JP2005036135A - Flame retardant resin composition and molding composed of it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin having excellent flame retardance, heat resistance and color tone not at the expense of the mechanical properties inherent to a rubber-reinforced styrenic resin. <P>SOLUTION: The flame retardant resin composition is a resin composition containing 1-30 pts.wt. phosphorus-based flame retardant and 0.1-20 pts.wt. specific modified phenolic resin to 100 pts.wt. rubber-reinforced styrenic resin. The modified phenolic resin satisfies the following conditions: (a) the viscosity of its 50% 1,4-dioxane solution at 25°C is 30-100 mm<SP>2</SP>/s; (b) the amount of the 600°C residual carbonized product determined by TGA measurement in an air atmosphere at a temperature rising rate of 40°C/min is not less than 30%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a flame retardant resin composition, and more particularly, to a flame retardant resin composition excellent in flame retardancy, heat resistance and color without impairing the original mechanical properties of a rubber-reinforced styrene resin, and a molded article comprising the same. .

  Conventionally, thermoplastic resins have been used in a wide range of fields such as home electric appliances, OA appliances, automobiles and the like due to their excellent mechanical properties, molding processability, and electrical insulation properties. However, depending on the application, flame retardancy is necessary from the viewpoint of safety, and various techniques have been proposed for this flame retardancy. In general, a method of flame retardant by incorporating a halogen-based flame retardant such as bromine compound with high flame retardant efficiency and antimony oxide into the resin is adopted, but the amount of smoke generated during combustion is large. Has a problem.

  Therefore, as a non-halogen flame retardant, a typical phosphoric ester of a phosphorus flame retardant has been frequently used. However, the flame retardant effect of the phosphate ester is extremely low, and in order to impart flame retardancy to the thermoplastic resin, it is necessary to add a large amount of the phosphate ester. Due to the bleed-out, there are problems such as mold contamination during molding and gas generation during molding.

  Therefore, as a technique for solving these problems, a method of adding a novolak phenol resin and a compound containing a triazine skeleton as a carbonized layer-forming polymer to a hydroxyl group-containing phosphate is disclosed (see Patent Document 1). However, this technique also cannot solve the problem that the mechanical properties, impact resistance, and moldability inherent in the thermoplastic resin are impaired. Furthermore, since the phenol resin is a material that is extremely inferior in light resistance, there is a problem that the light resistance of the resulting resin composition is lowered.

  A method using a modified phenolic resin has been disclosed as a method for suppressing the deterioration of mechanical properties and light resistance (see Patent Documents 2 and 3). However, the modified phenolic resin described in the patent document has a large amount of residual carbide at 600 ° C. by TGA measurement when heated at 40 ° C./min in an air atmosphere, and forms a strong carbonized coating at the time of combustion. In order to increase the time until the carbonization coating is formed due to its high mobility, it is necessary to add a large amount of flame retardant in order to develop the desired flame retardancy, resulting in a decrease in mechanical properties. It has not yet been solved.

  Also, a method using a phosphorus flame retardant and an epoxy group-containing compound for a resin composed of a polycarbonate resin and a styrene resin (see Patent Document 4), and a phosphorus-containing compound and a polyarylate resin or an aromatic epoxy resin for a thermoplastic resin. A method (Patent Document 5) is disclosed. However, both the epoxy group-containing compound and the aromatic epoxy resin described in the patent document have a low amount of residual carbide at 600 ° C. by TGA measurement when heated at 40 ° C./min in an air atmosphere, and can exhibit flame retardancy. It wasn't.

  Thus, the modified phenolic resin used in the present invention described later has a correlation between the molecular weight and the amount of residual carbide, and it is found that the amount of residual carbide increases proportionally when the molecular weight is increased. ing. When the molecular weight is increased, the mobility tends to be inhibited and the surface mobility during combustion decreases, but the carbonized coating tends to be formed because of the large amount of residual carbide. However, in fact, none of the commercially available modified phenolic resins has achieved the desired flame retardancy.

Furthermore, a method of blending a specific resin with a specific Tg (glass transition temperature) and a heat loss polymer or oligomer in a thermoplastic resin is disclosed (see Patent Document 6). However, in the invention described in the patent document, as in the past, high flame retardancy cannot be obtained unless a large amount of flame retardant is added.
JP-A-7-70448 JP 2002-121405 A JP 2002-188001 A JP 2000-103950 A JP 2000-239543 A JP 2001-146554 A

  An object of the present invention is to solve such problems and to provide a resin composition having excellent mechanical properties, heat resistance, and color tone as well as imparting high flame retardancy to a rubber-reinforced styrene resin.

  As a result of intensive studies to achieve the above-mentioned object, the present invention has found a specific modified phenolic resin with a small decrease in the amount of residual carbides even when the molecular weight is lowered, and a rubber-reinforced styrene resin and a phosphorus flame retardant In combination with the modified phenolic resin, excellent flame retardancy can be imparted even if the amount of phosphorus flame retardant added is reduced, and a flame retardant resin composition having excellent mechanical properties, heat resistance, and color tone is obtained. It has been found that it can be obtained.

That is, the flame-retardant resin composition according to the present invention is 1 to 30 parts by weight of a phosphorus-based flame retardant (B) and 100% by weight of the rubber-reinforced styrene resin (A) and the following general formula (1). A modified phenolic resin (C) represented by 0.1 to 20 parts by weight, wherein the modified phenolic resin (C) represented by the following general formula (1) has the following conditions: It consists of what is characterized by satisfying.
(A) Solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution is 30 to 100 mm ² / s
(B) The amount of residual carbide at 600 ° C. is 30% or more by TGA measurement when the temperature is raised at 40 ° C./min in an air atmosphere.

