins. Resin, polyarylate resin (amorphous polyarylate, liquid crystal polyarylate) and other engineering plastics, polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, polyphenylene sulfide Ether and the like are thermoplastic resins called super engineering plastics. In addition, thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.

In the resin composition of the present invention, in order to impart various functions to the product and improve its properties, a small amount of its original additives can also be compounded. As long as the purpose of the present invention is not affected, these additives can be compounded in general amounts.

These additives include flame retardants other than component B (phosphate esters, red phosphorus, metal hydroxides, etc.), anti-dripping agents (fluorine-containing polymers that can form fibrils, etc.), heat stabilizers, and ultraviolet absorbers. , light stabilizer, release agent, lubricant, slip agent (PTFE particles, etc.), colorant (pigments, dyes such as carbon black, titanium oxide, etc.), light diffusing agent (acrylate cross-linked particles, silicon cross-linked particles, polar Thin glass flakes, calcium carbonate particles, etc.), fluorescent whitening agents, luminous pigments, fluorescent dyes, antistatic agents, fluidity improvers, crystal nucleating agents, inorganic or organic antibacterial agents, photocatalyst antifouling agents (oxidation Titanium particles, zinc oxide particles, etc.), impact resistance modifiers represented by graft rubber, infrared absorbers and photochromic agents.

In the resin composition of the present invention, the aromatic polycarbonate resin accounts for 50 to 100% by weight as the resin component. Therefore, in order to improve thermal stability, oxidation resistance, light stability (ultraviolet stability) and mold releasability of the resin composition, additives useful for improving these properties are used in the aromatic polycarbonate resin. The details of these additives are described below.

In the resin composition of the present invention, a phosphorus-containing stabilizer can be blended as a heat stabilizer, and any one of a phosphoric acid ester compound, a phosphite compound, and a phosphonate compound can be used as the phosphorus-containing stabilizer. stabilizer.

[式中，R⁸表示氢原子或碳数为1～20的烷基、碳数为6～20的芳基或烷芳基、碳数为7～30的芳烷基或它们的卤、烷硫基(烷基的碳数为1～30)或羟基取代基，可以选择3个R⁸是相同的或不同的，还可以选择由二元酚类衍生的环状结构。]Various phosphoric acid ester compounds can be used as the heat stabilizer, and specific examples include phosphoric acid ester compounds represented by the general formula (8).

[wherein, R ⁸ represents a hydrogen atom or an alkyl group with 1 to 20 carbons, an aryl or alkaryl group with 6 to 20 carbons, an aralkyl group with 7 to 30 carbons, or their halogen, alkane As a thio group (the carbon number of the alkyl group is 1-30) or a hydroxyl substituent, three R ⁸ can be selected to be the same or different, and a ring structure derived from a dihydric phenol can also be selected. ]

[式中，R⁹、R¹⁰分别表示氢原子、碳数为1～20的烷基、碳数为6～20的芳基或烷芳基、碳数为7～30的芳烷基、碳数为4～20的环烷基、碳数为15～25的2-(4-羟基苯基)丙基取代芳基。环烷基和芳基可以选择被烷基取代的，或者不被烷基取代的基团。]There are also phosphoric acid ester compounds represented by the general formula (9).

[In the formula, R ⁹ and R ¹⁰ respectively represent a hydrogen atom, an alkyl group with 1 to 20 carbons, an aryl or alkaryl group with 6 to 20 carbons, an aralkyl group with 7 to 30 carbons, a carbon A cycloalkyl group with 4 to 20 carbon atoms and a 2-(4-hydroxyphenyl)propyl group with 15 to 25 carbon atoms replace the aryl group. Cycloalkyl and aryl groups can be optionally substituted by or not substituted by an alkyl group. ]

[式中，R¹¹、R¹²是碳数为12～25的烷基。R¹¹和R¹²可以是相同的，也可以是不同的]Phosphate ester compounds represented by the general formula (10) are also included.

[In the formula, R ¹¹ and R ¹² are alkyl groups having 12 to 25 carbon atoms. ^R11 and ^R12 may be the same or different]

[式中，Ar¹、Ar²表示碳数为6～20的芳基或烷芳基、或碳数为15～25的2-(4-羟苯基)丙基取代芳基，可以选择四个Ar¹是相同的，或不同的。也可以选择两个Ar²是相同的，或不同的。]Phosphonate compounds used as heat stabilizers include phosphonate compounds represented by the following general formula (11) and phosphonate compounds represented by the following general formula (12).

[In the formula, Ar ¹ and Ar ² represent aryl or alkaryl with 6 to 20 carbons, or 2-(4-hydroxyphenyl) propyl substituted aryl with 15 to 25 carbons, and four Ar ¹ are the same, or different. It is also possible to choose that the two Ar ² are the same, or different. ]

Preferred examples of phosphoric acid ester compounds corresponding to the above general formula (8) include diphenyl isooctyl phosphate, 2,2'-methylene bis(4,6-di-tert-butylphenyl)octyl phosphorous acid ester, diphenyl mono(tridecyl) phosphate, phenyl diisodecyl phosphate, phenyl di(tridecyl) phosphate, etc.

Preferred examples of the phosphoric acid ester compound corresponding to the above general formula (9) include distearyl pentaerythritol diphosphate, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphate, bis(2,6-di tert-butyl-4-methylphenyl) pentaerythritol diphosphate, phenyl bisphenol A pentaerythritol diphosphate, dicyclohexyl pentaerythritol diphosphate, etc., preferred examples are distearyl pentaerythritol diphosphate, bis(2 , 4-di-tert-butylphenyl)pentaerythritol diphosphate, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate and the like. These phosphate ester compounds may be used singly or in combination of two or more.

Preferable examples of the phosphoric acid ester compound corresponding to the above general formula (10) include 4,4'-isopropylidene diphenol tetrakis(tridecyl)ate and the like.

Concrete preferred examples corresponding to the phosphonate compound of the above-mentioned general formula (11) have four (2,4-diisopropylphenyl)-4,4'-biphenylene diphosphonate, four (2, 4-Di-n-butylphenyl)-4,4'-biphenylene diphosphonate, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonic acid Esters, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonate, tetrakis(2,4-di-tert-butylphenyl)-3,3'- Biphenyl diphosphonate, tetrakis(2,6-diisopropylphenyl)-4,4'-biphenylene diphosphonate, tetrakis(2,6-di-n-butylphenyl)- 4,4'-biphenylene diphosphonate, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonate, tetrakis(2,6-di-tert Butylphenyl)-4,3'-biphenylene diphosphonate, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonate, and the like. Among them, tetrakis(di-tert-butylphenyl)-biphenylene diphosphonate is preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonate is more preferred. The tetrakis (2,4-di-tert-butylphenyl)-biphenylene diphosphonate is preferably a mixture of two or more, and a specific example has tetrakis (2,4-di-tert-butylphenyl)-4, 4'-biphenylene diphosphonate (E2-1 component), tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonate (E2-2 component ) and tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonate (E2-3 component), these phosphonates can be used one or two at the same time more than one species. Mixtures of these three phosphonates are preferably used. The mixing ratio when using three kinds of phosphonate mixtures, the preferred range of E2-1 component, E2-2 component and E2-3 component by weight ratio is 100:37～64:4～14, and the more preferred range is 100: 40～60:5～11.

Specific preferred examples of phosphonate compounds corresponding to the above general formula (12) are bis(2,4-diisopropylphenyl)-4-phenyl-phenylphosphonate, bis(2,4-di n-Butylphenyl)-3-phenyl-phenylphosphonate, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonate, bis(2,4-di tert-butylphenyl)-3-phenyl-phenylphosphonate, bis(2,6-diisopropylphenyl)-4-phenyl-phenylphosphonate, bis(2,6-di n-Butylphenyl)-3-phenyl-phenylphosphonate, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonate, bis(2,6-di tert-butylphenyl)-3-phenyl-phenylphosphonate and the like, preferably bis(2-tert-butylphenyl)-phenyl-phenylphosphonate, more preferably bis(2,4-di-tert Butylphenyl)-phenyl-phenylphosphonate. The bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonate is preferably a mixture of two or more, and specific examples include (2,4-di-tert-butylphenyl)-4-phenyl phenyl-phenylphosphonate and bis(2,4-di-tert-butylphenyl) 3-phenyl-phenylphosphonate. These phosphonate esters can be used alone or in combination. Preference is given to using mixtures of these two phosphonates. When the mixture of the two phosphonates is used, the mixing ratio preferably ranges from 5:1 to 4, more preferably 5:2 to 3 in terms of weight ratio.

Phosphate ester compounds used as heat stabilizers include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate ester, diphenyl mono-n-biphenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc., preferably trimethyl phosphate.

More preferable compounds of the above-mentioned phosphorus-containing heat stabilizers include compounds represented by the following general formulas (13) and (14). (In formula (13), R ¹³ and R ¹⁴ are each independently, and represent an alkyl group, cycloalkyl group, aryl group or aralkyl group with a carbon number of 1 to 12.) (In formula (14), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² and R ²³ are each independently representing a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group , aryl, or aralkyl, R ¹⁹ represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, R ²⁰ represents a hydrogen atom or a methyl group.)

