JP2002173581A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant thermoplastic resin composition having excellent flame resistance. SOLUTION: This flam-retardant thermoplastic resin composition has far advanced high-level flame resistance and excellent impact resistance and is obtained by compounding (A) 100 pts.wt. thermoplastic resin containing >=50 wt.% one or more kinds selected from thermoplastic polyester-based resins, polyphenylene ether-based resins and thermoplastic polyamide-based resins, with a combination of (B) 0.5-30 pt(s). wt. silicon resin having a T unit or a Q unit and (C) 0.5-40 pt(s).wt. condensed polycyclic aromatic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant resin composition using a non-halogen flame retardant. Further, when a reinforcing filler is blended, the impact resistance is excellent.

[0002]

2. Description of the Related Art Thermoplastic polyester resins, polyphenylene ether resins, and thermoplastic polyamide resins are:
Taking advantage of its excellent properties, it is being used in a wide range of fields as an injection molding material. However, since these thermoplastic resins are inherently flammable, it is necessary to impart flame safety, that is, flame retardancy, in addition to the general balance of chemical and physical properties in order to use them as industrial materials. was there. In addition, since it has been strongly desired to use a flame retardant containing no halogen in consideration of the environment, silicone compounds and condensed polycyclic aromatic resins have been used as a method of making these thermoplastic resins flame retardant. Attention has been paid to a method using. For example, JP-A-10-139964
JP-A 54-36365, JP-A 54-36365
No. 25000 proposes a technique for adding a silicone resin, and JP-A-2000-53867 proposes a condensed polycyclic aromatic.

[0003] Further, Japanese Patent No. 2755240 discloses a polycarbonate-based resin composition flame-retarded by specific petroleum heavy oils or pitches and a silicone-based resin.

[0004]

However, the thermoplastic polyester-based resin, polyphenylene ether-based resin, and thermoplastic polyamide-based resin obtained by these techniques have difficulty in practical use which can be used for electric and electronic parts. It did not lead to flammability.

[0005]

The inventors of the present invention have as a first invention (A) a thermoplastic polyester resin, a polyphenylene ether resin, a thermoplastic polyamide resin, a silicone resin having a specific structure, It has been found that by using a specific amount of a condensed polycyclic aromatic resin in a specific ratio, a resin material having practically excellent flame retardancy can be obtained, and the present invention has been achieved. As a second invention, a flame-retardant thermoplastic resin composition having impact resistance when a specific amount of a reinforcing filler is added is obtained.

That is, a first aspect of the present invention is that (A) 100 parts by weight of a thermoplastic resin containing 50% by weight or more of at least one selected from thermoplastic polyester resins, polyphenylene ether resins, and thermoplastic polyamide resins. for,
(B) 0.5 to 30 parts by weight of a silicone resin having a T unit or a Q unit, (C) 0.5 of a condensed polycyclic aromatic resin
The present invention relates to a flame-retardant thermoplastic resin composition containing about 40 parts by weight.

A second aspect of the present invention is that (A) 100 parts by weight of a thermoplastic resin containing 50% by weight or more of at least one selected from a thermoplastic polyester resin, a polyphenylene ether resin, and a thermoplastic polyamide resin. And (B)
Silicone resin having T unit or Q unit 0.5
To 30 parts by weight, (C) condensed polycyclic aromatic resin 0.5 to 40
Part (D) relates to a flame-retardant thermoplastic resin composition comprising 1 to 150 parts by weight of a reinforcing filler.

In a preferred embodiment, the thermoplastic resin (C) is obtained by polycondensing heavy oils or pitches and an aldehyde compound in the presence of an acid catalyst. It relates to a resin composition.

In a further preferred embodiment, (B) T
In the silicone resin having a unit or a Q unit, 80 mol% or more of all the organic groups are a methyl group and a phenyl group, and the molar ratio of phenyl group: methyl group is 1: 4 to
The ratio according to any one of the above, wherein the ratio of the components soluble in methyl isobutyl ketone at 23 ° C. is 80% by weight or more and the number average molecular weight of the soluble components is 1500 or more. The present invention relates to a flame-retardant thermoplastic resin composition.

In a further preferred embodiment, (B) T
The silicone resin having a unit or a Q unit is Si
The flame-retardant thermoplastic resin composition according to any one of the above, wherein the total of the alkoxy groups and the hydroxyl groups directly bonded to the atoms is a molar ratio of 3/20 or less based on all the organic groups.

In a further preferred embodiment, (B) T
The addition ratio of the silicone resin having a unit or a Q unit and the (C) condensed polycyclic aromatic resin is 0.1% by weight.
The present invention relates to the flame-retardant thermoplastic resin composition according to any one of the above, wherein the ratio is 5:10 to 5: 1.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition of the present invention will be specifically described below.

The thermoplastic polyester resin composition used in the component (A) of the present invention is obtained by polycondensing a divalent or higher carboxylic acid component, a divalent or higher valent alcohol and / or phenol component by a known method. Is a thermoplastic polyester obtained by Specific examples of the thermoplastic polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. Among these thermoplastic polyesters, heat resistance,
From the viewpoint of moldability, polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate are preferred.

As the divalent or higher valent aromatic carboxylic acid component, a divalent or higher valent aromatic carboxylic acid having 8 to 22 carbon atoms, or an ester-forming derivative thereof is used. Specific examples of these include phthalic acid such as terephthalic acid and isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methaneanthracene dicarboxylic acid,
4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, diphenylsulfonedicarboxylic acid, trimesic acid, trimellitic acid,
Examples thereof include carboxylic acids such as pyromellitic acid, and derivatives thereof having an ester forming ability. These are used alone or in combination of two or more. Preferred are terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. This is because they are excellent in ease of handling, ease of reaction, physical properties of the obtained resin, and the like.

The dihydric or higher alcohol and / or phenol component includes aliphatic compounds having 2 to 15 carbon atoms, alicyclic compounds having 6 to 20 carbon atoms, and aromatic compounds having 6 to 40 carbon atoms. And compounds having two or more hydroxyl groups therein, as well as ester-forming derivatives thereof. Specific examples of such alcohol and / or phenol components include ethylene glycol, propylene glycol, butanediol, hexanediol,
Decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2 '
-Bis (4-hydroxyphenyl) propane, 2,2 '
Compounds such as -bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and the like, and derivatives thereof having an ester-forming ability are exemplified. Preferred alcohol and / or phenol components are ethylene glycol, butanediol,
Cyclohexanedimethanol. Ease of handling,
This is because the easiness of the reaction, the physical properties of the obtained resin, and the like are excellent.

