JP2002146171A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new flame-retardant resin composition not containing a compound having an atom of a halogen, phosphorus or the like, and capable of exhibiting extremely high flame-retardant effects. SOLUTION: This flame retardant polycarbonate resin composition comprises (A) 100 pts.wt. polycarbonate resin, (B) 0.01-10 pts.wt. polymer having a skeleton composed of silicon, boron and oxygen, and substantially formed by a silicon- oxygen bond and a boron-oxygen bond, and having an aromatic ring in the molecule, and (C) 0.03-5 pts.wt. metal salt of an aromatic sulfur compound or (D) 0.01-5 pts.wt. metal salt of a perfluoroalkanesulfonic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a highly flame-retardant polycarbonate resin composition containing no atoms such as halogen and phosphorus.

[0002]

2. Description of the Related Art Polycarbonate resins have mechanical properties,
It has excellent heat resistance and transparency, and is widely used as a material for electric and electronic parts, a material for automobile parts, a material for construction, a sheet material, a food container material and the like. When used in the above-mentioned electronic and electrical fields, strict flame retardancy standards are set for safety considerations in the event of fire, and advanced standards that comply with UL-94 V-0 (U.S. Underwriters Laboratory Standard). In many cases, high flame retardancy is required. In order to satisfy the flame retardancy standards, various flame retardants such as halogen-based and phosphorus-based have been added to polycarbonate-based resins.

However, in recent years, halogen-based flame retardants,
In particular, from the growing concern about environmental problems mainly in Europe concerning flame retardants containing chlorine or bromine, various kinds of development of non-halogen flame-retardant resin compositions containing no organic compounds containing chlorine or bromine have been studied. I have.

Examples of the non-halogen flame-retardant polycarbonate resin include a resin composition containing a phosphoric acid ester, a phosphorus-containing compound such as red phosphorus, and a metal hydroxide such as aluminum hydroxide and magnesium hydroxide. But,
When a resin composition containing a phosphorus-containing compound is used, there is a problem that heat resistance and strength are reduced, and when a metal hydroxide is used, there is a problem that decomposition of the resin occurs.

On the other hand, silicone compounds have high heat resistance,
Since harmful gas is hardly generated at the time of combustion and its safety is high, many attempts have been made to use it as a flame retardant. As examples of using a silicone compound as a flame retardant, silicone compounds such as those described in JP-A-1-318069 and JP-B-62-60421 have been tried. Very few of them have a flame-retardant effect, and even if they have a relatively effective effect, they must be added in large amounts to meet the strict flame-retardant standards for electrical and electronic equipment. It was not practical because of adverse effects on properties and other necessary properties, and disadvantages in cost.

[0006] On the other hand, as an attempt to improve the flame retardant effect of a silicone compound and to reduce the amount of addition, a method of using a silicone compound and a metal salt in combination has been reported. Regarding this, a combination use of polydimethylsilicone, a metal hydroxide and a zinc compound (JP-A-2-150436) and a combination use of polydimethylsilicone and a group IIa metal salt of an organic acid (JP-A-56-100853) And silicone resins, particularly those represented by M and Q units, and a combination of silicone oil and a metal salt of Group IIa of an organic acid (Japanese Patent Publication No. 3-48947), all of which are flame retardant. There is a fundamental problem that the effect is inferior and it is difficult to significantly reduce the amount of addition. In addition, when a metal salt compound is used, the decomposition of the resin is generally promoted, so that there has been a problem that the surface appearance of the molded article is deteriorated and the resin properties such as poor heat and moisture resistance are deteriorated.

[0007]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a highly flame-retardant polycarbonate resin composition containing no halogen or phosphorus atoms.

[0008]

The inventors of the present invention have conducted intensive studies on additives that exhibit higher flame retardancy than silicone compounds alone. It was found that the compound having the structure exhibited excellent flame retardancy, and then, by using this flame retardant in combination with a minute amount of a metal salt of an aromatic sulfur compound or a metal salt of perfluoroalkanesulfonic acid, a dramatic effect was obtained. Even if the amount of flame retardant added is reduced, it has high flame retardancy,
In addition, they have found that a flame-retardant polycarbonate resin composition having no reduction in resin properties can be obtained, and have completed the present invention.