In the general formula (13), R ¹³ and R ¹⁴ are preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound of general formula (13) can enumerate three (dimethylphenyl) phosphite, three (diethylphenyl) phosphite, three (diisopropylphenyl) phosphite, three ( Di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, etc. Particular preference is given to tris(2,4-di-tert-butylphenyl)phosphite.

(式(15)中，R¹⁵、R¹⁶、R¹⁷和R¹⁸分别表示氢原子、碳原子数为1～12的烷基、氯代烷基、芳基或芳烷基、R¹⁹表示氢原子或碳原子数为1～4的烷基，R²⁰表示氢原子或甲基。)(式(16)中，R²¹、R²²和R²³分别表示氢原子、碳原子数为1～12的烷基、环烷基、芳基或芳烷基。)The compound represented by the general formula (14) can be produced by a known method. For example: react the bisphenol compound represented by the following general formula (15) with phosphorus trichloride to obtain the corresponding chlorophosphate, and then react it with the phenol represented by the following general formula (16).

(In formula (15), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ represent a hydrogen atom, an alkyl group, chloroalkyl group, aryl group or aralkyl group with 1 to 12 carbon atoms, R ¹⁹ represents a hydrogen atom atom or an alkyl group with 1 to 4 carbon atoms, and ^R20 represents a hydrogen atom or a methyl group.) (In formula (16), R ²¹ , R ²² and R ²³ respectively represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.)

Specific examples of the compound represented by the above general formula (15) include 2,2'-methylene bisphenol, 2,2'-methylenebis(4-methylphenol), 2,2'-methylene Bis(6-methylphenol), 2,2'-methylenebis(4,6-dimethylphenol), 2,2'-ethylenebisphenol, 2,2'-ethylenebis( 4-methylphenol), 2,2'-isopropylidene bisphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebisphenol (4-Ethyl-6 tert-butylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6 -cyclohexylphenol), 2,2′-dihydroxy-3,3′-bis(α-methylcyclohexyl)-5,5′-dimethylphenylmethane, 2,2′-methylenebis (6-α-methyl-benzyl-p-cresol), 2,2′-ethylene-bis(4,6-di-tert-butylphenol) and 2,2′-butylene-bis(4 -methyl-6-tert-butylphenol) and the like, and can be preferably used.

Compounds shown in general formula (15) more preferably use 2,2'-methylene bis(4-methyl-6 tert-butylphenol), 2,2'-methylene bis(4-ethyl-6 tert-butylphenol), 2,2'-methylene bis(4,6-di-tert-butylphenol), 2,2'-ethylene-bis(4,6-di-tert-butylphenol) and 2 , 2'-butylene-bis(4-methyl-6-tert-butylphenol).

Specific examples of the compound represented by the general formula (16) include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol , 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4 -Dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol and 2,6-di-tert-butyl-4-sec Butylphenol and the like are preferably used. Specific examples of the compound represented by the general formula (16) are more preferably compounds having two or more alkyl substituents.

Examples of antioxidants that can be blended in the resin composition of the present invention include phenolic antioxidants. By using phenolic antioxidants, it is possible to control discoloration when exposed to heat conditions, and it also has a certain effect on improving flame retardancy. Various phenols can be used as the phenolic antioxidant.

Specific examples of the phenolic antioxidant include vitamin E, n-octadecyl-β-(4'-hydroxyl-3', 5'-di-tert-butylphenyl (fur)) propionate, 2- tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-tert-butyl-4-(N , N-di-methylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 2,2'-methylenebis(4-methyl-6 -tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol) , 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol) 2,2'-ethylene-bis(4,6-di-tert-butylphenol), 2,2'-butylene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylene Bis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6 -Hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis[2-tert-butyl-4-methyl-6-(3-tert-butyl-5- Methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-s-methylphenyl)propionyloxy base]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4′-thiobis(6 tert-butyl-m -cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3 , 5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis( 2,6-di-tert-butylphenol), 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5 -Triazine, N,N'-hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid amide), N,N'-bis[3-(3,5-di-tert-butyl Base-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl- 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanate, tris(3,5- Di-tert-butyl-4-hydroxybenzyl) isocyanate, 1,3,5-tri(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanate, 1,3,5-tri-2 [3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanate, tetrakis[methylene-3-(3′,5′-di-tert-butyl-4-hydroxy Phenyl)propionate]methane and the like can be preferably used.

It is more preferred to use n-octadecyl-β-(4'-hydroxyl-3', 5'-di-tert-butylphenyl (fur)) propionate, 2-tert-butyl-6-(3'- tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 3,9-bis{2-[3-(3 tert-butyl-4-hydroxy-5- Methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane and tetrakis[methylene-3 -(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane, more preferably n-octadecyl-β-(4'-hydroxy-3',5'-di-tert Butylphenyl (feel) propionate.

Antioxidant A sulfur-containing antioxidant can also be used. Especially when the resin combination is used for rotational molding and compression molding, it is more suitable to use sulfur-containing antioxidants. Specific examples of the sulfur-containing antioxidant include didodecanyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, ditetradecyl Dioctadecyl-3,3'-thiodipropionate, Dioctadecyl-3,3'-thiodipropionate, Dodecyl octadecyl-3,3'-thiodipropionate ester, pentaerythritol tetrakis(β-dodecylthiopropionate) ester, bis[2-methyl-4-(3-dodecylthiopropionyloxy)-5 tert-butylphenyl ]sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1'-thiobis(2-naphthol) and the like. Pentaerythritol tetrakis(β-dodecylthiopropionate) ester and the like may be more preferable.

The phosphorus-containing heat stabilizers, phenolic antioxidants, and sulfur-containing antioxidants listed above may be used alone, or two or more additives may be used in combination. It is more preferable to use a phosphorus-containing heat stabilizer, and it is particularly preferable to use a phosphorus-containing heat stabilizer containing a compound represented by the above-mentioned general formula (13).

The compounding ratio of these stabilizers in the composition is 0.0001 to 1 part by weight of the phosphorus-containing stabilizer, phenolic antioxidant, or sulfur-containing antioxidant per 100 parts by weight of the resin component (component A). It is appropriate. More preferably, the compounding ratio is 0.0005-0.5 weight part per 100 weight part of resin components, More preferably, it is 0.001-0.2 weight part.

In the resin composition of the present invention, a release agent may also be blended as needed. In the present invention, component B has flame retardancy, so even if a mold release agent that generally tends to adversely affect flame retardancy is used, good flame retardancy can still be obtained. As the release agent, a known release agent can be used. For example: saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax or 1-chain olefin polymer. Polyethylene wax or 1 -chain olefin polymer), siloxane compound (siloxane other than component B of the present invention. For example: linear or cyclic polydimethylsiloxane oil and polymethylphenyl silicone oil, etc. Also Acid-modified silicones modified with functional group-containing compounds, etc.), fluorides (fluorine oil typified by polyfluoroalkyl ethers, etc.), paraffin, beeswax (yellow wax), and the like can be used. Among them, saturated fatty acid esters, linear or cyclic polymethicone oil, polymethylphenyl silicone oil, fluorine oil, and the like are exemplified. The amount of the release agent used is preferably 0.01 to 0.3 parts by weight relative to 100 parts by weight of the resin component (component A).

Ideal release agents are saturated fatty acid esters, for example, monoglycerides such as monoglyceryl stearate, polyglyceryl fatty acid esters such as decaglyceryl decastearate and decaglyceryl tetrastearate, stearic acid polyglycerides, etc. Lower fatty acid esters such as fatty stearyl, higher fatty acid esters such as behenyl sebacate, and erythritol esters such as pentaerythritol tetrastearyl.

Since the composition of the present invention is often used for housings of office automation equipment, it is preferable to contain an ultraviolet absorber. Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecane Oxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-Hydroxy-4-methoxy-5-sulfoxide benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxy Benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium benzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl) A benzophenone-based ultraviolet absorber represented by methane or the like.

As ultraviolet absorbers, there are 2-(2'-hydroxyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxyl-5'tert-butylphenyl)benzotriazole, 2 -(2'-hydroxyl-5'tert-octylphenyl)benzotriazole, 2-(2'-hydroxyl-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2 '-Hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-3'-dodecyl-5'-methylphenyl)benzotriazole , 2-(2'-hydroxyl-3',5'-bis(α,α'-dimethylbenzyl)phenylbenzotriazole, 2-[2'-hydroxyl-3'-(3", 4", 5", 6"-tetraphthalimidomethyl)-5'-methylphenyl]benzotriazole, 2-(2'-hydroxy-3'tert-butyl-5'-methyl Phenyl 1-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,2'-methylene Bis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol, methyl-3-(3-tert-butyl-5- A benzotriazole-based ultraviolet absorber represented by a condensation product of (2H-benzotriazol-2-yl)-4-hydroxyphenylpropionate and polyethylene glycol.