The thermoplastic polyester resin used in the component (A) of the present invention may be any of known copolymerizable copolymers other than the above-mentioned acid component and alcohol and / or phenol component as long as the desired properties are not impaired. The components may be copolymerized. Examples of such copolymerizable components include carboxylic acids such as divalent or higher valent aliphatic carboxylic acids having 4 to 12 carbon atoms, divalent or higher valent alicyclic carboxylic acids having 8 to 15 carbon atoms, and esters thereof. Forming derivatives. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and other dicarboxylic acids, and esters thereof. Derivatives having the same.

Also, oxyacids such as p-oxybenzoic acid and p-hydroxybenzoic acid and their ester-forming derivatives, cyclic esters such as ε-caprolactone, and the like can be used as the copolymerization component. Furthermore, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) blocks and / or random copolymers, bisphenol A copolymerized polyethylene oxide addition polymers, propylene oxide addition polymers, tetrahydrofuran addition polymers, polytetraethylene A polymer obtained by partially copolymerizing a polyalkylene glycol unit such as methylene glycol in a polymer chain can also be used. As the copolymerization amount of the above components,
It is generally at most 20% by weight, preferably at most 15% by weight, more preferably at most 10% by weight.

The thermoplastic polyester resin used in the component (A) of the present invention contains an alkylene terephthalate unit in an amount of preferably 80% by weight or more, more preferably 85% by weight or more.
It is a polyalkylene terephthalate having at least 90% by weight, most preferably at least 90% by weight. This is because the obtained composition has an excellent balance of physical properties (eg, moldability, mechanical properties).

The logarithmic viscosity (IV) of the thermoplastic polyester resin used in the component (A) of the present invention measured at 25 ° C. in a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solvent is as follows: Preferably 0.30 to 2.0
0 dl / g or more, preferably 0.40 to 1.80.
dl / g, more preferably 0.50 to 1.60 dl /
g. If the logarithmic viscosity is less than 0.30, the mechanical strength of the molded article is often insufficient, and if it exceeds 2.00 dl / g, the moldability tends to decrease.

The thermoplastic polyester resin used in the component (A) of the present invention may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination is not limited. For example, those having different copolymer components and different molar ratios and / or those having different molecular weights are arbitrarily combined.

The polyphenylene ether resin used in the component (A) of the present invention comprises, as a main component, a single monomer or a copolymer having a repeating unit represented by the following general formula (1) and / or (2). Is a thermoplastic resin.

[0022]

Embedded image

[0023]

Embedded image (Wherein, R 1, R 2, R 3, R 4, R 5, and R 6 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Except when R5 and R6 both represent a hydrogen atom.) The polyphenylene ether homopolymer is not particularly limited, and typical examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether,
Poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-)
1,4-phenylene) ether, poly (2-methyl-6)
-Hydroxyethyl-1,4-phenylene) ether and the like. On the other hand, the polyphenylene ether-based copolymer (copolymer having a phenylene ether structure as a main unit) is not particularly limited, and examples thereof include 2,6-dimethylphenol and 2,3,6-trimethylphenol. A copolymer of 2,6-dimethylphenol and o-cresol, 2,6-dimethylphenol and 2,
And copolymers of 3,6-trimethylphenol and o-cresol.

The thermoplastic polyamide resin used in the component (A) of the present invention includes nylon 6, nylon 66, nylon 11, nylon 12, and the like, and may be a mixture or copolymer thereof.

The thermoplastic resin (A) used in the present invention is selected from thermoplastic polyester resins, polyphenylene ether resins, and thermoplastic polyamide resins.
One or more kinds of other thermoplastic resins or thermosetting resins may be used insofar as the properties (flame retardancy, impact resistance, etc.) are not impaired as long as they contain at least 50% by weight of at least one kind. They may be used in combination. Such resins are not particularly limited, and include, for example, polycarbonate resins, ABS resins, polystyrene resins, liquid crystal polyester resins, polyester ester elastomer resins, polyester ether elastomer resins, polyolefin resins, polyphenylene sulfide resins, polyacetals. Resins, polysulfone resins, and the like.

The (B) silicone resin used in the present invention has a three-dimensional knit structure having a T unit represented by the following general formula (3) and / or a Q unit represented by the following formula (4). It is a silicone resin, and D units (R2 SiO2 / 2) and M units (R3 SiO1 / 2) can be used as required, such as molecular weight control and characteristics. Formula 3: RSiO3 / 2 (3) Formula 4: SiO4 / 2 (4) In the formula, R represents 1 carbon atom modified with a reactive group selected from an epoxy group, a hydroxyl group, a vinyl group, an acrylic group, and a methacryl group. To 16 modified alkyl groups or 1 to 10 carbon atoms
Represents a monovalent hydrocarbon group. When a plurality of Rs are included, they may be the same or different.

In general, a silicone resin has an alkyl group,
Although it has a hydrocarbon-based organic group such as an aromatic group, the silicone-based resin (B) used in the present invention has a phenyl group and a methyl group in which at least 80 mol% of all organic groups are economically economical. In order to control the phase structure of the resin composition for effectively exhibiting the effects of the present invention, the molar ratio of phenyl group: methyl group is preferably 1: 4 to 7: 3, and further, Preferably, the phenyl group and the methyl group are at least 85 mol%, and the molar ratio is from 1: 3 to 3: 2. The ratio of phenyl group: methyl group is 0: 1 to 1: 4
Or, when the ratio is 7: 3 to 1: 0, the moldability of the obtained thermoplastic resin composition is reduced, the appearance is poor, and the effect of the present invention (flame retardancy or impact resistance) cannot be obtained. Because there is.

In the silicone resin (B) used in the present invention, the component soluble in methyl isobutyl ketone at 23 ° C. is 80% by weight or more, and the number average molecular weight of the soluble component is 1500 or more. It is more preferable that 85% by weight or more is soluble and the number average molecular weight of the soluble component is 2000 or more. It contains insoluble components exceeding 20% by weight or has a number average molecular weight of 150.
If it is less than 0, the effect of the present invention may not be obtained.

The structure of the silicone resin (B) used in the present invention is represented by the above general formula (3), which is a structural unit, from the viewpoint of physical property balance (moldability, mechanical properties, flame retardancy, etc.). The total of the units and / or the units represented by the above formula (4) is preferably at least 20 mol%, more preferably at least 30 mol%.