That is, the present invention comprises 100 parts by weight of a polycarbonate resin (A), silicon, boron and oxygen, has a skeleton substantially formed of silicon-oxygen bonds and boron-oxygen bonds, and has a molecular structure. 0.01 to 10 parts by weight of a polymer (B) having an aromatic ring therein, and 0.03 to 5 parts by weight of a metal salt of an aromatic sulfur compound (C) or perfluoroalkanesulfonic acid A flame-retardant polycarbonate resin composition containing 0.01 to 5 parts by weight of a metal salt (D) of the present invention. Hereinafter, the present invention will be described in detail.

The polycarbonate resin (A) used in the present invention is obtained by reacting a phenol compound having a valency of 2 or more with phosgene or a carbonic acid diester such as diphenyl carbonate.

The dihydric or higher phenol compound is not particularly limited.
2-bis (4-hydroxyphenyl) propane [commonly known as:
Bisphenol A], bis (4-hydroxyphenyl)
Methane; bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane;
Bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; bis (3,5-dimethyl-4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1-naphthyl-1, 1-bis (4
-Hydroxyphenyl) ethane; 1-phenyl-1,1
-Bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl) ethane; 2-methyl-
1,1-bis (4-hydroxyphenyl) propane;
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3-methyl-4-hydroxyphenyl) ) Propane; 2,2-bis (3-fluoro-4-hydroxyphenyl) propane;
1,1-bis (4-hydroxyphenyl) butane; 2,
2-bis (4-hydroxyphenyl) butane; 1,4-
Bis (4-hydroxyphenyl) butane; 2,2-bis (4-hydroxyphenyl) pentane; 4-methyl-
2,2-bis (4-hydroxyphenyl) pentane;
2,2-bis (4-hydroxyphenyl) hexane;
4,4-bis (4-hydroxyphenyl) heptane;
2,2-bis (4-hydroxyphenyl) nonane; 1,
10-bis (4-hydroxyphenyl) decane; 1,1
-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; dihydroxydiarylalkanes such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Kind,
1,1-bis (4-hydroxyphenyl) cyclohexane; dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclodecane;
Bis (4-hydroxyphenyl) sulfone; bis (3,
Dihydroxydiarylsulfones such as 5-dimethyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-
Dihydroxydiaryl ethers such as 4-hydroxyphenyl) ether, 4,4'-dihydroxybenzophenone; 3,3 ', 5,5'-tetramethyl-4,
Dihydroxydiaryl ketones such as 4'-dihydroxybenzophenone, bis (4-hydroxyphenyl)
Sulfide; bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, and dihydroxy diaryl sulfoxides such as bis (4-hydroxyphenyl) sulphoxide And dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl, and dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene. In addition to the above-mentioned dihydric phenols, dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone; dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene; and 2,6-dihydroxynaphthalene are also included.

Among these, 2,2-bis (4-hydroxydiphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (3,5-dimethyl-4-) Hydroxyphenyl) methane, 1-phenyl-1,1-bis (4-
Hydroxyphenyl) ethane, 2,2-bis (3,5-
Dimethyl-4-hydroxyphenyl) propane, 1,1
-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) sulfone, and 4,4'-dihydroxybenzophenone are useful for forming the flame-retardant polycarbonate resin composition of the present invention. It is preferable from the viewpoints of flame retardancy, mechanical strength of the obtained molded article, and flame retardancy. These dihydric phenols and the like may be used alone or in combination of two or more.