（上記式中、Ｒ¹は炭素数１〜１０の有機残基を表す。また、Ｒ²は水素原子あるいは炭素数１〜５のアルキル基を表す。）

(In the above formula, R ¹ represents an organic residue having 1 to 10 carbon atoms. R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

  Moreover, the molded article which concerns on this invention consists of the above flame-retardant resin compositions.

  According to the present invention, a flame retardant composition excellent in flame retardancy, heat resistance and color tone can be obtained without impairing the original mechanical properties of the resin. Moreover, the molded article which consists of such a flame-retardant composition becomes a thing excellent in a mechanical characteristic, heat resistance, and color tone while having a flame retardance.

Hereinafter, the flame retardant resin composition according to the present invention and a molded product made thereof will be described in detail.
The rubber-modified styrenic resin (A) in the present invention is a monomer mixture obtained by adding an aromatic vinyl monomer and, if necessary, a vinyl monomer copolymerizable therewith in the presence of a rubber-like polymer. Is obtained by subjecting to a known block polymerization, block suspension polymerization, solution polymerization or emulsion polymerization.

  Specific examples of such a rubber-modified styrene resin include, for example, impact-resistant polystyrene, ABS resin, AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), MBS resin (methyl methacrylate-butadiene rubber-styrene copolymer). Polymer) and AES resin (acrylonitrile-ethylenepropylene rubber-styrene copolymer).

  As such a rubber-modified styrenic resin, a polymer or copolymer containing a styrene monomer (hereinafter sometimes referred to as (co) polymer) is grafted to a rubbery polymer. These include those having a structure and those having a structure in which a (co) polymer containing a styrene monomer is non-grafted to a rubbery polymer.

  Specifically, it is obtained by graft polymerization of 95 to 20 parts by weight of a monomer or monomer mixture containing 20% by weight or more of an aromatic vinyl monomer with respect to 5 to 80 parts by weight of a rubbery polymer. 10% to 100% by weight of the graft (co) polymer (A-1) to be obtained and a vinyl type obtained by polymerizing a monomer or monomer mixture containing 20% by weight or more of an aromatic vinyl type monomer ( Co) The polymer (A-2) is preferably composed of 0 to 90% by weight.

  As the rubber polymer, those having a glass transition temperature of 0 ° C. or lower are suitable, and diene rubber is preferably used. Specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, diene rubber such as butyl acrylate-butadiene copolymer, acrylic such as polybutyl acrylate, etc. Rubber, polyisoprene, and ethylene-propylene-diene terpolymer. Of these, the use of polybutadiene or butadiene copolymer is preferred.

  The rubber particle diameter of the rubber polymer is not particularly limited, but the impact resistance is excellent when the weight average particle diameter of the rubber particles is 0.15 to 0.6 μm, particularly 0.2 to 0.55 μm. To preferred. Among them, those having a weight average particle diameter of 0.20 to 0.25 μm and a weight ratio of 0.50 to 0.65 μm are 90:10 to 60:40. It is preferable because the drop weight impact is remarkably excellent.

  The average weight particle diameter of the rubber particles is determined by the sodium alginate method described in “Rubber Age Vol. 88 p. 484 to 490 (1960) by E. Schmidt, PH Biddison” according to the concentration of sodium alginate. The particle diameter of the cumulative weight fraction of 50% is obtained from the weight ratio of the cream and the cumulative weight fraction of the sodium alginate concentration by utilizing the fact that the particle size of the polybutadiene is different.

  Specific examples of the aromatic vinyl monomer include styrene, α-methyl styrene, vinyl toluene, o-ethyl styrene, pt-butyl styrene, and the like, and the use of styrene is particularly preferable.

  As monomers other than aromatic vinyl monomers, vinyl cyanide monomers are used for the purpose of further improving impact resistance and chemical resistance, and for the purpose of improving toughness and color tone. In this case, a (meth) acrylic acid ester monomer is preferably used.

  Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferably used.

  Specific examples of the (meth) acrylic acid ester monomer include methyl, ethyl, propyl, n-butyl, isobutyl ester and the like of acrylic acid and methacrylic acid, and methyl methacrylate is particularly preferably used.

  Further, if necessary, other vinyl monomers such as maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide can also be used.

  From the viewpoint of impact resistance of the resin composition, the monomer or monomer mixture used in the graft (co) polymer (A-1) contains 20% by weight or more of an aromatic vinyl monomer. It is preferably 50% by weight or more. In the case of mixing a vinyl cyanide monomer, it is preferably 60% by weight or less, particularly preferably 50% by weight or less, from the viewpoint of moldability of the resin composition. Moreover, when mixing a (meth) acrylic acid ester-type monomer, it is preferable that it is 80 weight% or less from a viewpoint of toughness and impact resistance, and especially 75 weight% or less is used preferably. The total amount of aromatic vinyl monomer, vinyl cyanide monomer and (meth) acrylic acid ester monomer in the monomer or monomer mixture is 95 to 20% by weight. Is more preferable, and 90 to 30% by weight is more preferable.

  The blending ratio of the rubbery polymer and the monomer mixture in obtaining the graft (co) polymer (A-1) is 100 parts by weight of the total graft copolymer from the viewpoint of impact resistance of the resin composition. Further, the rubber-like polymer is preferably 5 parts by weight or more, more preferably 10 parts by weight or more. Further, from the viewpoint of the impact resistance of the resin composition and the appearance of the molded product, it is preferably 80 parts by weight or less, more preferably 70 parts by weight or less. The blending ratio of the monomer or monomer mixture is 95 parts by weight or less, preferably 90 parts by weight or less, or 20 parts by weight or more, preferably 30 parts by weight or more.

  The graft (co) polymer (A-1) can be obtained by a known polymerization method. For example, it can be obtained by a method of emulsion polymerization by continuously supplying a mixture of a monomer and a chain transfer agent and a solution of a radical generator dissolved in an emulsifier to a polymerization vessel in the presence of a rubbery polymer latex. .