The structure of the silicone resin (B) used in the present invention is such that an alkoxy group directly bonded to a Si atom is preferred in view of thermal stability and physical balance (moldability, impact resistance, flame retardancy, etc.). And the total of the hydroxyl groups is preferably not more than 3/20 in terms of molar ratio with respect to all organic groups,
More preferably, it is 10 or less.

The unit (B) other than the general formulas (3) and (4) of the silicone resin used in the present invention may be a unit for sealing a terminal reactive group such as a silanol group or an alkoxy group. , M units (R ₃ SiO _1/2 ) can be used. Other constituent units of the thermoplastic silicone resin used for the component (B) include a D unit (R ₂ SiO _2/2 ), but can be used as long as the effects of the present invention are not impaired. The ratio, the organic substituent and the like are not particularly limited.

The method for producing the silicone resin (B) used in the present invention may be any of various known methods. For example, a dehydration condensation reaction following hydrolysis of alkoxysilanes such as methyltrialkoxysilane, trimethylalkoxysilane, phenyltrialkoxysilane, triphenylalkoxysilane, and tetraalkoxysilane and an alkoxysilane represented by the following general formula (5), Hydrolysis of chlorosilanes such as methyltrichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, triphenylchlorosilane, and dimethylphenylchlorosilane, followed by a dehydration condensation reaction, and a commercially available silicate oligomer having a silanol group, or neutralized water glass under strong acid to obtain It can be produced by any method such as a dehydration condensation reaction between the obtained silicate having a silanol group and the above-mentioned alkoxysilanes and chlorosilanes. Formula 5: R ⁷ _a R ⁸ _b Si (—OR ⁸ ) _4-n (5) (wherein R ⁷ is modified with a reactive group selected from an epoxy group, a hydroxyl group, a vinyl group, an acrylic group, and a methacryl group) indicates the modified alkyl group having 1 to 16 carbon atoms, R7 is sometimes a plurality may be the same or different, R ⁸ is a carbon number 1
Represents a monovalent hydrocarbon group of 10 to 10, and when there are a plurality of R ^{8 s} , they may be the same or different. In the formula, n represents an integer of 1, 3; a represents an integer of 1, 2, 3; b represents an integer of 0, 1, 2; and n = a + b. The silicone resin (B) used in the present invention may be used alone or in combination of two or more. 2
When used in combination of more than one kind, the combination is not limited. For example, as long as the object of the present invention is not inhibited,
Those having different polymerization components, different molar ratios, and different molecular weights can be arbitrarily combined. The silicone resin used for the component (B) is not particularly limited in shape as long as the object of the present invention is not impaired, and may be any of oil, gum, varnish, powder, pellet, and the like. Things are available.

In the present invention, the amount of the silicone resin having (B) a T unit or a Q unit is one kind selected from (A) a thermoplastic polyester resin, a polyphenylene ether resin, and a thermoplastic polyamide resin. The amount is 0.5 to 30 parts by weight, preferably 0.7 to 100 parts by weight of a thermoplastic resin containing 50% by weight or more of the above.
If it is 5 to 25 parts by weight, more preferably 1 to 20 parts by weight, and if it is less than 0.5 part by weight, the resulting molded article will not have flame retardancy and impact resistance. On the other hand, if it exceeds 30 parts by weight, the appearance of the molded product and the processability of the molded product are reduced.

The condensed polycyclic aromatic resin (C) used in the present invention is a polymer having a structure in which heavy oils or pitches are crosslinked mainly via a methylene group. Pitches and polycondensates of formaldehyde compounds and heavy oils or pitches and polycondensates of formaldehyde compounds and phenols are exemplified. The condensed polycyclic aromatic resin is produced by polycondensing heavy oils or pitches with a formaldehyde compound in the presence of an acid catalyst. In the case of a modified phenol resin, it is produced by polycondensing heavy oils or pitches and a formaldehyde compound with phenols in the presence of an acid catalyst.

As the heavy oils or pitches used as a raw material in such a polycondensation reaction, any of petroleum-based and coal-based raw oils may be used. Petroleum heavy oils or pitches include crude oil distillation residue, hydrogenolysis residue, catalytic cracking residue, catalytic reforming residue, naphtha or LPG
And the distillates under reduced pressure of these residual oils, extracts or heat-treated products obtained by solvent extraction, and specific distillates obtained in cracking steps such as thermal cracking and catalytic cracking in petroleum refining processes. Examples of the coal-based heavy oils or pitches include a specific fractionated component obtained by distilling coal tar in coal dry distillation, heavy oil in coal liquefaction, and the like.

In the case of petroleum heavy oils or pitches, it is preferable to select and use an appropriate aromatic hydrocarbon fraction fa value and aromatic ring hydrogen amount Ha value. For example, petroleum heavy oils or pitches are 0.40 to 0.95, preferably 0.5 to 0.8, more preferably 0.55 to 0.8.
A fa value of 0.75 and 20-80%, preferably 25-6
It is desirable to have a Ha value of 0%, more preferably 25-50%. The fa value and the Ha value are calculated from the data obtained by ¹³ C-NMR measurement and the data obtained by ¹ H-NMR of petroleum heavy oils or pitches, respectively, based on the following formula. Fa value = Aromatic carbon number / Total carbon number Ha value = Aromatic hydrogen number / Total hydrogen number × 100 Fa value of petroleum heavy oil or pitch as raw material is 0.4.
If the particle size is smaller, the aromatic component is reduced, so that the effect of modifying the obtained resin, particularly the effect of improving the flame retardancy, tends to be reduced.

In the case of petroleum heavy oils or pitches having a fa value larger than 0.95, the reactivity between aromatic carbon and formaldehyde tends to be low. If the Ha value of the raw petroleum heavy oils or pitches is less than 20%, the amount of aromatic ring hydrogen that reacts with formaldehyde decreases, and the yield of condensed polycyclic aromatic resin or modified phenol resin tends to decrease. There is.

When a petroleum heavy oil or a pitch having a Ha value of more than 80% is used as a raw material, the resulting resin has a very high softening point, which tends to deteriorate the moldability of the resin.

The fractionated component obtained by distillation of coal tar described above as a coal-based raw material is a fractionated component having a boiling point exceeding 200 ° C., preferably a boiling point of 200 to 360 ° C.
In the present invention, coal tar as a raw material of a fractionation component used as coal-based heavy oils or pitches is not particularly limited, but from the viewpoint of a high content of a desired fractionation component, a coke oven is particularly preferred. High temperature tars such as tars are preferred.