There are also 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, 2-(4,6-bis-(2 , 4-dimethylphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol and other hydroxyphenyl triazine compounds.

In the resin composition of the present invention, a photostabilizer may also be blended. Specific examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentylmethyl- 4-piperidinyl) sebacate, bis(1,2,2,6,6-pentylmethyl-4-piperidinyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl base)-2n-butylmalonate, condensates of 1,2,3,4-butanecarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and tridecanol, Condensate of 1,2,3,4-butanecarboxylic acid and 1,2,2,6,6-pentylmethyl-4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6- Tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentylmethyl-4-piperidinyl)-1 , 2,3,4-butane tetracarboxylate, poly{[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-di Base][(2,2,6,6-tetramethylpiperidinyl)imino]hexamethylene[(2,2,6,6-tetramethylpiperidinyl)imino]}, poly{ [6-Morpholino-s-triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidinyl)imino]hexamethylene[(2,2,6 , 6-tetramethylpiperidinyl) imino]}, 1,2,3,4-butane tetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and β, β, β', β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane)diethanol condensate, N,N'-bis(3 -aminopropyl)ethylenediamine and 2,4-bis[N-butyl-N-(1,2,2,6,6-pentylmethyl-4-piperidinyl)amino]-chloro- Condensates of 1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentylmethyl-4-piperidinol and β, β, β Condensate of ',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane)diethanol, polymethylpropyl-3-hydroxy A hindered amine represented by -[4-(2,2,6,6-tetramethylpiperidinyl]siloxane.

The proportions of the aforementioned ultraviolet absorber and light stabilizer are 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight, per 100 parts of the resin component (component A).

In the resin composition of the present invention, a bluing agent may be added in order to prevent yellowing caused by the ultraviolet absorber. As long as it is a bluing agent generally used for polycarbonate resins, there is no particularly adverse effect. It is generally preferred to use anthraquinone dyes, which are readily available. Concrete bluing agent can enumerate general name soluble violet (SolvenViolet) 13 [CA. , manufactured by Mitsubishi Chemical Co., Ltd., "Day Alekin (Diaregin) Blue G", manufactured by Sumitomo Chemical Industries, Ltd., "Smipulast Biolet (Sumipulast Biolet) B"]; common name It is soluble violet (Solvent Villet) 31 [CA.No.68210: trade name, manufactured by Mitsubishi Chemical Co., Ltd., "Day Alejin Biolet (ダイアレジンバイオレット) D"]; the general name is soluble violet (Solvent Villet) Violet) 33 [CA.No.60725: Trademark name, manufactured by Mitsubishi Chemical Co., Ltd. "Day Alejin (ダイアレジン) Blue-J"]; common name is soluble blue (Solvent Blue) 94 [CA.No.6150 : Trade name, manufactured by Mitsubishi Chemical Co., Ltd. "Day Alejin (ダイアレジン) Blue-N"]; common name is soluble violet (Solvent Violet) 36 [CA.No.68210: Trade name, manufactured by Bayer AG "Mark Rolex Biolet (Macrorex バイオレット) 3R"]; general name Soluble Blue (Solvent Blue) 97 [trade name, manufactured by Bayer Corporation "Macrorex (Macrorex) Blue-RR"] and general name Soluble blue (Solvent Blue) 45 [CA. No. 61110: trade name, "Trazoll (Telazol) Blue-RLS" manufactured by Sundo Co., Ltd.], etc., Macrorex (Macrorex) Blue RR is particularly preferable , Macrolex Biolet (Macrorexバイオレット) B and Trazol (テラゾ一ル) blue-RLS] and other bluing agents.

The anti-dripping performance of the resin composition of the present invention is good, and in order to further improve the performance, a common anti-dripping agent can also be used at the same time. However, the most preferred embodiment of the present invention is a transparent resin composition. In order not to impair the transparency, the compounding amount of the general anti-dripping agent is preferably 0.1 part by weight or less, preferably less than 0.08 part by weight, more preferably less than 0.05 part by weight, based on 100 parts by weight of component A. Examples of the anti-dripping agent include fluorine-containing polymers capable of forming fibrils, and polytetrafluoroethylene (hereinafter referred to as PTFE) is particularly preferable.

PTFE with the ability to form fibrils has a very high molecular weight, and PTFE tends to combine with each other to form fibers under the action of external forces such as shear force. The molecular weight is 1 million to 10 million, preferably 2 million to 9 million, based on the number average molecular weight calculated from the standard specific gravity. As such PTFE resins, not only solid resins but also aqueous dispersion liquid resins can be used. In order to improve the dispersibility of the fibril-forming PTFE in the resin and further obtain excellent flame retardancy and transparency, it is also possible to use a PTFE mixture mixed with other resins. Commercially available blended PTFE includes "Metaburen A3000" (trade name) from Mitsubishi Rayon Co., Ltd., "BLENDEX B449" (trade name) from GE Specialty Chemicals, and the like.

Any method can be used to prepare the resin composition of the present invention. Can use V-type mixer, Hanschel mixer, chemical power equipment, extrusion mixer and other pre-mixing methods to fully mix A component, B component and any other components, and then pass through extrusion granulator and granulate as needed extruder, etc., and then melt kneading with a melt kneader represented by a vented twin-screw extruder, and granulation with a granulator.

Other methods include separately supplying component A, component B and other components to a melt kneader represented by a vented twin-screw extruder, premixing component A and some other components, and then separately The method of supplying the premixed components and the remaining other components to the melt kneader, dilute and mix component B with water or an organic solvent and supply it to the melt kneader, or premix the diluted mixture with other components and supply it to the melt kneader Machine method and so on. In addition, when there is a liquid component among the compounding components, it is necessary to use a liquid injection device or a liquid addition device that feeds the liquid to the melt-kneader.

The resin composition of the present invention is usually produced into various articles by injection molding using pellets to obtain molded articles. In injection molding, not only ordinary cold runner molding method but also hot runner method without shank can be used. In injection molding, not only ordinary molding methods but also gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, injection compression molding, two-color molding, sandwich molding, in-mold cladding molding, and insert molding can be used. Plastic molding, foam molding (including the use of supercritical fluid), rapid heating and cooling mold molding, heat insulation mold molding and in-mold remelting molding, and the combination of these molding methods.

The resin composition of the present invention can also be made into various special-shaped extrusion moldings by extrusion molding, and used in the form of sheets, films, and the like. In the forming of sheets and films, methods such as inflation and casting can be used. It can also be made into a heat shrinkable hose by performing a specific stretching operation. Molded products can also be produced by rotational molding without melting and kneading the resin.

Various surface treatments can be applied to molded articles made of resin compositions. Surface treatments include decorative coatings, hard coatings, water- and oil-repellent coatings, hydrophilic coatings, UV-absorbing coatings, and infrared-absorbing coatings. Coatings, electromagnetic wave absorbing coatings, heating coatings, antistatic coatings, insulating coatings, conductive coatings and metallized coatings ((electro) plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), flame spraying) and so on. It is especially suitable for attaching a transparent conductive layer on a transparent sheet.

The effect of the invention

The flame-retardant aromatic polycarbonate resin composition of the present invention contains a siloxane compound (component B) as a flame retardant, has excellent anti-dripping performance, and has excellent dyeability when colored and printing characters and characters by laser printing. When marking, the clarity of the text and the logo is very good. These characteristics are beyond the reach of conventional flame-retardant aromatic polycarbonate resins, and this resin composition also has high thermal stability during high-temperature melting such as injection molding. Therefore, it is very useful in various industrial fields such as office automation equipment and electronic and electrical equipment.

In particular, according to a preferred aspect of the present invention, a flame-retardant aromatic polycarbonate resin composition excellent in transparency can be obtained. Since this flame-retardant resin composition contains a specific siloxane compound (component B) as a flame retardant, it has anti-dripping properties, transparency, and heat-and-moisture resistance at the same time. The resin composition having these several properties at the same time is not the ordinary polycarbonate resin composition in the past. This kind of resin composition with good transparency can be used as a transparent sheet after being molded, not only as a lighting lampshade, a protective cover for transparent display, but also as a light guide component, a solar cell cover and a substrate, and a lens. , lens group, coupler, touch control panel, resin window, amusement machine parts (front panel of pinball machine, circuit cover, etc.), prism, reflector and other applications. That is to say, it has great application value in various industrial fields such as office automation equipment, electronic and electrical equipment, vehicles, agriculture, fishery and civil engineering.

Example

The following examples further illustrate the present invention, but the present invention should not be limited among the scope of the examples, and the performance evaluation is carried out according to the following items. (1) Material properties (1-I) Drip resistance

The test was carried out according to UL standard 94 using a test piece with a thickness of 1.6 mm prepared according to UL standard. Measure the time for dripping after the first ignition and the second ignition, and evaluate with the shortest time (seconds). (1-II) Dyeability

Divide the square plate molded product with a size of 150mm×150mm and a thickness of 2.0mm into 9 parts, and measure the L value of the nine positions with the color discriminator TCM-1800 of Tokyo Denshoku Industry Co., Ltd., and measure at nine positions Among the L values, the difference (ΔL) is obtained by subtracting the minimum value from the maximum value, and the difference (ΔL) is obtained by observing the appearance of the molded product with the naked eye, and evaluated according to the following criteria.