The graft (co) polymer (A-1) contains an ungrafted copolymer in addition to a graft copolymer having a structure in which a monomer or a monomer mixture is grafted to a rubbery polymer. It is a thing. The graft ratio of the graft (co) polymer is not particularly limited, but in order to obtain a resin composition having an excellent balance between impact resistance and gloss, it is in the range of 20 to 80% by weight, particularly 25 to 50% by weight. It is preferable that Here, the graft ratio is a value calculated by the following equation.
Graft rate (%) = [<Amount of vinyl copolymer graft-polymerized to rubbery polymer> / <Rubber content of graft copolymer>] × 100

  The characteristics of the ungrafted (co) polymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone-soluble component is 0.25 to 0.6 dl / g, particularly 0.25 to A range of 0.5 dl / g is a preferable condition for obtaining a resin composition having excellent impact resistance.

  The vinyl (co) polymer (A-2) is a copolymer essentially comprising an aromatic vinyl monomer. Examples of the aromatic vinyl monomer include styrene, α-methyl styrene, p-methyl styrene, t-butyl styrene, vinyl toluene and o-ethyl styrene, and styrene is particularly preferably used. These can use 1 type (s) or 2 or more types.

  As monomers other than aromatic vinyl monomers, vinyl cyanide monomers are used for the purpose of further improving impact resistance and chemical resistance, and for the purpose of improving toughness and color tone. In this case, a (meth) acrylic acid ester monomer is preferably used.

  Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferably used. Specific examples of the (meth) acrylic acid ester monomer include methyl, ethyl, propyl, n-butyl, and isobutyl esterified products of acrylic acid and methacrylic acid. In particular, methyl methacrylate is preferably used. .

  Further, other vinyl monomers copolymerizable with these used as necessary include maleimide monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide.

  In the present invention, a vinyl copolymer obtained by copolymerizing a maleimide monomer, that is, a maleimide group-modified vinyl copolymer is used by being contained in a polystyrene resin. Can be improved, and the flame retardancy can also be specifically improved, so that it can be preferably used.

  From the viewpoint of impact resistance of the resin composition, the proportion of the aromatic vinyl monomer that is a constituent component of the vinyl (co) polymer (A-2) is 20% by weight or more based on the total monomers. Preferably, it is in the range of 50% by weight or more. When a vinyl cyanide monomer is mixed, it is preferably 60% by weight or less, more preferably 50% by weight or less from the viewpoint of impact resistance and fluidity. Moreover, when mixing a (meth) acrylic-ester monomer, 80 weight% or less is preferable from a viewpoint of toughness and impact resistance, More preferably, it is the range of 75 weight% or less. Furthermore, when other vinyl monomers copolymerizable with these are mixed, the content is preferably 60% by weight or less, and particularly preferably 50% by weight or less.

  Although there is no restriction | limiting in the characteristic of a vinyl type (co) polymer (A-2), The intrinsic viscosity [(eta)] measured at 30 degreeC using the methyl ethyl ketone solvent is 0.4-0.65 dl / g, especially Those in the range of 0.45 to 0.55 dl / g, and 0.35 to 0.85 dl / g, particularly 0.45 when measured at 30 ° C. using N, N-dimethylformamide solvent. The range of ˜0.7 dl / g is preferable because a resin composition having excellent impact resistance and molding processability can be obtained.

  There is no restriction | limiting in particular in the manufacturing method of a vinyl type (co) polymer (A-2), Bulk polymerization method, suspension polymerization method, emulsion polymerization method, block-suspension polymerization method, solution-bulk polymerization method, etc. are normal. The method can be used.

  In the present invention, a modified vinyl polymer containing at least one functional group selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group and an oxazoline group (hereinafter referred to as a modified vinyl polymer). Can be used as well.

  This modified vinyl polymer has a structure obtained by polymerizing or copolymerizing one or two or more kinds of vinyl monomers, and has a carboxyl group, hydroxyl group, epoxy group, amino group and It is a polymer containing at least one functional group selected from oxazoline groups. The content of the compound containing these functional groups is not limited, but is particularly preferably in the range of 0.01 to 20% by weight per 100 parts by weight of the modified vinyl polymer.

  The method for introducing a carboxyl group into the modified vinyl polymer is not particularly limited, but a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, maleic acid monoethyl ester, maleic anhydride, phthalic acid and itaconic acid, or A method of copolymerizing a vinyl monomer having an anhydrous carboxyl group with a predetermined vinyl monomer, γ, γ′-azobis (γ-cyanovaleric acid), α, α′-azobis (α-cyanoethyl) -p -Polymerization initiators and / or thioglycolic acid, [alpha] -mercaptopropionic acid, [beta] -mercaptopropionic acid, [alpha] -mercapto-isobutyric acid and 2,3 or 4-mercapto having a carboxyl group, such as benzoic acid and peroxysuccinic acid Using a polymerization degree regulator having a carboxyl group, such as benzoic acid, And a copolymer of a (meth) acrylic acid ester monomer such as methyl methacrylate or methyl acrylate and an aromatic vinyl monomer, and, if necessary, a vinyl cyanide monomer. A method of saponifying with an alkali can be used.

  The method for introducing the hydroxyl group is not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3, acrylic acid 4,5,6-pentahydroxyhexyl, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5-methacrylic acid Tetrahydroxypentyl, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1- Propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pente , 4-dihydroxy-2-butene a vinyl monomer having a hydroxyl group such as, a method of copolymerizing with a predetermined vinyl monomer can be used.