By distillation of coal tar, various fractionated components can be obtained. Among them, the fractionated components having a boiling point exceeding 200 ° C. are naphthalene oil, absorbent oil, heavy oil, anthracene oil and pitch.

As the heavy coal oils or pitches, such fractionated components having the above-mentioned boiling points may be used alone or in combination of two or more. Further, a specific component may be separated and recovered from the mixture of these fractionated components and then remixed.For example, a mixture of fractions having a boiling point equal to or higher than naphthalene oil may be used, and naphthalene, anthracene, tar acids and tar bases Etc.
Creosote oil obtained by recovery can also be used.

However, coal-based (coal-tar) heavy oils or pitches generally have higher fa and Ha values than petroleum-based heavy oils, but do not react with formaldehyde compounds. From the progress, it is presumed that the coal-based feedstock has a fundamental difference in reactivity with a formaldehyde compound based on the molecular structure.

When a fractionated component having a boiling point of 200 ° C. or less is used, the amount of the condensed polycyclic aromatic component contained in the raw material oil is small, the reactivity is reduced, and the flame retardancy of the obtained resin is reduced. Tends to decrease the reforming effect.

In the present invention, heavy oil produced by coal liquefaction can also be used as the heavy coal oils or pitches. May be used in admixture with one or more of the above coal tar fractionation components.

The coal-based heavy oils or pitches described above are products that are stably produced in a common process in the coal chemical industry. Can be supplied.

The coal-based heavy oils or pitches are
This may be used as it is, but it may contain acidic compounds such as phenols and carboxylic acids and basic compounds such as carbazoles, pyridines, anilines and quinolines, and these are removed. It is desirable.

The removal of such acidic compounds and basic compounds can be carried out, for example, by extraction with sulfuric acid or caustic soda. The petroleum-based and coal-based heavy oils or pitches described above are not particularly limited in the number of condensed aromatic hydrocarbons constituting the heavy oils or pitches, but are mainly 2 to 6 condensed polycyclic aromatic hydrocarbons. It is preferred to be constituted.

Further, these heavy oils or pitches are:
This may be used as it is in the polycondensation reaction, but a low-reactivity paraffin fraction, that is, having 15 to 4 carbon atoms including normal paraffin, isoparaffin, cycloparaffin and the like.
It may be used after performing the treatment for removing the saturated hydrocarbon fraction of 0.

The removal treatment of the paraffin fraction is as follows:
For example, according to a conventional method, using furfural, 80 ° C. to 1
The reaction can be carried out at 20 ° C. or by column chromatography.

By performing such a paraffin fraction removal treatment, the yield of the condensed polycyclic aromatic resin or the modified phenol resin can be improved, and unreacted components contained in the reaction mixture after the polycondensation reaction are obtained. Can be reduced and the purification process can be facilitated.

In the production of the (C) condensed polycyclic aromatic resin used in the present invention, the formaldehyde compound used together with such heavy oils or pitches acts as a crosslinking agent, and in particular, paraformaldehyde and formalin ( Concentration of 35% or more).

In the production of the (C) condensed polycyclic aromatic resin used in the present invention, such a formaldehyde compound is converted into formaldehyde in terms of formaldehyde with respect to 1 mol of heavy oils or pitches calculated from the average molecular weight. , 0.2 mol or more, preferably 0.5 mol or more, and 15 mol or less, preferably 10 mol or less, more preferably 5 mol or less.
It is desirable to use it in an amount of not more than mol.

When the amount of the formaldehyde compound is less than 0.2 mol per 1 mol of the heavy oils or pitches, the yield of the resin tends to decrease, and the performance of the obtained resin tends to decrease.

On the other hand, when it is more than 15 mol, the obtained condensed polycyclic aromatic resin or modified phenol resin is polymerized, and not only a desired viscosity cannot be obtained, but also the reaction mixture solidifies extremely. Sometimes.

The condensed polycyclic aromatic resin (C) used in the present invention can be obtained by polycondensing such heavy oils or pitches with a formaldehyde compound. A modified phenolic resin using the same may be used.

Examples of such phenols include hydroxybenzene compounds and hydroxynaphthalene compounds. As hydroxybenzene compounds,
Examples include phenol, cresol, xylenol, resorcin, hydroquinone, catechol, phenylphenol, vinylphenol, nonylphenol, p-tert-butylphenol, bisphenol A, bisphenol F and the like. Examples of the hydroxynaphthalene compound include monohydroxynaphthalene compounds such as α-naphthol and β-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-
Dihydroxynaphthalene and 2,3-dihydroxynaphthalene, 3,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-
Dihydroxynaphthalene compounds such as dihydroxynaphthalene, and the above mono- or dihydroxynaphthalene compounds having a substituent such as an alkyl group or an aromatic group, for example, 2-
Examples thereof include methyl-1-naphthol and 4-phenyl-1-naphthol. These phenols may be used alone or in combination of two or more.

By dropping phenols, the molecular weight can be controlled, and the moldability of the resulting modified phenolic resin composition can be further improved. The lower limit of such phenols is not particularly limited with respect to 1 mol of heavy oils or pitches calculated from the average molecular weight, but is not more than 10 mol, preferably not more than 7 mol, more preferably not more than 5 mol. It is desirable to use it.

When the amount of phenols exceeds 10 mol, the effect of reforming with heavy oil or pitch tends to be small. An acid catalyst is used for the polycondensation of heavy oils or pitches, a formaldehyde compound and optionally added phenols. As such an acid catalyst, a Bronsted acid or a Lewis acid can be used, but a Bronsted acid is preferably used.
Examples of Bronsted acids include organic acids such as oxalic acid, toluenesulfonic acid, xylenesulfonic acid and formic acid, inorganic acids such as hydrochloric acid and sulfuric acid, and solid acids such as acidic cation exchange resins.

Among such Bronsted acids, oxalic acid, toluenesulfonic acid, and sulfuric acid are preferable as the organic acid and the inorganic acid. The acidic cation exchange resin used as the solid acid is a resin in which a cation exchange group is covalently bonded to a base resin having a three-dimensional network structure.

When such a solid acid is used as an acid catalyst, since the acid is not contained in a free state in the reaction mixture, the solid acid is removed from the polycondensation reaction product by a simple method such as filtration. Thus, there is an advantage that a condensed polycyclic aromatic resin or a modified phenol resin containing substantially no acid can be obtained.