○: Good. No peeling, glossy, well-toned, even appearance.

X: not good. There is peeling, dullness, poor tone, and uneven appearance. (1-III) Laser printing property

Use the laser printer SL475E manufactured by NEC Corporation to print on a 2.00mm thick test piece made in accordance with the UL standard at a scanning speed of 100mm/s and a character speed of 30μm, and observe with the naked eye at the minimum current value that can be printed The clarity of the blot was evaluated according to the following criteria.

○: Good. The text can be judged to be clear.

X: not good. There are scribbles in the text, etc. (1-IV) Transparency

According to JIS K7105, the transparency of a square molded product with a size of 150 mm × 150 mm and a thickness of 2.0 mm was measured, and the transparency was evaluated using the measured haze value and the color tone of the molded product observed with the naked eye. (1-V) Moisture and heat resistance

The haze value was measured in accordance with the method of JIS K7105 after leaving the rectangular molded product for measurement in 1-IV for 500 hours in an environment of temperature: 65° C. and humidity: 85%. The wet heat resistance was evaluated by the difference (ΔH) between the obtained haze value and the initial haze value and the color tone of the molded article after the wet heat treatment observed with the naked eye. (White turbidity refers to the degree of light transmission confirmed by naked eyes. "Opacity" means that light transmission cannot be seen by naked eyes. The haze is not measured).

[Examples 1 to 25 and Comparative Examples 1 to 18]

The resin compositions listed in Tables 1 to 9 were prepared in the following manner. Instructions are given in the order of numbers in the table below.

Each component is measured according to the ratio listed in Tables 1 to 9, and then to phosphite antioxidant (IRGAFOS168 manufactured by Japan's チバガイギ-company): 0.01 parts by weight; ): 0.01 parts by weight; UV absorber (Chemisorbu 79 manufactured by Chemipro Chemical Industry Co., Ltd.): 0.3 parts by weight;リケマール) SL900): 0.3 parts by weight was measured, uniformly mixed with a drum mixer, and then the mixture was sent to an extruder to prepare a resin composition.

As the extruder, a vented twin-screw extruder (Kobe Steel Works KTX-30) with a screw diameter of φ30 mm was used. Screw structure, there is a first kneading section (consisting of feeding kneading disc × 2, feeding rotor × 1, return rotor × 1 and return kneading disc × 1) before the exhaust position, and a second kneading section after the exhaust position. Two kneading sections (consisting of feed rotor × 1 and return rotor × 2). Extrude strands under the conditions of cylinder temperature and head temperature of 280°C and exhaust port suction pressure of 3,000Pa, cool in a water bath, and then cut strands into granules with a pelletizer to complete the granulation process .

The obtained pellets were dried at 110° C. for 5 hours with a hot air circulation dryer, and then injected into test pieces with an injection molding machine [FANUC T-150D]. Injection molding conditions: barrel temperature: 290°C, mold temperature: 70°C.

The raw materials and the like used for each number in Tables 1 to 9 are as follows. (The number of the raw material also indicates the same content in the description content other than the table). (A) Ingredient (A-1 Ingredient) PC-1: Linear polycarbonate resin (made by phosgene method, aromatic polycarbonate composed of bisphenol A and p-tert-butylphenol as chain terminator) Carbonate resin. The aromatic polycarbonate resin does not use an amine catalyst in the preparation, and in the terminal group of the aromatic polycarbonate resin, the hydroxyl end group ratio is 10 mol%, and the aromatic polycarbonate resin contains 25ppm Phosphonate antioxidant [Clariant (Clariant) Co., Ltd., Sand stabb P-EPQ], viscosity average molecular weight: 22,500) PC-2: branched aromatic polycarbonate resin (Idemitsu Petrochemical Co., Ltd., Taffron (Taflon) IB2500) PC-3: In the presence of dichloromethane, 10% aqueous sodium hydroxide solution, and triethylamine, bisphenol A, chain terminator p-tert-butylphenol and light Gas reaction to prepare polycarbonate resin. In this process, for bisphenol A, using 0.058 molar ratio of p-tert-butylphenol, polycarbonate resin PC-4 with a viscosity-average molecular weight of 15,500 was obtained: in dichloromethane, 10% sodium hydroxide aqueous solution 1. Under the condition of the presence of triethylamine, the polycarbonate resin was prepared by reacting bisphenol A, chain terminator p-tert-butylphenol and phosgene by common method. In this process, a polycarbonate resin having a viscosity average molecular weight of 121,000 was obtained using p-tert-butylphenol in a molar ratio of 0.0004 to bisphenol A. (Component A-2) ABS: Styrene-butadiene-acrylonitrile copolymer (manufactured by Japan A&L (Eiandel) Co., Ltd., Santuck (Santack) UT-61) AS: Styrene-acrylonitrile copolymer ( Manufactured by Asahi Kasei Industry Co., Ltd., Staylak (Staylac-AS767R27) MBS: methyl methacrylate-butadiene-styrene copolymer (manufactured by Zhongyuan Chemical Industry Co., Ltd., Kanae 1ス) B-56) (Component A-3) PET: Polyethylene terephthalate resin (TR-8580 manufactured by Teijin Co., Ltd., intrinsic viscosity: 0.8) PBT: Polybutylene terephthalate Ester resin (TRB-H manufactured by Teijin Co., Ltd., intrinsic viscosity: 1.07) (component B) Synthesis example-1

In a 1L flask equipped with a stirring device, a cooling device and a thermometer, 15.9 g of hexamethyldisiloxane, 147.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 147.3 g of octamethylcyclotetrasiloxane, and 14.5 g of tetrasiloxane and 395.1 g of diphenyldimethoxysilane were added with 25.0 g of concentrated sulfuric acid while stirring. After cooling the temperature in the system to 10° C., 29.7 g of water was dropped into the flask over 30 minutes while stirring. Continue cooling during this process to keep the temperature in the system below 20°C. After the titration, keep the temperature of the system at 10-20°C, continue to stir for 5 hours, add 8.5g of water and 300g of toluene after aging, leave it still after stirring for 30 minutes, remove the separated water layer, and then use 5% sodium sulfate The aqueous solution was washed four times, and it was confirmed that the toluene layer was neutral. This toluene solution was heated under reduced pressure to bring the system temperature to 120° C., toluene and low-boiling components were removed, and insoluble matter was removed by filtration to obtain siloxane compound B-1. Synthesis example-2

538.2 g of water and 120 g of toluene were placed in a 1 L flask equipped with a stirring device, a cooling device, and a thermometer, and cooled to 5°C. Put a mixture of 22.6g of trimethylchlorosilane, 119.6g of methyldichlorosilane and 34.2g of diphenyldichlorosilane into the dropping funnel, and drop the above mixture into the flask while stirring the contents of the flask , dripping time is 2 hours. Continue cooling during this process to keep the temperature in the system below 20°C. After the titration, continue stirring at 20° C. for 4 hours to make it mature, then place it still, remove the separated hydrochloric acid aqueous layer, add 10% sodium carbonate aqueous solution and stir for 5 minutes, place it still, and remove the separated aqueous layer. Thereafter, it was further washed three times with ion-exchanged water, and it was confirmed that the toluene layer was neutral. This toluene solution was heated under reduced pressure to bring the temperature in the system to 120° C., toluene and low-boiling components were removed, and insoluble matter was removed by filtration to obtain siloxane compound B-2. Synthesis example-3

452.8 g of water and 120 g of toluene were charged into the flask, and a mixture of 21.7 g of trimethylchlorosilane, 23.0 g of methyldichlorosilane, 80.0 g of dimethyldichlorosilane and 32.9 g of diphenyldichlorosilane was added dropwise, Other than that, the same operation as in Synthesis Example-2 was carried out to obtain siloxane compound B-3. Synthesis example-4

100.7g of 1,1,3,3-tetramethyldisiloxane, 60.1g of 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane 129.8g, 143.8g of octaphenylcyclotetrasiloxane and 99.1g of phenyltrimethoxysilane, then add 25.0g of concentrated sulfuric acid, drop in water 13.8g, except that, carry out the same operation as Synthesis Example 1- , to obtain the siloxane compound B-4. Synthesis example-5

Fill the flask with 454.9g of water and 140g of toluene, drop 47.3g of dimethylchlorosilane, 34.5g of methyldichlorosilane, 1.4g of dimethyldichlorosilane, 11.3g of diphenyldichlorosilane and phenyl Except for the mixture of 63.5 g of trichlorosilane, the same operation as in Synthesis Example-2 was performed to obtain siloxane compound B-5. Synthesis example-6

26.0 g of hexamethyldisiloxane, 57.7 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 26.1 g of octamethylcyclotetrasiloxane and diphenyldimethylsiloxane were charged into the flask Except having added 456.3 g of oxysilanes, 25.0 g of concentrated sulfuric acid, and dripping water 34.3 g, the operation similar to synthesis example-1 was performed, and the siloxane compound B-6 was obtained. Synthesis example-7