  The method for introducing the epoxy group is not particularly limited. For example, epoxies such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether and p-glycidyl styrene For example, a method of copolymerizing a vinyl monomer having a group with a predetermined vinyl monomer can be used. Among them, the epoxy-modified vinyl copolymer into which an epoxy group is introduced by copolymerizing glycidyl methacrylate is used when incorporated in a polystyrene-based resin, the flame retardancy and impact strength of the resin composition of the present invention. Can be improved.

  The method for introducing the amino group is not particularly limited. For example, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, dimethyl methacrylate. Amino groups such as aminoethyl, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene And a method of copolymerizing a vinyl monomer having a derivative thereof and a predetermined vinyl monomer.

  The method for introducing the oxazoline group is not particularly limited. For example, a vinyl-based monomer having an oxazoline group such as 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, and 2-styryl-oxazoline. For example, a method of copolymerizing the body with a predetermined vinyl monomer can be used.

  The properties of the modified vinyl polymer are not limited, but the intrinsic viscosity [η] measured at 30 ° C. using a methyl ethyl ketone solvent is 0.2 to 0.65 dl / g, particularly 0.35 to 0.6 dl. / G range, and when measured at 30 ° C. using N, N-dimethylformamide solvent, it is 0.3-0.9 dl / g, especially 0.4-0.75 dl / g. Those in the range are preferable because a resin composition having excellent flame retardancy, impact resistance, and moldability can be obtained.

  The phosphorus-based flame retardant (B) used in the present invention is not particularly limited as long as it is an organic or inorganic compound containing phosphorus, such as ammonium polyphosphate, polyphosphazene, phosphate, phosphonate, phosphinate, and phosphine oxide. Is mentioned. Among these, polyphosphazenes and phosphates are preferable, and aromatic phosphates can be particularly preferably used.

Of the phosphorus-based flame retardant (B) used in the present invention, the aromatic phosphate is represented by the following general formula (3).

  First, the structure of the flame retardant represented by the formula (3) will be described. In the formula (3), n is an integer of 0 or more, and a mixture of different n may be used. K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with an organic residue containing no halogen. Specific examples include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, naphthyl group, indenyl group, anthryl group, etc., but phenyl group, tolyl group, xylyl group, cumenyl group, naphthyl group are preferable. In particular, a phenyl group, a tolyl group, and a xylyl group are preferable.

Moreover, in X of said Formula (3), R < ⁴ > -R < ¹¹ > represents the same or different hydrogen or a C1-C5 alkyl group. Specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Hydrogen, a methyl group, and an ethyl group are preferable, and hydrogen is particularly preferable. Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group.

  The usage-amount of the said aromatic phosphate is 1-30 weight part normally with respect to 100 weight part of rubber reinforced styrene resin (A), Preferably it is 2-20 weight part. When the addition amount is less than 1 part by weight, a high flame retardancy imparting effect is not seen, which is not preferable. On the other hand, when the amount exceeds 30 parts by weight, the impact resistance is deteriorated and the surface appearance of the molded product is impaired.

The modified phenolic resin (C) used in the present invention is represented by the following general formula (1) and further satisfies the following conditions.
(A) Solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution is 30 to 100 mm ² / s
(B) The amount of residual carbide at 600 ° C. is 30% or more by TGA measurement when the temperature is raised at 40 ° C./min in an air atmosphere.

（上記式中、Ｒ¹は炭素数１〜１０の有機残基を表す。また、Ｒ²は水素原子あるいは炭素数１〜５のアルキル基を表す。）

(In the above formula, R ¹ represents an organic residue having 1 to 10 carbon atoms. R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

The structure of the formula (1) will be described. In the above formula, R ¹ represents any organic residue having 1 to 10 carbon atoms, preferably an alkyl group, an aryl group, a glycidyl group, or —C (═O) R. Here, R ¹ represents an alkyl group having 1 to 9 carbon atoms or an aryl group. That is, a phenolic resin obtained by etherification or esterification of a phenolic hydroxyl group can be preferably used. R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

  There is no restriction | limiting in particular about the manufacturing method of the modified phenol-type resin shown to the said Formula (1), For example, it can obtain by etherifying and esterifying a well-known publicly used phenol-type resin.

  The phenolic resin used for producing the modified phenolic resin represented by the formula (1) is not particularly limited, and novolak type, resol type and thermal reaction type commercially available ones can be used. The novolak type is preferable in terms of flame retardancy and fluidity.

  As a method for obtaining the phenolic resin, the case of a novolak type phenolic resin is exemplified. The molar ratio of phenols to aldehydes is charged into the reaction vessel at a ratio of 1: 0.1 to 1: 0.9, It is possible to apply a method of heating and reacting in the presence of a catalyst such as an acid, a metal salt, or a metal oxide, and removing low-boiling substances such as condensed water and unreacted raw material produced by distillation or the like. In that case, when a catalyst remains as an acid, it is preferable to neutralize with a basic substance.

  The phenols used to obtain these phenolic resins include phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, and o-methoxy. Examples include phenol, 4,4′-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, and 2,6-di-tert-butyl-p-cresol. These phenols may be used alone or in combination of two or more. On the other hand, aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. These aldehydes can be used alone or in combination of two or more as required.

  The catalyst used in the above reaction is not particularly limited, but examples thereof include sulfonic acids such as hydrochloric acid, sulfuric acid, toluenesulfonic acid, and phenolsulfonic acid, carboxylic acids such as oxalic acid and salicylic acid, zinc acetate, and zinc naphthenate. Examples thereof include metal salts and metal oxides such as zinc oxide, which may be used alone or in combination of two or more.

  Next, a method for obtaining the modified phenol resin represented by the formula (1) will be described. A method in which the above-described phenolic resin is used as a raw material, and a method in which any alkyl halide, epihalohydrin, or the like is reacted in a basic catalyst for etherification, or a method in which any acid halide or acid anhydride is reacted to perform esterification However, it is not limited to these methods.