The acid catalyst is used in an amount of 0.01 mol or more based on 1 mol of heavy oils or pitches calculated from the average molecular weight.
And it is desirable that it is used in an amount of 3 mol or less, preferably 2.5 mol or less, more preferably 2 mol or less. When an acidic cation exchange resin is used as the acid catalyst, the amount of the acid catalyst is an amount in terms of a cation exchange group.

The modified phenol resin of the condensed polycyclic aromatic resin (C) used in the present invention is obtained by heating and stirring the above-described specific amounts of heavy oils or pitches, formaldehyde compound and acid catalyst while heating. It can be produced by sequentially adding a specific amount of phenols and performing a polycondensation reaction.

In such a polycondensation reaction of heavy oils or pitches, formaldehyde compounds and optionally added phenols in the presence of an acid catalyst, the raw materials are adjusted according to the raw material composition and the properties of the obtained resin. The mixing temperature and the mixing time, and the polycondensation reaction temperature and the reaction time are controlled. It goes without saying that the reaction temperature and the reaction time also affect each other.

Such a polycondensation reaction can be carried out, for example, by the following method. That is, first, the specific amount of the heavy oils or pitches, the formaldehyde compound and the acid catalyst are stirred at a specific temperature, for example, 50 to 50.
The temperature is gradually raised to a temperature of 140 ° C, preferably 60 to 120 ° C, more preferably 80 to 100 ° C, for 30 minutes to 8 hours.
The polycondensation reaction is performed for a time, preferably 30 minutes to 6 hours.

The sequential addition of the phenols is carried out successively at a rate of from 0.001% to 8% by weight, preferably from 0.01% to 5% by weight, based on the total weight of the reaction mixture. It is desirable to add.

When the rate of addition is less than 0.001% by weight / minute, the time required for addition is too long, and the cost increases. On the other hand, if the rate of addition exceeds 8% by weight / minute, the added phenol rapidly reacts with free formaldehyde, so that it is difficult to form a uniform mixture or polycondensate.

(C) In the production of the condensed polycyclic aromatic resin, the reaction of such a polycondensation raw material can be carried out without using a solvent, but the reaction mixture (reaction system) is prepared using an appropriate solvent. May be reduced so that a uniform reaction occurs.

Examples of such a solvent include nitrated aromatic hydrocarbons such as nitrobenzene; nitrated aliphatic hydrocarbons such as nitroethane and nitropropane;
Halogenated aliphatic hydrocarbons such as perchrene, trichlene and carbon tetrachloride; and aromatic hydrocarbons such as benzene, toluene and para-xylene can be mentioned.

The condensed polycyclic aromatic resin (C) used in the present invention may have an unreacted component or an acid catalyst remaining in the resin. It is desirable to remove molecular components, acid catalysts, reaction solvents and the like.

As a method for purifying a reaction mixture, that is, a crude condensed polycyclic aromatic resin containing an acid catalyst, unreacted materials, low molecular components and a reaction solvent, for example, (i) removing unreacted components from the reaction mixture A purification treatment and (ii) a purification treatment for removing a catalyst residue from the reaction mixture can be exemplified. If phenols are used as desired,
(Iii) A purification treatment for removing residual phenols by any of steam distillation, nitrogen gas blowing and vacuum distillation may be performed.

In the refining treatment (i), of the components contained in the heavy oils or pitches used as a raw material, the reactivity is low, and the reaction product is in an unreacted state or in an insufficiently reacted state. The remaining components and the reaction solvent appropriately used during the reaction are removed.

In the above-mentioned purification treatment (ii), the acid catalyst remaining in the reaction mixture is removed, and a condensed polycyclic aromatic resin substantially containing no acid is obtained. Further purification treatment (iii)
In the above, by removing the unreacted components and the acid catalyst and the like in the reaction mixture as it is or in the purification treatment (i) and / or the purification treatment (ii), steam distillation, blowing of nitrogen, or distillation under reduced pressure is performed. The remaining unreacted phenols are removed.

The purification treatments (i), (ii) and (iii)
May be used as a method for purifying a modified phenol resin, for example, any of the methods described in
29823, JP-B-6-89092, JP-A-7-2966, JP-A-8-247616, JP-A-9-95597, etc. It can be changed and applied as needed.

In the present invention, the amount of the condensed polycyclic aromatic resin (C) to be added is (A) a thermoplastic polyester resin,
0.5 to 40 parts by weight, preferably 1 to 35 parts by weight, based on 100 parts by weight of a thermoplastic resin containing 50% by weight or more of one or more selected from a polyphenylene ether-based resin and a thermoplastic polyamide-based resin. More preferably, it is 2 to 30 parts by weight, and if it is less than 0.5 part by weight, the flame retardancy of the obtained molded product cannot be obtained. On the other hand, if it exceeds 30 parts by weight, the appearance of the molded product, the formability and the heat resistance are reduced.

In the present invention, the proportions of (B) the silicone resin having a T unit or a Q unit and (C) the condensed polycyclic aromatic resin are set so that the flame retardancy can be made effective.
The weight ratio is preferably 0.5: 10 to 5: 1, and more preferably 1: 0.5.
More preferably, the ratio is 10 to 4: 1.

In the present invention, the total amount of (B) the silicone resin having a T unit or a Q unit and (C) the condensed polycyclic aromatic resin is not particularly limited as long as it is within the scope of the claims. However, it is 2-50 in terms of economic and physical balance.
Part.

Further, the flame-retardant resin composition of the present invention further comprises (D) a reinforcing material used in combination with a reinforcing filler in order to further improve heat resistance, mechanical strength and the like. Little decrease in impact resistance due to addition of reinforcing filler.

The reinforcing filler (D) used in the present invention includes, for example, fibrous fillers such as glass fiber, carbon fiber and potassium titanate fiber; glass beads, glass flakes; talc, mica, kaolin, and wollast. Silicate compounds such as knight, smectite and diatomaceous earth; calcium carbonate, calcium sulfate, barium sulfate and the like. Of these, silicate compounds and fibrous fillers are preferred.

The silicate compound preferable as the reinforcing filler refers to a compound having a chemical composition having a shape such as powder, granules, needles, and plates containing SiO ₂ units. Specifically, for example, talc, mica, magnesium silicate, aluminum silicate, calcium silicate, wollastonite, kaolin, diatomaceous earth, smectite and the like, and even natural or synthesized ones Good. Among them, talc, mica and smectite are preferred.

The average diameter of such a silicate compound [the particle diameter in terms of a circle determined by image processing of a micrograph, which is obtained by image processing] is not particularly limited, but is preferably 0.01 to 100 μm. , More preferably 0.
The thickness is from 0.5 to 50 μm, and more preferably from 0.1 to 40 μm. If the average particle size is less than 0.01 μm, the effect of improving the strength may not be sufficient, and if it exceeds 100 μm, the toughness tends to decrease.