Charge hexamethyldisiloxane 81.2g, 1,3,5,7-tetramethylcyclotetrasiloxane 30.1g, octamethylcyclotetrasiloxane 129.8g and diphenyldimethylsiloxane in the flask Except having added 317.7 g of oxysilanes, 25.0 g of concentrated sulfuric acid, and dripping water 23.9 g, the same operation as Synthesis Example-1 was performed, and the siloxane compound B-7 was obtained. Synthesis example-8

511.3 g of water and 120 g of toluene are charged in the flask, and 14.8 g of dimethyl dichlorosilane, 17.9 g of methyl dichlorosilane, 112.7 g of dimethyl dichlorosilane and 19.7 g of diphenyl dichlorosilane are added dropwise, Except for that, the same operation as in Synthesis Example-2 was performed to obtain siloxane compound B-8. Synthesis example-9

6.7 g of 1,1,3,3-tetramethyldisiloxane, 60.1 g of 1,3,5,7-tetramethylcyclotetrasiloxane and diphenyldimethoxysilane were placed in the flask 533.9 g, except that 40.0 g of concentrated sulfuric acid was added, and 40.2 g of water was dripped, the operation similar to synthesis example-1 was performed, and the siloxane compound B-9 was obtained. B-1: A siloxane compound having a Si-H content of 0.49 mol/100 g, an aryl group content of 50% by weight, and a refractive index of 1.5313 prepared according to Synthesis Example-1. B-2: Prepared according to Synthesis Example-2 Siloxane compound B-3 with a Si-H content of 1.00 mol/100g, an aryl group content of 20% by weight, and a refractive index of 1.4480: the Si-H content obtained according to Synthesis Example-3 is 0.20 mol/100g, Siloxane compound B-4 with an aryl group content of 20% by weight and a refractive index of 1.4502: Si-H content of 0.50 mol/100g, an aryl group content of 30% by weight, and a refractive index of 1.4750 siloxane compound B-5: Siloxane compound B-6 with a Si-H content of 0.80 mol/100 g, an aryl group content of 30 wt %, and a refractive index of 1.4770 obtained according to Synthesis Example-5: according to Siloxane compound B-7 with Si-H content of 0.20 mol/100g, aryl group content of 60% by weight, and refractive index of 1.5583 obtained in Synthesis Example-6: Si-H content obtained in accordance with Synthesis Example-7 Siloxane compound B-8 with 0.10 mol/100g, 40% by weight aryl group, and 1.4970 refractive index: Si-H content of 0.31 mol/100g and 12 aryl group obtained according to Synthesis Example-8 Siloxane compound B-9 with a weight % and a refractive index of 1.4188: a siloxane with a Si-H content of 0.22 mol/100 g, an aryl group content of 67 weight %, and a refractive index of 1.5839 prepared according to Synthesis Example-9 Compound Other (B) Component Synthesis Example-10

97.4 g of hexamethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane 180.4 g and octamethylcyclotetrasiloxane 222.5 g were charged into the flask, and then 25.0 g of concentrated sulfuric acid was added. g, except that water was not dropped, the same operation as in Synthesis Example-1 was carried out to obtain siloxane compound B-10. Synthesis example-11

39.9 g of hexamethyldisiloxane, 14.8 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 200.6 g of octamethylcyclotetrasiloxane and diphenyldimethylsiloxane were charged into the flask. Except having added 300.6 g of oxysilanes, 25.0 g of concentrated sulfuric acid, and dripping water 22.6 g, the operation similar to synthesis example-1 was performed, and the siloxane compound B-11 was obtained. Synthesis example-12

560.6 g of water and 140 g of toluene were placed in the flask, and a mixture of 18.9 g of dimethylchlorosilane, 126.5 g of methyldichlorosilane, and 25.3 g of diphenyldichlorosilane was added dropwise. Other than that, the same operation as in Synthesis Example-2 was carried out to obtain siloxane compound B-12. B-10 (comparison): According to Synthesis Example-10, the Si-H content is 0.60mol/100g, the aryl group content is 0% by weight, and the siloxane compound B-11 (comparison) with a refractive index of 1.3956: according to Synthesis Example-11 produced a siloxane compound having an Si—H content of 0.05 mol/100 g, an aryl group content of 38% by weight, and a refractive index of 1.4915. B-12 (comparison): According to Synthesis Example-12, a siloxane compound having a Si-H content of 1.31 mol/100 g, an aryl group content of 16% by weight, and a refractive index of 1.4419 <shown for each siloxane compound Formula>B-1: M ₂ D ^H ₂₅ D ₂ D ^φ2 _16.5 B-2: M ₂ D ^H ₁₀ D ^φ2 _1.3 B-3: M ₂ D ^H ₂ D _6.2 D ^φ2 _1.3 B-4: M ^H ₃ D ^H ₂ D _3.5 D ^φ2 _1.45 T ^φ ₁ B-5: M ^H ₅ D ^H ₃ D _0.107 D ^φ2 _0.445 T ^φ ₃ B-6: M ₂ D ^H ₆ D _2.2 D ^φ2 _11.67 B-7: M ₂ D ^H ₁ D _3.5 D ^φ2 _2.6 B-8: M ^H ₂ D ^H ₂ D _11.2 D ^φ2 ₁ B-9: M ^H ₂ D ^H ₂₀ D ^φ2 _43.7 B-10: M ₂ D ^H ₅ D ₅ (comparison) B -11: M ₂ D ^H ₁ D ₁₁ D ¹¹ ₅ (comparison) B-12: M ^H ₂ D ^H ₁₁ D ^φ2 ₁ (comparison)

Each symbol in the said schematic formula represents the following siloxane unit, and the lower angle coefficient of each symbol represents the degree of polymerization of each siloxane unit in one molecule. M: (CH ₃ ) ₃ SiO _1/2 M ^H : H(CH ₃ ) ₂ SiO _1/2 D: (CH ₃ ) ₂ SiOD ^H : H(CH ₃ )SiOD ^φ2 : (C ₆ H ₅ ) ₂ SiOT ^φ2 : (C ₆ H ₅ )SiO _3/2 (C) Component C-1: 2,3-dimethyl-2,3-diphenylbutane (commonly known as dicumyl, manufactured by NOF Co., Ltd. , Nofuma (Nofuma one) BC) C-2: Potassium perfluorobutane sulfonate (manufactured by Dainippon Ink Chemical Industry Co., Ltd., Mecca Fake (Megaphak) F-114P) C-3: Diphenyl Potassium Sulfone Sulfonate (UCB (ュシビビ1) made in Japan, KSS)

Table 1 unit Example 1 Example 2 Example 3 Example 4 Example 5 (A) Ingredients PC-1 parts by weight 100 70 80 97 PC-2 " 100 ABS " 30 AS " 20 MBS " 3 (B) Ingredients B-4 " 2 2 2 2 2 droplet generation time After 1 fire Second no drip no drip no drip no drip no drip after 2 fires Second 8 15 6 6 8 Dyeing Sharpness - ○ ○ ○ ○ ○ ΔL - 0.1 0.1 0.1 0.1 0.1 Laser printing clarity - ○ ○ ○ ○ ○ current value A 19.0 19.3 19.5 19.0 19.2 transparency tone - Colorless and transparent Colorless and transparent opaque opaque opaque Haze - 1.1 1.1 - - -

Table 2 unit Example 6 Example 7 Example 8 Example 9 Example 10 (A) Ingredients PC-1 parts by weight 90 90 100 100 100 PET " 10 PBT " 10 (B) Ingredients B-1 " 2 B-2 " 2 B-3 " 2 B-4 " 2 2 droplet generation time After 1 fire Second no drip no drip no drip no drip no drip after 2 fires Second 7 7 10 14 6 Dyeing Sharpness - ○ ○ ○ ○ ○ ΔL - 0.1 0.1 0.1 0.5 0.4 Laser printing clarity - ○ ○ ○ ○ ○ current value A 19.6 19.4 19.2 18.8 19.6 transparency tone - opaque opaque Colorless and transparent Colorless and transparent Colorless and transparent Haze - - - 1.6 1.6 1.6

table 3 unit Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 (A) Ingredients PC-1 parts by weight 100 100 100 100 100 100 (B) Ingredients B-4 " 1 3 5 2 B-5 " 2 1 B-6 " 2 (C) Ingredients C-1 " 0.1 droplet generation time After 1 fire Second no drip no drip no drip no drip no drip no drip after 2 fires Second 11 9 10 15 17 no drip Dyeing Sharpness - ○ ○ ○ ○ ○ ○ ΔL - 0.1 0.1 0.1 0.1 0.1 0.1 Laser printing clarity - ○ ○ ○ ○ ○ ○ current value A 19.0 19.2 19.5 19.0 18.5 19.6 transparency tone - Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Haze - 1.3 0.8 1.1 1.2 1.3 1.2