As a method for producing the modified phenolic resin represented by the general formula (1), the solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution of the obtained modified phenol resin is 30 to 100 mm ² / s. There is no particular restriction except that there is. An example of a method of etherifying a phenolic resin with epihalohydrin is as follows: a 50% n-butanol solution having a solution viscosity at 25 ° C. of 110 to 440 mm ² / s, and an epihalohydrin such as epichlorohydrin or epibromohydrin An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the dissolved mixture of or a reaction is carried out at 20 to 120 ° C. for 1 to 10 hours while being added. The addition amount of epihalohydrin is usually in the range of 0.3 to 20 equivalents relative to 1 equivalent of hydroxyl group in the phenol resin as a raw material. When the epihalohydrin is less than 2.5 equivalents, the epoxy group and the unreacted hydroxyl group are likely to react with each other. Therefore, a group formed by the addition reaction of the epoxy group and the unreacted hydroxyl group (—CH ₂ CR (OH) CH ₂ —, A high molecular weight product containing R: a hydrogen atom or an organic carbon group is obtained. On the other hand, when it is more than 2.5 equivalents, the content of the theoretical structure becomes high. The amount of epihalohydrin may be appropriately adjusted according to desired characteristics.

  In the above reaction, an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and continuously under reduced pressure or normal pressure. A method may be used in which water and epihalohydrin are distilled off, and further separated to remove water, and epihalohydrin is continuously returned to the reaction system. Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to the dissolved mixture of the polyhydric phenol compound and epihalohydrin and allowed to react at 50 to 150 ° C. for 1 to 5 hours. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product of the phenol resin obtained and reacting again at 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) may be used.

  Furthermore, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide, etc. are used in order to facilitate the reaction. It is preferable to carry out the reaction by adding. The amount of the solvent used is usually 5 to 50% by weight, preferably 10 to 30% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 10-60 weight%. After the epoxidation reaction product is washed with water or without washing with water, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 10 mmHg or less under reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the crude epoxy resin obtained after recovering epihalohydrin or the like is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali such as sodium hydroxide or potassium hydroxide is obtained. An aqueous solution of a metal hydroxide can be added and further reacted to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.5 to 10 mol, preferably 1.2 to 5.0 mol, per 1 mol of hydrolyzable chlorine remaining in the crude epoxy resin. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 3 hours. For the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by weight based on the roughly modified phenol resin. After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain the modified phenolic resin of the present invention.

  Among the modified phenolic resins represented by the general formula (1), a modified phenolic resin etherified with a glycidyl group represented by the following general formula (2) is particularly preferable in terms of flame retardancy and light resistance. Can be used.

（上記式中、Ｒ³は水素原子あるいは炭素数１〜５のアルキル基を表す。）

(In the above formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

The solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution of the (C) modified phenolic resin of the present invention is 30 to 100 mm ² / s, preferably 35 to 90 mm ² / s, particularly 40 to 80 mm. Those of ² / s are preferable because of excellent flame retardancy. Here, the solution viscosity at 25 ° C. of a 50% by weight 1,4-dioxane solution is a 50% by weight solution of the resin using 1,4-dioxane of a modified phenolic resin represented by the general formula (1) as a solvent. Is a kinematic viscosity at 25 ± 0.01 ° C. measured using a Canon-Fenske viscometer in accordance with JISK2283.

  (C) The amount of residual carbide at 600 ° C. measured by TGA when heated at 40 ° C./min in an air atmosphere of a modified phenolic resin is 30% or more, preferably 33% or more, particularly 35% or more. Is preferable because of its excellent flame retardancy.

  The above modified phenolic resins can be used alone or in combination of two or more as required. The shape is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, liquids, and the like can be used.

  The addition amount of the modified phenolic resin (C) is usually 0.1 to 20 parts by weight, preferably 0.5 to 18 parts by weight, more preferably 1 with respect to 100 parts by weight of the rubber-reinforced styrene resin (A). ~ 15 parts by weight. When the amount of the modified phenolic resin (C) added is less than 0.1 parts by weight, a high flame retardancy imparting effect is not seen, which is not preferable. On the other hand, when the amount exceeds 20 parts by weight, impact resistance and heat resistance are deteriorated, and the surface appearance of the molded product is impaired.

  In addition, when the silicone compound (D) is further added to the flame retardant resin composition of the present invention, it is possible to suppress the drop (drip) of the droplets during combustion, to suppress the flame spread during combustion, and to improve the impact resistance. can do.

  The silicone compound (D) used in the present invention is a silicone resin and / or silicone oil.

  The silicone resin used in the present invention is a chemically bonded siloxane unit selected from units represented by the following general formulas (4) to (7) and mixtures thereof (wherein R is saturated or Represents a group selected from an unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or an allyl group.), And has a viscosity of about 200 to 300,000,000 centipoise at room temperature. Although those are preferable, as long as they are the above-mentioned silicone resins, they are not limited thereto.

The silicone oil used in the present invention is represented by the following general formula (8) (wherein R represents an alkyl group or a phenyl group, and n is an integer of 1 or more). The silicone oil to be used preferably has a viscosity of 0.65 to 100,000 centistokes, but is not limited thereto as long as it is the above-described silicone oil.

  As the silicone compound used in the present invention, a silicone resin and / or a silicone oil can be used, and a silicone oil is preferable from the viewpoint of improving flame retardancy and impact resistance.

  The addition amount of the silicone compound (D) is 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, more preferably 0.1 to 100 parts by weight of the rubber-reinforced styrene resin (A). ~ 5 parts by weight.