The silicate compound may be surface-treated with a surface treating agent such as a silane coupling agent or a titanate coupling agent. The silane coupling agent is not particularly limited, and examples thereof include an epoxy silane, an amino silane, and a vinyl silane. The titanate-based coupling agent is not particularly limited, and includes, for example, monoalkoxy type, chelate type, coordinate type and the like. The method for treating the silicate compound with the surface treatment agent is not particularly limited, and can be carried out by an ordinary method. For example, it can be performed by adding the surface treating agent to the layered silicate, and stirring or mixing the solution in a solution or while heating.

The fibrous filler preferable as the reinforcing filler is not particularly limited, and examples thereof include glass fibers, carbon fibers, and potassium titanate fibers. Above all,
From the viewpoint of workability, it is preferable to use chopped strand glass fibers treated with a sizing agent. In addition, in order to enhance the adhesion between the resin and the fibrous filler, it is preferable that the surface of the fibrous filler is treated with a coupling agent, and a binder may be used. Examples of the coupling agent include the same compounds as described above.

When glass fibers are used as the reinforcing filler, the diameter is about 1 to 20 μm and the length is 0.01 to 50 μm.
mm is preferable. If the fiber length is too short, the effect of reinforcement may not be sufficient, and if it is too long, the surface properties, extrudability, and moldability of the molded article tend to be poor.

As the above reinforcing fillers, only one kind may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, there is no particular limitation, but a preferable combination is two or more kinds selected from the group consisting of kaolin, smectite and glass fiber. The amount of the reinforcing filler (D) used in the present invention is preferably at least 50% by weight of at least one selected from the group consisting of (A) a thermoplastic polyester resin, a polyphenylene ether resin, and a thermoplastic polyamide resin. Resin 1
The reinforcing filler (D) is used in an amount of 1 to 150 parts by weight with respect to 00 parts by weight.
130 parts, more preferably 120 parts.

In order to further increase the impact strength, toughness, etc. of the obtained molded article, the flame-retardant resin composition of the present invention must have a rubber-like elasticity as long as the properties (flame retardancy, etc.) of the present invention are not impaired. The body may be further added. The rubber-like elastic body is not particularly limited, but is preferably at least one soft resin selected from graft rubber and / or olefin-based resin. In order to further improve the impact strength of the obtained resin composition, the rubber-like elastic body preferably has a glass transition temperature of 0 ° C or lower, more preferably -20 ° C or lower.

[0086] Of the preferred rubber-like elastic materials, the term "graft rubber" refers to a rubber obtained by graft copolymerizing a vinyl-based monomer with a general rubber-like elastic material. Here, the general rubber-like elastic body is not particularly limited, for example,
Diene rubbers such as polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and alkyl (meth) acrylate-butadiene rubber; acrylic rubber, ethylene-propylene rubber, and siloxane rubber.

The vinyl monomer to be graft-copolymerized is not particularly limited as long as it is a vinyl compound which can be graft-copolymerized with a general rubber-like elastic material. For example, an aromatic vinyl compound , Vinyl cyanide compounds, alkyl (meth) acrylates, and the like.

The aromatic vinyl compound is not particularly restricted but includes, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, chlorostyrene, bromostyrene, vinyltoluene and the like. . The vinyl cyanide compound is not particularly limited, and includes, for example, acrylonitrile, methacrylonitrile and the like. The alkyl (meth) acrylate is not particularly limited, and examples thereof include butyl acrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, methyl acrylate, and methyl methacrylate. Other vinyl compounds that can be graft-copolymerized on the rubber-like elastic material include, for example, unsaturated acids such as acrylic acid and methacrylic acid;
(Meth) acrylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl acetate, maleic anhydride, N-phenylmaleimide and the like.

There is no particular limitation on the ratio of the general rubbery elastic body and the vinyl monomer when they are copolymerized.
To increase the impact strength, the weight ratio is 10 / 90-9.
It is preferably 0/10, more preferably 30 /
70-80 / 20. If the proportion of the rubber-like elastic body is less than 10, the effect of improving the impact resistance may be reduced. On the other hand, if it exceeds 90, the compatibility with the resin tends to decrease.

Among the preferred rubber-like elastic materials, olefin-based resins include polyolefins, copolymers composed of two or more of them, copolymers composed of olefin monomers and two or more diene monomers, olefins, in addition to polyolefins in a narrow sense. It is used as a broad concept including a copolymer of at least one other vinyl monomer copolymerizable with a monomer and an olefin. Specifically, for example, ethylene,
Propylene, 1-butene, 1-pentene, isobutene,
Butadiene, isoprene, chloropyrene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, α , Ω-non-conjugated dienes and the like, and at least one homopolymer or copolymer selected from the group of monomers, and a mixture of two or more thereof. Among these, polyethylene, polypropylene and the like are preferred because the resulting composition has improved chemical resistance.

The olefin-based resin is composed of the above-mentioned olefin monomer, (meth) acrylic acid, alkyl (meth) acrylate, glycidyl (meth) acrylate, vinyl acetate, maleic anhydride, N-phenylmaleimide, It may be a copolymer with a copolymerizable vinyl monomer such as carbon oxide. Specific examples of such a copolymer include an ethylene / ethyl acrylate copolymer, an ethylene / butyl acrylate / carbon monoxide terpolymer, an ethylene / glycidyl methacrylate copolymer, and an ethylene / glycidyl methacrylate / vinyl acetate copolymer. Polymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-acrylic acid copolymer, ethylene-maleic anhydride copolymer, ethylene
And maleic anhydride / N-phenylmaleimide copolymer.

The method of polymerizing these polyolefin resins is not particularly limited, and various known methods can be used. As long as it is polyethylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene and the like can be obtained by a polymerization method, and any of them can be preferably used.

The flame-retardant resin composition of the present invention may further comprise a silicone other than the additive flame retardant of the present invention as far as the properties (flame retardancy, etc.) of the present invention are not impaired in order to further enhance the molding fluidity. Etc. can be added.