Table 4 unit Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 (A) Ingredients PC-1 parts by weight 100 100 100 100 PC-2 " 80 PC-3 " 20 85 PC-4 " 15 (B) Ingredients B-4 " 2 1 2 1 1 1 B-5 " 1 (C) Ingredients C-2 " 0.1 0.1 0.1 0.1 0.1 C-3 " 0.1 droplet generation time After 1 fire Second no drip no drip no drip no drip no drip no drip after 2 fires Second no drip no drip no drip no drip no drip no drip Dyeing Sharpness - ○ ○ ○ ○ ○ ○ ΔL - 0.1 0.1 0.5 0.4 0.1 0.1 Laser printing clarity - ○ ○ ○ ○ ○ ○ current value A 19.4 19.8 19.4 19.3 19.2 19.2 transparency tone - Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Haze - 2.8 1.9 1.1 2.8 1.9 1.9

table 5 unit Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 (A) Ingredients PC-1 parts by weight 100 70 80 97 PC-2 " 100 ABS " 30 AS " 20 MBS " 3 (B) Other than the ingredient B-12 " 2 2 2 2 2 droplet generation time After 1 fire Second no drip no drip no drip no drip no drip after 2 fires Second 13 20 11 9 14 Dyeing Sharpness - ○ ○ ○ ○ ○ ΔL - 0.1 0.1 0.1 0.1 0.1 Laser printing clarity - x x x x x current value A 18.8 19.0 18.9 18.8 19.0 transparency tone - Colorless and transparent Colorless and transparent opaque opaque opaque Haze - 1.8 1.8 - - -

Table 6 unit Comparative example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 (A) Ingredients PC-1 parts by weight 90 90 100 100 PET " 10 PBT " 10 Total (A) " 100 100 100 100 (B) Other than the ingredient B-10 " 2 B-11 " 2 B-12 " 2 2 Total (B) " 2 2 2 2 droplet generation time After 1 fire Second no drip no drip no drip 1 after 2 fires Second 10 9 9 1 Dyeing Sharpness - ○ ○ x ○ ΔL - 0.1 0.1 3.8 0.1 Laser printing clarity - x x x x current value A 19.1 19.2 19.2 22.0 transparency tone - opaque opaque cloudy Colorless and transparent Haze - - - 61.0 1.1

Table 7 unit Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 (A) Ingredients PC-1 parts by weight 100 100 100 100 (B) Ingredients B-4 " 0.05 15 (B) Other than the ingredient B-12 " 5 droplet generation time After 1 fire Second no drip 2 no drip 1 after 2 fires Second 28 1 36 1 Dyeing Sharpness - ○ ○ ○ ○ ΔL - 0.1 0.1 0.1 0.1 Laser printing clarity - x x x x current value A 18.1 21.9 18.0 22.2 transparency tone - Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Haze - 9.9 0.4 6.5 0.3

Table 8 unit Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 (A) Ingredients PC-1 parts by weight 70 97 90 30 40 ABS " 30 70 MBS " 3 PET " 10 60 (B) Ingredients B-4 " 2 2 droplet generation time After 1 fire Second 1 1 1 3 2 after 2 fires Second 1 1 1 1 1 Dyeing Sharpness - ○ ○ ○ ○ ○ ΔL - 0.1 0.1 0.1 0.1 0.1 Laser printing clarity - x x x ○ ○ current value A 21.7 22.2 22.3 18.8 19.0 transparency tone - opaque opaque opaque opaque opaque Haze - - - - - -

Table 9 unit Example 23 Example 24 Example 25 (A) Ingredients PC-1 parts by weight 100 100 100 (B) Ingredients B-7 " 2 B-8 " 2 1 B-9 " 2 (C) Ingredients C-2 " 0.1 0.1 0.1 droplet generation time After 1 fire Second no drip no drip no drip after 2 fires Second no drip no drip no drip Dyeing Sharpness - ○ ○ ○ ΔL - 0.1 0.1 0.1 Laser printing clarity - ○ ○ ○ current value A 19.4 19.4 19.4 transparency tone - Colorless and transparent Colorless and transparent Colorless and transparent Haze - 2.3 2.8 3.1

[Examples 26 to 38 and Comparative Examples 19 to 24]

For each component listed in Tables 10 to 14, measure according to the mixing ratio shown in the table, measure other components not listed in the table according to the same composition ratio as in Example 1, and use the same method as in Example 1 A resin composition and a test piece were prepared.

The raw materials etc. listed in Tables 10 to 14 are as follows. (B) Component Synthesis Example-13

301.9 g of water and 150 g of toluene were charged into the flask, and a mixture of 21.7 g of trimethylchlorosilane, 23.0 g of methyldichlorosilane, 12.9 g of dimethyldichlorosilane and 76.0 g of diphenyldichlorosilane was added dropwise, Other than that, the same operation as in Synthesis Example 2 was performed to obtain siloxane compound B-13. Synthesis example-14

16.2 g of hexamethyldisiloxane, 61.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 103.8 g of octamethylcyclotetrasiloxane and diphenyldimethylsiloxane were charged into the flask Except having added 391.0 g of oxysilanes, 25.0 g of concentrated sulfuric acid, and dripping 29.4 g of water, the same operation as Synthesis Example-1 was performed, and the siloxane compound B-14 was obtained. Synthesis example-15

167.9 g of 1,1,3,3-tetramethyldisiloxane, 92.7 g of octamethylcyclotetrasiloxane, 49.6 g of octaphenylcyclotetrasiloxane and phenyltrimethoxy Silane compound B-15 was obtained by performing the same operation as synthesis example-1 except having added 297.4 g of silanes, 25.5 g of concentrated sulfuric acid, and adding 41.3 g of water dropwise. Synthesis example-16

403.2g of water and 120g of toluene are charged in the flask, and a mixture of 48.3g of dimethylchlorosilane, 43.9g of dimethyldichlorosilane, 21.5g of diphenyldichlorosilane and 36.0g of phenyltrichlorosilane is added dropwise, Other than that, the same operation as in Synthesis Example-2 was carried out to obtain siloxane compound B-16. Synthesis example-17

70.5 g of 1,1,3,3-tetramethyldisiloxane, 126.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane and diphenyldimethoxysilane were placed in the flask 243.8 g and 25.0 g of concentrated sulfuric acid were added, and 18.3 g of water was added dropwise, and the same operation as in Synthesis Example-1 was performed to obtain siloxane compound B-17. Synthesis example-18

87.3 g of 1,1,3,3-tetramethyldisiloxane, 211.1 g of hexamethyldisiloxane, 31.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane were charged into the flask g and 257.8 g of phenyltrimethoxysilane, except that 25.0 g of concentrated sulfuric acid was added, and 35.8 g of water was added dropwise, the same operation as in Synthesis Example-1 was performed to obtain silane oxygenation B-18. Synthesis example-19

Fill the flask with 447.2g of water and 200g of toluene, drop 22.2g of trimethylchlorosilane, 39.1g of methyldichlorosilane, 21.9g of dimethyldichlorosilane, 43.0g of diphenyldichlorosilane, methyl Except for the mixture of 12.7 g of trichlorosilane and 18.0 g of phenyltrichlorosilane, the same operation as in Synthesis Example-2 was performed to obtain siloxane compound B-19. Synthesis example-20

Charge hexamethyldisiloxane 8.1g, 1,3,5,7-tetramethylcyclotetrasiloxane 120.3g, octamethylcyclotetrasiloxane 111.2g and diphenyldimethylsiloxane in the flask Except having added 195.5 g of oxysilanes, 20.0 g of concentrated sulfuric acid, and dripping water 14.7 g, the same operation as Synthesis Example-1 was performed, and the siloxane compound B-20 was obtained. B-13: A siloxane compound having an Si-H content of 0.21 mol/100 g, an aryl group content of 49% by weight, and an average degree of polymerization of 8.0 prepared according to Synthesis Example-13. B-14: Prepared according to Synthesis Example-14 The obtained Si-H amount is 0.20 mol/100g, the aryl group amount is 50% by weight, and the siloxane compound B-15 whose average degree of polymerization is 42.0: the Si-H amount obtained according to Synthesis Example-15 is 0.50 mol/ 100 g of siloxane compound B-16 with an aryl group content of 31% by weight and an average polymerization degree of 11.0: Si-H content of 0.52 mol/100g, aryl group content of 27% by weight, and Silicone compound B-17 with an average degree of polymerization of 6.5: a siloxane compound with an amount of Si-H of 0.80 mol/100 g, an amount of aryl groups of 39% by weight, and an average degree of polymerization of 7.9, prepared according to Synthesis Example-17 B-18: A siloxane compound having an Si-H content of 0.37 mol/100 g, an aryl group content of 20% by weight, and an average degree of polymerization of 4.4 prepared according to Synthesis Example-18. B-19: Prepared according to Synthesis Example-19 The amount of Si-H obtained is 0.34mol/100g, the amount of aryl groups is 33% by weight, and the average degree of polymerization is 62.0. The amount of Si-H obtained is 0.50mol/ 100 g of a siloxane compound having an aryl group content of 31% by weight and an average degree of polymerization of 88.0 Other (B) component synthesis example-21