  Furthermore, the flame retardant resin composition of the present invention is made of glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, wollastonite, glass flake, glass bead, talc, mica, clay as required. In addition, fillers such as calcium carbonate, barium sulfate, titanium oxide and aluminum oxide can be blended. Of these, glass fiber, carbon fiber, and metal fiber can be preferably used, and carbon fiber is most preferable. The type of the fibrous filler is not particularly limited as long as it is generally used for resin reinforcement. For example, the fibrous filler may be selected from long fiber type, short fiber type chopped strand, milled fiber, and the like. it can.

  The surface of the fibrous, powdery, granular or plate filler used in the present invention is a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.), and other surfaces. It can also be used after being treated with a treating agent.

  Further, the glass fiber and the carbon fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, or a thermosetting resin such as a polyurethane resin or an epoxy resin.

Furthermore, ultraviolet absorbers (for example, resorcinol, salicylate, benzotriazole, benzophenone, etc.) and antioxidants (for example, phenol-based, phosphite-based) within the range that does not impair the object of the present invention for the flame-retardant resin composition of the present invention. , Sulfur, thioether, etc.), lubricants and mold release agents (such as montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, stellar amide and ethylene wax), anti-coloring agents (phosphite, hypoxia) Phosphates, etc.), anti-dripping agents (fluorine resins, high molecular weight vinyl copolymers and / or acrylic copolymers having a weight average molecular weight of 5 to 1000 × 10 ⁴ measured by GPC), nucleating agents, Plasticizers, flame retardants, antistatic agents, and colorants including dyes and pigments (cadmium sulfide, phthalocyanine, One or more conventional additives such as titanium oxide can be added.

  Moreover, the flame-retardant resin composition of the present invention is usually produced by a known method. For example, rubber-reinforced styrene resin (A), phosphorus flame retardant (B), modified phenolic resin (C), and other necessary additives are supplied to an extruder or the like with or without premixing. It is prepared by sufficiently melting and kneading in a temperature range of 150 ° C to 350 ° C. In this case, for example, a single-screw extruder, twin-screw or three-screw extruder equipped with a “unimelt” type screw, a kneader type kneader, etc. can be used. It is preferable to use by inserting several elements or not inserting them.

  The flame retardant resin composition of the present invention is not only flame retardant but also excellent in mechanical properties, heat resistance, retention stability and molding processability, and can be melt-molded, so it can be used for extrusion molding, injection molding, press molding, etc. It can be used by forming into a film, a tube, a rod or a molded product having any desired shape and size. Furthermore, taking advantage of flame retardancy, it can be used in various applications such as housings and parts of electrical / electronic parts, automobile parts, mechanical mechanism parts, OA equipment, home appliances and the like.

  For example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards , Tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts ; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, Houses represented by acon parts, typewriter parts, word processor parts, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, cleaning jigs, oilless bearings, stern bearings, Various bearings such as underwater bearings, motor-related parts such as motor parts, lighters and typewriters, optical equipment such as microscopes, binoculars, cameras and watches, precision machine-related parts; alternator terminals, alternator connectors, IC regulators, various valves such as exhaust gas valves, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor space -Exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, Water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wiring harness, window washer nozzle, air conditioner panel switch board, coil for fuel related solenoid valve, fuse connector, horn terminal , Electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, blur For storage devices such as vacuum pistons, solenoid bobbins, engine oil filters, ignition device cases, personal computers, printers, displays, CRT displays, fax machines, copy machines, word processors, notebook computers, mobile phones, PHS, DVD drives, PD drives, flexible disk drives, etc. It is useful for electrical / electronic equipment parts such as housings, chassis, relays, switches, case members, transformer members, coil bobbins, automobile parts, machine parts, and other various applications.

  In order to describe the present invention more specifically, examples and comparative examples will be described below. In addition, the number of parts and% in an Example show a weight part and weight%, respectively.

Reference example 1
(A) Rubber Reinforced Styrene Resin <A-1> Graft (Co) polymer A method for preparing the graft copolymer is shown below. The graft ratio was determined by the following method. Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 4 hours. This solution was centrifuged at 8000 rpm (centrifugal force 10,000 G (about 100 × 10 3 m / s 2)) for 30 minutes, and the insoluble matter was filtered off. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and the weight (n) was measured.
Graft ratio = [(n) − (m) × L] / [(m) × L] × 100
Here, L means the rubber content of the graft copolymer.
In the presence of 60 parts (in terms of solid content) of polybutadiene latex (average rubber particle size 0.3 μm, gel content 85%), 40 parts of a monomer mixture composed of 70% styrene and 30% acrylonitrile was added to carry out emulsion polymerization. The obtained graft copolymer was solidified with sulfuric acid and dried to obtain a powder.
The graft ratio of the obtained graft copolymer was 36%, and it contained 18.1% of a non-graft copolymer consisting of 70% styrene structural units and 30% acrylonitrile. The intrinsic viscosity of the methyl ethyl ketone soluble component was 0.34 dl / g.

<A-2> Preparation of vinyl copolymer <A-2-1>
A monomer mixture composed of 70% styrene and 30% acrylonitrile was subjected to suspension polymerization to prepare a vinyl copolymer <A-2-1>. The obtained vinyl copolymer <A-2-1> had an intrinsic viscosity of 0.53 dl / g of methyl ethyl ketone soluble matter.

<A-2-2>
A monomer mixture composed of 69.7% styrene, 30% acrylonitrile, and 0.3% glycidyl methacrylate was subjected to suspension polymerization to prepare a vinyl copolymer <A-2-2>. The obtained vinyl copolymer <A-2-2> had an intrinsic viscosity of 0.54 dl / g of methyl ethyl ketone soluble matter.

<A-2-3>
A monomer mixture consisting of 51% styrene, 9% acrylonitrile, and 40% N-phenylmaleimide was solution polymerized in a cyclohexanone solvent to prepare a vinyl copolymer <A-2-3>. The obtained vinyl copolymer <A-2-3> had an intrinsic viscosity of 0.59 dl / g of a methyl ethyl ketone-soluble component.