The silicone other than the flame retardant for addition of the present invention means a polyorganosiloxane in a broad sense excluding the flame retardant for addition of the present invention. Specifically, (silicon) such as dimethylsiloxane and phenylmethylsiloxane Poly) diorganosiloxane compounds; copolymers obtained by polymerizing these;
Examples thereof include polydimethylsiloxane and polyphenylmethylsiloxane. In the case of a polyorganosiloxane, a modified silicone having a molecular terminal substituted by an epoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, an ether group or the like is also useful. The shape of the silicone is not particularly limited, and any shape such as an oil, a gum, a varnish, a powder, and a pellet can be used.

Further, in order to make the flame-retardant resin composition of the present invention higher in performance, an antioxidant such as a phenolic antioxidant and a thioether antioxidant; And the like are preferably used alone or in combination of two or more. Further, if necessary, generally well-known flame retardants such as lubricants, release agents, plasticizers, phosphorus compounds (phosphate esters, red phosphorus), and melamine cyanuric acid adducts;
Flame retardant aids, anti-dripping agents, ultraviolet absorbers, light stabilizers, pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants,
Additives such as compatibilizers and antibacterial agents can be used alone or in combination of two or more.

The method for producing the flame-retardant resin composition of the present invention is not particularly limited. For example, it can be produced by a method in which the above-mentioned components are dried as necessary, and then melt-kneaded by a melt-kneading machine such as a single-screw or twin-screw extruder. When the compounding agent is a liquid, it can be manufactured by adding the compounding agent to a twin screw extruder in the middle using a liquid supply pump or the like.

The method of molding the flame-retardant resin composition produced by the present invention is not particularly limited, and generally used molding methods such as injection molding, blow molding, extrusion molding, and the like.
Vacuum molding, press molding, calender molding, foam molding and the like can be used. The flame-retardant resin composition of the present invention,
It can be suitably used for various applications. Preferred applications include injection molded products such as home appliances, OA equipment components, and automobile components, blow molded products, extruded molded products, and foam molded products.

[0098]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, “parts” refers to parts by weight,
“%” Indicates% by weight. Reference Example 1 Production of Silicone Resin (B-1) 902 g of phenyltrichlorosilane, 177 g of methyltrichlorosilane, 2500 ml of methyl isobutyl ketone
In a flask, and ion-exchanged water 1000 at ice temperature.
ml was added slowly with stirring. After the addition is completed, 50
The mixture was heated to 200 ° C., and 200 ml of triethylamine and 321 g of trimethylchlorosilane were gradually added dropwise. After completion of the dropwise addition, stirring was continued for 15 hours at room temperature. The obtained reaction solution was filtered and the pressure was reduced at 170 ° C. to remove the solvent and low volatile components, and then the remaining reaction product was cooled to obtain a solid silicone resin (B-1). Varian XL-
As a result of measuring an NMR spectrum using a 300 apparatus, the structural unit represented by the general formula (3) was 88 mol%, a phenyl group: methyl group = 56: 44, an alkoxy group and a hydroxyl group remaining in all organic substituents. Was 2.6% by molar ratio. In addition, the number average molecular weight in terms of styrene measured by gel permeation chromatography (GPC) was 3,500. Reference Example 2 Production of Silicone Resin (B-2) Phenyltrichlorosilane (190 g) and dichlorodiphenylsilane (102 g) were dissolved in a methyl isobutyl ketone solution (1 L), and 250 ml of pure water was added under ice cooling. After the dropwise addition, a reflux reaction was performed for 5 hours. Thereafter, trimethylchlorosilane (150 g) was added, and the mixture was refluxed for another 3 hours to complete the reaction. After the completion, washing with pure water was repeated until the washing water became neutral. The obtained reaction solution is filtered,
After reducing the pressure at 170 ° C to remove the solvent and low volatile components,
The remaining reaction product was cooled to obtain a solid silicone resin (B-2). As a result of measuring an NMR spectrum using an XL-300 apparatus manufactured by Varian, a general formula (3) was obtained.
Was 48 mol%, phenyl group: methyl group = 53: 47, and the total ratio of the alkoxy group and hydroxyl group remaining in all the organic substituents was 1.3% in molar ratio. Gel permeation chromatography (GPC)
The number average molecular weight in terms of styrene measured by the method is 3520.
Met. Reference Example 3 Production of Silicone Resin (B-3) 0.2N HCl (1.1 g) was added to a mixture of trimethoxyphenylsilane (80 g), dimethoxydiphenylsilane (122 g), and tetraethoxysilane (42 g). Water (43 g, 2.4 mol) was added and the mixture was stirred at 60 ° C. for 3 hours. After returning the reaction mixture to room temperature, chlorotrimethylsilane (109 g, 1 mol) was added, and the mixture was added at 60 ° C for 2 hours.
Reacted for hours. Thereafter, methyl isobutyl ketone was added, and the mixture was washed several times with water. The obtained reaction solution was filtered, and 17
After reducing the pressure at 0 ° C. to remove the solvent and low volatile components, the remaining reaction product was cooled to obtain a solid silicone resin (B
-3) was obtained. As a result of measuring an NMR spectrum using an XL-300 apparatus manufactured by Varian, the structural unit represented by the general formula (3) was 20 mol%, the structural unit represented by the general formula (4) was 20 mol%, and a phenyl group: methyl Group = 4
At 0:60, the total ratio of alkoxy groups and hydroxyl groups remaining in all organic substituents was 10.3% in molar ratio. The number average molecular weight in terms of styrene measured by gel permeation chromatography (GPC) was 2,844. Reference Example 4 Production of Silicone Resin (B-4) 0.2N HCl was added to a mixture of dimethoxydiphenylsilane (244 g) and tetraethoxysilane (312 g).
(1.1 g) in water (122 g) was added and stirred at 60 ° C. for 3 hours. After returning the reaction mixture to room temperature, chlorotrimethylsilane (216 g) was added, and the mixture was reacted at 60 ° C. for 2 hours. Thereafter, toluene was added and the mixture was washed several times with water. The obtained reaction solution was filtered and the pressure was reduced at 170 ° C. to remove the solvent and low volatile components, and then the remaining reaction product was cooled to obtain a solid silicone resin (B-4). Varia
As a result of measuring an NMR spectrum using an XL-300 device manufactured by n Company, the structural unit represented by the general formula (4) was 43 mo.
1%, phenyl group: methyl group = 37: 63, and the total ratio of the alkoxy group and hydroxyl group remaining in all the organic substituents was 11.2% in molar ratio. In addition, the number average molecular weight in terms of styrene measured by gel permeation chromatography (GPC) was 3,756. (B) Silicone resin ・ Silicone (B-5) dimethyl silicone (KF-9
6H-10,000; Shin-Etsu Chemical Co., Ltd.) Silicone (B-6) phenylmethylsilicone (K
F-53; manufactured by Shin-Etsu Chemical Co., Ltd.) (C) Condensed polycyclic aromatic resin ・ Fused polycyclic aromatic resin (C-2) FPI-5167 (manufactured by Kashima Oil Co., Ltd.) (D) Reinforcing filler 100 parts by weight of montmorillonite (Kunimine Kogyo-F, weight average particle diameter 20 μm, pH = 10.0) treated with 1 part by weight of γ-aminopropyltriethoxysilane (D-3) (Example) 1) Polyethylene which is sufficiently dried at 0.65 dl / g in (A) a thermoplastic resin having a logarithmic viscosity (measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane at a weight ratio of 1/1, the same applies hereinafter) as a thermoplastic resin. Terephthalate (A-1)
100 parts by weight, and (B) a silicone resin (B-
1) 12 parts by weight, (C) FP as a condensed polycyclic aromatic resin
After dry blending 13 parts by weight of I-5522 (manufactured by Kashima Oil Co., Ltd.) (C-1), the mixture was vented to a 45 mmφ co-rotating twin screw extruder (trade name: 250 to 280 ° C.) Nippon Steel Works Co., Ltd. TEX4
(4) 20 parts by weight of mica having a particle size of about 40 μm (A-41S: Yamaguchi Mica Co., Ltd.) (D-1) and glass fiber (D-2) as a reinforcing filler.
(T-195H / P manufactured by NEC Corporation) 10 parts by weight was added from the middle of the extruder using a side feeder.
Pellets were obtained by melt-kneading.