39.0 g of 1,1,3,3-tetramethyldisiloxane and 566.9 g of diphenyldimethoxysilane were charged into the flask, 25.0 g of concentrated sulfuric acid was added, and 42.6 g of water was added dropwise. , the same operation as in Synthesis Example-1 was carried out to obtain siloxane compound B-21. Synthesis example-22

560.6g of water and 130g of toluene are charged into the flask, and a mixture of 21.2g of trimethylchlorosilane, 52.3g of methyldichlorosilane, 83.9g of dimethyldichlorosilane and 13.8g of phenyltrichlorosilane is added dropwise, except Otherwise, the same operation as in Synthesis Example-2 was performed to obtain siloxane compound B-22. B-21 (comparison): Siloxane compound B-22 (comparison) with an Si-H content of 0.12 mol/100 g, an aryl group content of 72% by weight, and an average degree of polymerization of 10.0 according to Synthesis Example-21: A siloxane compound <Schematic formula of each siloxane compound> B-13 obtained according to Synthesis Example-22 with an Si-H amount of 0.45 mol/100 g, an aryl group amount of 5% by weight, and an average degree of polymerization of 21.0: M ₂ D ^H ₂ D ₁ D ^φ2 ₃ B-14: M ₂ D ^H ₁₀ D ₁₄ D ^φ2 ₁₆ B-15: M ^H ₅ D _2.5 D ^φ2 _0.5 T ^φ ₃ B-16: M ^H ₃ D ₂ D ^φ2 _0.5 T ^φ ₁ B-17: M ^H ₂ D ^H ₄ D ^φ2 _1.9 B-18: M ₂ M ^H ₁ D ^H _0.4 T ^φ ₁ B-19: M ₁₂ D ^H ₂₀ D ₁₀ D ^φ2 ₁₀ T ₅ T ^φ ₅ B-20: M ₂ D ^H ₄₀ D ₃₀ D ^φ2 ₁₆ B-21: M ^H ₂ D ^φ2 ₈ (comparison) B-22: M ₃ D ^H ₇ D ₁₀ T ^φ ₁ (comparison)

In the above schematic formula, each symbol represents the siloxane unit below, and the lower angle coefficient after each symbol represents the degree of polymerization of each siloxane unit in one molecule. M: (CH ₃ ) ₃ SiO _1/2 M ^H : H(CH ₃ ) ₂ SiO _1/2 D: (CH ₃ ) ₂ SiOD ^H : H(CH ₃ )SiOD ^φ2 : (C ₆ H ₅ ) ₂ SiOT : (CH ₃ )SiO _3/2 T ^φ : (C ₆ H ₅ )SiO _3/2

Table 10 unit Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 (A) Ingredients PC-1 parts by weight 100 100 100 100 PC-2 " 100 100 (B) Ingredients B-13 " 2 B-14 " 2 5 B-15 " 2 5 B-16 " 2 droplet generation time After 1 fire Second no drip no drip no drip no drip no drip no drip after 2 fires Second 7 18 twenty two 9 18 7 transparency tone - Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Haze - 0.3 1.6 9.1 1.1 1.3 0.8 Moisture resistance tone - Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Δ haze - 1.0 0.9 2.6 1.9 2.5 0.8 Laser printing clarity - ○ ○ ○ ○ ○ ○ current value A 19.2 19.4 18.6 19.6 18.5 19.7

Table 11 unit Example 32 Example 33 Example 34 Example 35 (A) Ingredients PC-1 parts by weight 100 100 100 100 (B) Ingredients B-13 " 1 B-15 " 2 1 2 2 (C) Ingredients C-1 " 0.1 C-2 " 0.1 0.1 C-3 " 0.1 droplet generation time After 1 fire Second no drip no drip no drip no drip after 2 fires Second no drip no drip no drip no drip transparency tone - Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Haze - 1.2 2.6 2.8 1.1 Moisture resistance tone - Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Δ haze - 2.0 1.6 1.6 4.1 Laser printing clarity - ○ ○ ○ ○ current value A 19.6 19.2 19.4 19.4

Table 12 unit Comparative Example 19 Comparative Example 20 Comparative Example 21 (A) Ingredients PC-1 parts by weight 100 100 100 (B) Ingredients B-15 " 0.05 20 (B) Other than the ingredient B-22 " 2 droplet generation time After 1 fire Second 1 no drip no drip after 2 fires Second 1 30 11 transparency tone - Colorless and transparent Colorless and transparent cloudy Haze - 0.4 7.9 77.7 Moisture resistance tone - Colorless and transparent Colorless and transparent cloudy Δ haze - 0.3 11.3 1.8 Laser printing clarity - x x x current value A 21.9 17.5 19.1

Table 13 unit Comparative Example 22 Comparative Example 23 Comparative Example 24 (A) Ingredients PC-1 parts by weight 100 100 100 (B) Other than the ingredient B-11 " 10 B-21 " 2 droplet generation time After 1 fire Second no drip 3 1 after 2 fires Second 13 1 1 transparency tone - cloudy Colorless and transparent Colorless and transparent Haze - 31.6 0.9 0.3 Moisture resistance tone - cloudy Colorless and transparent Colorless and transparent Δ haze - 2.0 1.3 0.3 Laser printing clarity - x x x current value A 19.1 21.6 22.2

Table 14 unit Example 36 Example 37 Example 38 (A) Ingredients PC-1 parts by weight 100 100 100 (B) Ingredients B-17 " 2 B-18 " 2 B-19 " 2 (C) Ingredients C-2 " 0.1 0.1 0.1 droplet generation time After 1 fire Second no drip no drip no drip after 2 fires Second no drip no drip no drip transparency tone - Colorless and transparent Colorless and transparent Colorless and transparent Haze - 2.4 1.6 2.9 Moisture resistance tone - Colorless and transparent Colorless and transparent Colorless and transparent Δ haze - 1.4 2.1 2.0 Laser printing clarity - ○ ○ ○ current value A 18.7 19.1 19.1 [Examples 39-42] According to the ratio shown in Table 15, each component is measured, and then the phosphite antioxidant (IRGAFOS168 manufactured by Japan Chiba Gaigi Co.): 0.01 parts by weight, the phenol antioxidant (Ciba・Specialty chemicals (Ciba Specialty Chemicals) IRGANOX1076): 0.05 parts by weight, mold release agent (manufactured by Cognis Japan Co., Ltd., Lokisioll (VPG861): 0.3 parts by weight, Bayer's Marcoro Macrolex bioretto B: 0.00005 parts by weight was measured, then uniformly mixed with a tumbler mixer, and the mixture was prepared into a resin composition and a test piece in the same manner as in Example 1.

The raw materials shown in Table 15 are as follows. (D) Component D-1: Talc (UPNHS-T0.8 manufactured by Hayashi Kasei Co., Ltd.)

Table 15 unit Example 39 Example 40 Example 41 Example 42 (A) Ingredients PC-1 parts by weight 100 100 PC-2 " 80 PC-3 " 20 85 PC-4 " 15 (B) Ingredients B-13 " 1 1 1 1 (C) Ingredients C-2 " 0.1 0.1 0.1 C-3 " 0.05 (D) Ingredients D-1 " 1 droplet generation time After 1 fire Second no drip no drip no drip no drip after 2 fires Second no drip no drip no drip no drip Laser printing clarity - ○ ○ ○ ○ current value A 19.1 19.2 19.2 19.2 transparency tone - Colorless and transparent Colorless and transparent Colorless and transparent Colorless and transparent Haze - 1.7 1.6 1.6 10.2

[Example 43]

Each component is measured according to the ratio shown in Table 16, then to phosphite antioxidant (IRGAFOS168 manufactured by Japan's チバガイギ-company): 0.01 parts by weight, phenol antioxidant (Ciba Specialty Chemicals (Ciba Specialty) Chemicals) IRGANOX1076): 0.05 parts by weight, release agent (manufactured by Cognis Japan Co., Ltd., Lokisioll) VPG816: 0.3 parts by weight, the concentration of polytetrafluoroethylene with fibril-forming ability is 2.5 weight % polycarbonate resin masterbatch granules (the above-mentioned PC-1: 97.5% by weight and Daikin Industry’s polyfluoron (Polyfloron) MPAFA500: 2.5% by weight are pelletized by the same twin-screw extruder as above. Material granules): 2 parts by weight, Macrorex Biolet (Macrorex Biolet) B of Bayer Company: 0.00003 parts by weight to measure, uniformly mix with a drum mixer, and use the same method as in Example 1 to mix the The mixture was made into a resin composition and a test piece.

[Example 44]

The above PC-1 and the above B-20 were dissolved in methylene chloride at a weight ratio of PC-1:B-20=100:10 to prepare a 10% by weight methylene chloride solution. The methylene chloride solution was sprayed with a GS-310 special type spray dryer using an organic solvent manufactured by Amatlabotec to obtain a mixed powder of polycarbonate resin and organosiloxane. Operating conditions: heat carrier: nitrogen, inlet temperature of heat carrier into the spray chamber: 70°C, flow rate of heat carrier: 0.5m ³ /min, spray pressure 100kPa, input speed of dichloromethane solution: 40g/min, spray Cavity bottom temperature: 70°C.