Reference example 2
(B) Phosphorus flame retardant <B-1> Aromatic bisphosphate “PX-200” (manufactured by Daihachi Chemical Co., Ltd.) was used.
<B-2> Oligomer type aromatic bisphosphate “CR733S” (manufactured by Daihachi Chemical Co., Ltd.) was used.

Reference example 3
(C) Modified phenolic resin <C-1> Production method-1-
While purging a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer with nitrogen gas, 104 parts of a phenol novolac resin having a viscosity of 205 mm ² / s of a 50 wt% n-butanol solution at 25 ° C. 0 equivalents), 370 parts (4.0 mol) of epichlorohydrin, 42 parts of n-butanol, and 2.3 parts of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to the azeotropic pressure, and 82 parts (1.0 mol) of 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Continued. During this time, the distillate distilled azeotropically was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 550 parts of methyl isobutyl ketone and 55 parts of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 15 parts of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 100 parts of water was repeated three times until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 144 parts of the desired modified phenolic resin <C-1>. The epoxy equivalent of the resulting modified phenolic resin is 185 g / eq, the solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution is 48 mm ² / s (measured using viscometer number: No. 200), and air The amount of residual carbide at 600 ° C. measured by TGA when the temperature was raised at 40 ° C./min in the atmosphere was 37%.

<C-2> Production method-2-
While purging a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer with a nitrogen gas purge, 104 parts of a phenol novolac resin having a viscosity of 300 mm ² / s at 25 ° C. in a 50 wt% n-butanol solution (hydroxyl group 1. 0 equivalents), 370 parts (4.0 mol) of epichlorohydrin, 42 parts of n-butanol, and 2.3 parts of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to the azeotropic pressure, and 82 parts (1.0 mol) of 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Continued. During this time, the distillate distilled azeotropically was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 550 parts of methyl isobutyl ketone and 55 parts of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 15 parts of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 100 parts of water was repeated three times until the pH of the washing liquid became neutral. Subsequently, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 144 parts of the desired modified phenolic resin <C-2>. The epoxy equivalent of the resulting modified phenolic resin is 186 g / eq, the solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution is 64 mm ² / s (measured using viscometer number: No. 200), and air The amount of residual carbide at 600 ° C. by TGA measurement when the temperature was raised at 40 ° C./min in the atmosphere was 39%.

<C-3> As a comparative example, glycidyl group-modified novolak phenol resin “EPPN-201H” (manufactured by Nippon Kayaku Co., Ltd.) was used. Solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution of the modified phenolic resin <C-3> is 110 mm ² / s (measured using a viscometer number: 300), and 40 ° C. in an air atmosphere. The amount of residual carbide at 600 ° C. measured by TGA when the temperature was raised at a rate of 43 minutes was 43%.

<C-4> As a comparative example, glycidyl group-modified novolak phenol resin “N-730-S” (Dainippon Ink & Chemicals, Inc.) was used. The solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution of the modified phenolic resin <C-4> is 13 mm ² / s (measured using a viscometer number: No. 150). The amount of residual carbide at 600 ° C. measured by TGA when the temperature was raised at 40 ° C./min was 15%.

<C-5> As a comparative example, a bisphenol A type epoxy resin “EPICLON AM-040-P” (manufactured by Dainippon Ink & Chemicals, Inc.) was used. The solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution of the epoxy resin <C-5> is 538 mm ² / s (measured using a viscometer number: No. 400), and 40 ° C./min in an air atmosphere. When the temperature was raised at 600 ° C., the amount of residual carbide at 600 ° C. by TGA measurement was 7%.

<C-6> As a comparative example, a novolac type epoxy resin (manufactured by Aldrich Co., Ltd.) was used. The solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution of the epoxy resin <C-6> is 14 mm ² / s (measured using a viscometer number: No. 150), and 40 ° C./min in an air atmosphere. When the temperature was raised at 600 ° C., the amount of residual carbide at 600 ° C. by TGA measurement was 18%.

<C-7> As a comparative example, a novolac type epoxy resin (manufactured by Aldrich Co., Ltd.) was used. The solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution of the epoxy resin <C-7> is 25 mm ² / s (measured using a viscometer number: No. 150), and 40 ° C./min in an air atmosphere. The amount of residual carbide at 600 ° C. measured by TGA when the temperature was raised at 32 ° C. was 32%.

Reference example 4
(D) Silicone compound <D-1> “DC4-7081” (manufactured by Toray Dow Corning Silicone), which is a silicone resin, was used.

<D-2> Silicone oil “SH200 (1000 cs)” (manufactured by Toray Dow Corning Silicone) was used.

Reference Example 5
Antioxidant “Adekastab AO-412S” (manufactured by Asahi Denka Kogyo Co., Ltd.), which is a thioether-based antioxidant, was used.

[Examples 1-8, Comparative Examples 1-11]
Vented with (A) rubber-reinforced styrene resin, (B) phosphorus flame retardant, (C) modified phenolic resin, and other necessary additives prepared in the reference example at the mixing ratio shown in the table. A pellet-shaped polymer was produced by performing melt kneading and extrusion at 220 to 270 ° C. using a 30 mmφ twin-screw extruder (Ikegai Iron Works, PCM-30). Next, each test piece was molded with an injection pressure (lower limit pressure + 1 MPa) using an injection molding machine (manufactured by Sumitomo Heavy Industries, Promat 40/25), and the physical properties were measured under the following conditions.

(1) Flame retardancy: Flame retardancy was evaluated for five test pieces in accordance with the evaluation standard defined in UL94 for the 1.6 mm thick flame retardance evaluation test piece obtained by injection molding. The flame retardancy level decreases in the order of V-0> V-1> V-2> HB.