After the obtained pellets were dried at 140 ° C. for 3 hours, the following test was conducted using an injection molding machine (clamping pressure: 75 tons) at a cylinder temperature of 280 ° C. to 250 ° C. and a mold temperature of 120 ° C. A piece was molded.・ Thickness 6.4mm, 2.0mm bar (each length: 127m
(m, width: 12.7 mm) Using these test pieces, physical properties were evaluated according to the following criteria. Table 1 shows the results. The evaluation method is as follows. (Flame retardancy) According to the UL-94 standard, the flame retardancy of a 2.0 mm thick bar was evaluated by a V test. In addition, the total number of combustion seconds and the presence or absence of a trickle of the five samples were measured. In addition,
The case where the fire was not extinguished was indicated as "measurement impossible". (Impact Test) After cutting a bar specimen having a thickness of 6.4 mm at the center, the Izod impact strength was measured by a notched Izod test. Examples 2 to 5, Comparative Examples 1 to 4 Except that each compounding agent was changed to the composition shown in Tables 1 and 2,
A resin composition was obtained in the same manner as in Example 1. The following compounding agents were used. Table 1 shows the evaluation results.

[0100]

[Table 1] In FIG. 1, 100 parts by weight of (A-1), a total of 25 parts by weight of (B-1) and (C-1), 30 parts by weight of (D-1),
(D-2) The evaluation result when 10 parts by weight was blended was expressed as Y
On the axis, the total number of combustion seconds (sec) is plotted, and on the X-axis, the content (% by weight) of (B-1) in the component ((B-1) + (C-1) = 25 parts by weight) used as the flame retardant ).

As shown in Table 1, each of the flame-retardant resin compositions of the present invention has excellent flame retardancy and impact resistance by using a specific silicone resin and a condensed polycyclic aromatic resin. It can be seen that they have

Further, as shown in FIG. 1, the synergistic effect of the silicon resin and the condensed polycyclic aromatic resin is particularly effective in a specific range.

[0103]

By using a specific silicone resin and a condensed polycyclic aromatic resin together, a flame-retardant thermoplastic resin composition having a remarkably high level of flame retardancy and excellent impact resistance can be obtained. . Further, when the silicone resin and the condensed polycyclic aromatic resin are added at a specific ratio, the flame retardant effect can be more effectively obtained. These are home appliances, OA equipment parts, A
It is suitably used for injection molded products such as V equipment parts and is industrially very useful.

[Brief description of the drawings]

FIG. 1 is a diagram showing a synergistic effect of a silicon resin and a condensed polycyclic aromatic resin.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AG003 CC123 CF051 CF061 CF071 CF081 CH071 CL011 CL031 CL051 CP032 DA036 DE136 DE236 DG046 DG056 DJ006 DJ036 DJ046 DJ056 DL006 FB096 FD016 FD130 FD133

Claims (6)

[Claims] (A) 100 parts by weight of a thermoplastic resin containing 50% by weight or more of at least one selected from a thermoplastic polyester resin, a polyphenylene ether resin, and a thermoplastic polyamide resin; 0.5 to 30 parts by weight of a silicone resin having a T unit or a Q unit,
(C) A flame-retardant thermoplastic resin composition containing 0.5 to 40 parts by weight of a condensed polycyclic aromatic resin. (A) 100 parts by weight of a thermoplastic resin containing 50% by weight or more of at least one selected from a thermoplastic polyester resin, a polyphenylene ether resin, and a thermoplastic polyamide resin; 0.5 to 30 parts by weight of a silicone resin having a T unit or a Q unit,
(C) condensed polycyclic aromatic resin 0.5 to 40 parts by weight, (D)
A flame-retardant thermoplastic resin composition comprising 1 to 150 parts by weight of a reinforcing filler. 3. The thermoplastic resin composition according to claim 1, wherein (C) the condensed polycyclic aromatic resin is obtained by polycondensing heavy oils or pitches and an aldehyde compound in the presence of an acid catalyst. object. 4. The silicone resin having (B) a T unit or a Q unit, wherein at least 80 mol% of all organic groups are a methyl group and a phenyl group, and a phenyl group: methyl group molar ratio is 1: 1. A ratio of 4 to 7: 3, and a component soluble in methyl isobutyl ketone at 23 ° C. is 80% by weight or more, and the number average molecular weight of the soluble component is 15
The flame-retardant thermoplastic resin composition according to claim 1, wherein the composition is not less than 00. 5. The silicone resin having (B) a T unit or a Q unit has a total of alkoxy groups and hydroxyl groups directly bonded to Si atoms in a molar ratio of 3/2 to all organic groups.
The flame-retardant thermoplastic resin composition according to claim 4, wherein the proportion is 0 or less. 6. The addition ratio of (B) a silicone resin having a T unit or a Q unit and (C) a condensed polycyclic aromatic resin in a weight ratio of 0.5: 10 to 5: 1. ~
5. The flame-retardant thermoplastic resin composition according to 5.