Measure the mixed powder and PC-1 according to the mixing ratio shown in Table 16, and then measure the other ingredients not shown in Table 16 according to the same ratio and composition as in Example 39, and use the same method as in Example 39 Methods A resin composition and a test piece were produced.

Table 16 unit Example 43 Example 44 (A) Ingredients PC-1 parts by weight 100 100 (B) Ingredients B-13 " 1 B-20 " 2 (C) Ingredients C-2 " 0.1 droplet generation time After 1 fire Second no drip no drip after 2 fires Second no drip no drip Laser printing clarity - ○ ○ current value A 19.2 19.7 transparency tone - Colorless and transparent Colorless and transparent Haze - 5.4 12.2 exam preparation Add PTFE Use a premix of A and B

The above-described embodiments can illustrate the following facts. When the flame-retardant aromatic polycarbonate resin composition of the present invention is used to print characters and logos by laser printing, the clarity of the characters and logos is high, and by adding the siloxane compound of the present invention, it prolongs the time from ignition to occurrence. The time of dripping, the anti-dripping performance of the resin when burning is also very good.

The following facts can also be further illustrated. The transparent flame-retardant aromatic polycarbonate resin composition of the present invention is excellent in transparency and heat-and-moisture resistance. Moreover, by adding the siloxane compound of the present invention, the time from ignition to dripping is prolonged, and the dripping resistance of the resin during burning is also very good. In particular, when the degree of polymerization of the siloxane compound satisfies prescribed conditions, excellent transparency and anti-dripping properties can be obtained.

[Example 45]

Use the granular material of embodiment 39, after 120 ℃ through the hot-air circulation drier drying 5 hours, extrude with the single-screw extruder that the diameter of sheet material T-shaped head is installed at the front is the single-screw extruder of φ 40mm, and screw speed is 40rpm, through the casting roll contacting the head surface, extruding to obtain a 100μm sheet. The sheet was excellent in transparency and excellent in surface smoothness. This sheet was cut into a molded product with a size of 50 mm x 50 mm, and the sheet molded product was placed in a DC magnetron sputtering device. A 40 nm metal oxide layer made of indium and tin oxide, a 9 nm silver and gold alloy layer, and a 40 nm metal oxide layer were laminated in this order to prepare a transparent conductive sheet.

Claims (25)

1. flame-retardant aromatic polycarbonate resin composition, composition comprises:

(1) resinous principle 100 weight parts comprise aromatic polycarbonate resin (A-1 composition) 50～100 weight %, phenylethylene resin series (A-2 composition) 0～50 weight % and aromatic polyester resins (A-3 composition) 0～50 weight %,

(2) at least a silicone compounds (B) 0.1～10 weight part that cooperates in per 100 parts by weight resin compositions, this silicone compounds is the silicone compounds that contains Si-H base and aryl in the molecule, wherein 1. the content of Si-H base (Si-H amount) is 0.1～1.2mol/100g, 2. the aryl content ratio shown in the following general formula (1) (aryl amount) is 10～70 weight % In the formula (1), X represents that independently of one another OH base, carbon number are 1～20 the organic residue of monovalence, and n represents 0～5 integer, and, in the general formula (1),, can choose the X that has nothing in common with each other when n is 2 when above.

2. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, the mean polymerisation degree of this silicone compounds (B composition) is 3～150.

3. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, the contained Si-H base unit weight (Si-H amount) of this silicone compounds (B composition) is 0.2～1.0mol/100g.

4. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, the aryl amount of this silicone compounds (B composition) is 15～60 weight %.

5. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, the specific refractory power of this silicone compounds (B composition) in the time of 25 ℃ is 1.40～1.60.

6. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, this silicone compounds (B composition) is the silicone compounds that contains at least a above structural unit among the structural unit shown in following general formula (2) and (3),

In formula (2) and (3), Z ¹～Z ³Represent that independently of one another hydrogen atom, carbon number are that 1～20 monovalence has basic residue, or the compound shown in the following general formula (4); α 1～α 3 is separately independently, represents 0 or 1 respectively; M1 represents 0 or be integer more than 1, in the formula (2), when m1 is that 2 repeating units when above can be chosen mutually different multiple repeating unit; In the formula (4), Z ⁴～Z ⁸Represent that independently of one another hydrogen atom, carbon number are 1～20 the organic residue of monovalence; α 4～α 8 is separately independently, represents 0 or 1 respectively; M2 represents the integer more than 0 or 1; In the formula (4), when m2 is that 2 repeating units when above can be chosen the multiple heavy again unit that has nothing in common with each other.

7. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, this silicone compounds B composition is the silicone compounds that is made of MD unit or MDT unit, in the formula, M represents that single functionality siloxane unit, D represent that difunctionality siloxane unit, T represent the three-functionality-degree siloxane unit.

8. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, concerning this resinous principle (A) 100 weight parts, also contain compound (C composition) 0.001～0.3 weight part more than from free radical generating agent, organic alkali metal salt and organic alkali earth metal salt, select at least a.

9. flame-retardant aromatic polycarbonate resin composition according to claim 1 wherein, concerning this resinous principle (A) 100 weight parts, also contains weighting agent (D composition) 1～100 weight part.

10. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, this resinous principle (A) is made up of aromatic polycarbonate resin (A-1 composition) 50～99.5 weight %, phenylethylene resin series (A-2 composition) 0～50 weight % and/or aromatic polyester resins (A-3 composition) 0～50 weight %, and the total amount of A-2 composition and A-3 composition is 0.5～50 weight %.

11. flame-retardant aromatic polycarbonate resin composition according to claim 1 wherein, is substantially devoid of halogenide as fire retardant.

12. transparent flame-retarding aromatic copolycarbonate resin composition, it constitutes by containing silicone compounds (B composition) 0.1～10 weight part in the 100 weight part aromatic polycarbonate resins (A-1 composition), this silicone compounds is selected from least a in the silicone compounds that contains Si-H base and aryl in the molecule, wherein 1. the basic content of Si-H (Si-H amount) be containing of the aryl shown in 0.1～1.2mol/100g and the 2. following general formula (1) proportional (aryl amount) 10～70 weight %, In the formula (1), X represents that independently of one another OH base, carbon number are 1～20 the organic residue of monovalence; N represents 0～5 integer; In the formula (1),, can choose the X that has nothing in common with each other when n is 2 when above.

13. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12, wherein, the mean polymerisation degree of this silicone compounds (B composition) is 3～80.

14. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12, wherein, the contained Si-H base unit weight (Si-H amount) of this silicone compounds (B composition) is 0.2～1.0mol/100g.

15. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12, wherein, the aryl amount of this silicone compounds (B composition) is 15～60 weight %.

16. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12, wherein, the mean polymerisation degree of this silicone compounds (B composition) is 3～60.

17. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12, wherein, the specific refractory power of this silicone compounds (B composition) in the time of 25 ℃ is 1.40～1.60.

18. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12, wherein, this silicone compounds (B composition) is the silicone compounds that contains at least a above structural unit among the structural unit shown in following general formula (2) and (3)

In formula (2) and the formula (3), Z ¹～Z ³Represent that independently of one another hydrogen atom, carbon number are 1～20 organic residue of monovalence or the compound shown in the following general formula (4); α 1～α 3 is separately independently, represents 0 or 1 respectively.M1 represents the integer more than 0 or 1; In the formula (2), when m1 is that 2 repeating units when above can be chosen the repeating unit that has nothing in common with each other; In the formula (4), Z ⁴～Z ⁸Represent that independently of one another hydrogen atom, carbonatoms are 1～20 the organic residue of monovalence; α 4～α 8 is separately independently, represents 0 or 1 respectively; M2 represents the integer more than 0 or 1; In the formula (4), when m2 is that 2 repeating units when above can be chosen the repeating unit that has nothing in common with each other.

19. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12, wherein, this silicone compounds (B composition) is the silicone compounds that is made of MD unit or MDT unit, wherein, M is that single functionality siloxane unit, D are that difunctionality siloxane unit, T are the three-functionality-degree siloxane unit.

20. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12 wherein, is 0.3～20% with the thick haze value of the 2mm of JIS K7105 standard test.

21. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12, wherein, thick in temperature 2mm: 65 ℃, humidity: placing under 85% the environment after 300 hours, is 0.01～10% with the haze value of JIS K7105 standard test and poor (the Δ H) of initial haze value.

22. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12, wherein, concerning aromatic polycarbonate resin 100 weight parts, cooperate at least a above compound (C) 0.001～0.3 weight part that is selected from free agent propellant, organic alkali metal salt and organic alkali earth metal salt (A) again.

23. transparent flame-retarding aromatic copolycarbonate resin composition according to claim 12 wherein, is substantially devoid of halogenide as fire retardant.

24. moulding product are made with claim 1 or the described aromatic copolycarbonate resin composition of claim 12.

25. a clear sheet is made by the described aromatic copolycarbonate resin composition of claim 12.