(2) Impact resistance: Impact resistance was evaluated according to ASTM D256-56A.

(3) Heat resistance: Heat resistance was evaluated according to ASTM D648 (load: 1.82 MPa).

(4) Color tone: The color tone of the test piece was visually judged. (○: white, △: light yellow, ×: yellow)

  Table 1 summarizes the measurement results of flame retardancy, impact resistance, heat resistance, and color tone of each sample.

  As can be seen from Example 1 and Example 2, the burning time can be shortened by using a part of the ABS resin as an epoxy group-modified vinyl copolymer and a maleimide group-modified vinyl copolymer. In addition, it can be seen that the impact resistance is greatly improved and the heat resistance is also improved.

  From the measurement results of Comparative Examples 1 to 3, flame retardancy cannot be obtained at all by simply adding a phosphorus flame retardant to the ABS resin.

  On the other hand, from the measurement results of Examples 1 to 5, the modified phenolic resins <C-1> and <C- of the present invention together with the phosphorus flame retardant <B-1> or <B-2> with respect to the ABS resin. By adding 2>, flame retardancy is improved, and a resin composition having good impact resistance, heat resistance, and color tone is obtained.

  From the comparison between Example 2 and Example 6, the ABS resin was changed to a flame retardant resin composition comprising a modified phenolic resin <C-1> together with a phosphorus flame retardant <B-1>, and a silicone resin ( It can be seen that the addition of D-1) not only shortens the combustion time but also improves the impact resistance. Furthermore, from comparison with Example 7, it can be seen that when silicone oil (D-2) is added, the reduction in combustion time is small, but the impact resistance is greatly improved.

  Furthermore, from the comparison between Example 2 and Example 8, with respect to the ABS resin, the flame retardant resin composition comprising the modified phenolic resin <C-1> together with the phosphorus flame retardant <B-1>, and further oxidation prevention It can be seen that the combustion time is greatly shortened by adding the agent.

  As a result of comparison between Example 2 and Comparative Example 4, when modified phenolic resin <C-3> having a solution viscosity outside the scope of the present invention was used, not only the combustion time was greatly extended, but also impact resistance. It can be seen that the property also decreases.

  Furthermore, by comparison between Example 2 and Comparative Examples 5 to 7, modified phenolic resins <C-4> to <C-6 having a solution viscosity outside the range of the present invention and a residual amount of 600 ° C. of 30% or less. When> is used, it can be seen that not only the test piece is dripped during combustion but the flame retardancy is significantly reduced, and the heat resistance is remarkably lowered.

  Further, according to the comparison between Example 2 and Comparative Example 8, the residual amount of 600 ° C. is 30% or more, but when a modified phenolic resin <C-7> having a solution viscosity outside the scope of the present invention is used, It can be seen that not only the test piece dripping during combustion cannot be suppressed, but also the heat resistance is lowered.

  According to the comparison between Example 2 and Comparative Example 9, when a large amount of the modified phenolic resin <C-1> is added, not only the test piece is dripped but the flame retardancy is lowered, and the mechanical properties are remarkably lowered. I understand that.

  According to the comparison between Example 2 and Comparative Example 10, the flame retardancy is not obtained when no phosphorus flame retardant is added, and the flame retardancy is added when a large amount of phosphorus flame retardant is added as in Comparative Example 11. However, the mechanical properties are significantly reduced and the material becomes impractical.

Claims (8)

1 to 30 parts by weight of a phosphorus-based flame retardant (B) and 0.1 parts of a modified phenolic resin (C) represented by the following general formula (1) with respect to 100 parts by weight of the rubber-reinforced styrene resin (A) A flame retardant resin composition comprising a resin composition comprising ˜20 parts by weight, wherein the modified phenolic resin (C) represented by the following general formula (1) satisfies the following conditions: .
(A) Solution viscosity at 25 ° C. of a 50 wt% 1,4-dioxane solution is 30 to 100 mm ² / s
(B) The amount of residual carbide at 600 ° C. is 30% or more by TGA measurement when the temperature is raised at 40 ° C./min in an air atmosphere.

(In the above formula, R ¹ represents an organic residue having 1 to 10 carbon atoms. R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) The flame retardant resin composition according to claim 1, wherein the modified phenolic resin (C) is a modified phenolic resin represented by the following general formula (2).

(In the above formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) The flame retardant resin composition according to claim 1 or 2, wherein the phosphorus-based flame retardant (B) is represented by the following general formula (3).

(In the above formula, R ^{4 to} R ¹¹ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same or different phenyl groups or Y represents a phenyl group substituted with a halogen-free organic residue, Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group. In addition, n is an integer of 0 or more and may be a mixture of different n. K and m are each an integer of 0 to 2, and k + m is an integer of 0 to 2.   A graft polymer or copolymer (A-1) obtained by graft-polymerizing a rubber-reinforced styrene resin (A) with a monomer or monomer mixture containing an aromatic vinyl monomer to a rubber polymer. From 10 to 100% by weight, and from 0 to 90% by weight of a vinyl polymer or copolymer (A-2) obtained by polymerizing a monomer or monomer mixture containing an aromatic vinyl monomer. The flame-retardant resin composition according to any one of claims 1 to 3, wherein   The flame retardant resin composition according to claim 4, wherein the vinyl polymer or copolymer (A-2) contains a maleimide group-modified vinyl copolymer.   The flame retardant resin composition according to claim 5, wherein the vinyl polymer or copolymer (A-2) contains a glycidyl group-modified vinyl copolymer.   The flame retardant resin composition according to any one of claims 1 to 6, further comprising 0.01 to 10 parts by weight of a silicone compound (D) with respect to 100 parts by weight of the rubber-reinforced styrene resin (A). object.   The molded article which consists of a flame-retardant resin composition in any one of Claims 1-7.