The carbonic acid diester compound is not particularly restricted but includes, for example, diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

If necessary, the polycarbonate resin (A) may contain a branching agent for the purpose of generating a branching property. Examples of the branching agent include phloroglucin, melitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β-resorcinic acid, resorcinaldehyde, trimethyl chloride, isatin bis (o-cresol), trimethyl trichloride, 4-chloroformylphthalic anhydride, benzophenonetetracarboxylic acid; 2,4,4′-trihydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone;2,4,4'-trihydroxyphenylether;2,2',4,4'-tetrahydroxyphenylether;2,4,4'-trihydroxydiphenyl-2-Propane;2,2'-bis (2,4-di 2,2 ′, 4,4′-tetrahydroxydiphenylmethane; 2,4,4′-trihydroxydiphenylmethane; 1- [α-methyl-α- (4′-dihydroxyphenyl) ethyl] -3- [Α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; 1
-[Α-methyl-α- (4′-dihydroxyphenyl)
Ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 2,6-bis (2-hydroxy-5 '
-Methylbenzyl) -4-methylphenol; 4,6-
Dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptene; 4,6-dimethyl-2,4,6
-Tris (4'-hydroxyphenyl) -2-heptane; 1,3,5-tris (4'-hydroxyphenyl)
Benzene; 1,1,1-tris (4-hydroxyphenyl) ethane; 2,2-bis [4,4-bis (4'-hydroxyphenyl) cyclohexyl] propane; 2,6-
Bis (2'-hydroxy-5'-isopropylbenzyl) -4-isopropylphenol; bis [2-hydroxy-3- (2'-hydroxy-5'-methylbenzyl) -5-methylphenyl] methane; bis [2 -Hydroxy-3- (2'-hydroxy-5'-isopropylbenzyl) -5-methylphenyl] methane; tetrakis (4-hydroxyphenyl) methane; tris (4-hydroxyphenyl) phenylmethane; 2 ', 4', 7-trihydroxyflavan; 2,4,4-trimethyl-
2 ', 4', 7-trihydroxyflavan; 1,3-bis (2 ', 4'-dihydroxyphenylisopropyl)
Benzene; and tris (4'-hydroxyphenyl) -amyl-s-triazine.

[0015] In some cases, the polycarbonate resin (A) may be a polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate part and a polyorganosiloxane part. At this time, the degree of polymerization of the polyorganosiloxane portion is preferably 5 or more.

As the terminal terminator at the time of polymerization of the polycarbonate resin (A), various known terminators can be used. Specifically, as a monohydric phenol, for example, phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, bromophenol, tribromophenol,
Nonylphenol and the like can be mentioned.

Further, in order to enhance the flame retardancy, a copolymer with a phosphorus-containing compound or a polycarbonate resin end-blocked with the phosphorus-containing compound may be used. Furthermore, in order to enhance the weather resistance, a copolymer with a dihydric phenol having a benzotriazole group or a polycarbonate resin end-capped with a monohydric phenol having a benzotriazole group can be used.

The polycarbonate resin (A) is preferably 2,2-bis (4-hydroxydiphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (3,5 -Dimethyl-4-hydroxyphenyl) methane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (3,5-dimethyl-4-)
1 selected from hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) sulfone and 4,4′-dihydroxybenzophenone
Or more phenolic compounds, more preferably 2,2-
Bis (4-hydroxydiphenyl) propane and 1,1
Polycarbonate resin or polycarbonate-polyorganosiloxane copolymer obtained by reacting one or more phenol compounds selected from -bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane with phosgene or a carbonic acid diester Is preferably used in view of the moldability of the flame-retardant polycarbonate resin composition of the present invention and the mechanical strength of the obtained molded article.

The viscosity average molecular weight of the polycarbonate resin (A) is preferably from 10,000 to 60,000, more preferably from 15,000 to 45,000, and most preferably from 18,000 to 35,000. Viscosity average molecular weight of 1
If the molecular weight is less than 0000, the resulting resin composition has insufficient flame retardancy and strength, and if the viscosity average molecular weight exceeds 60,000, there is a tendency that there is a problem in molding fluidity. Such a viscosity average molecular weight is calculated from an intrinsic viscosity obtained by a viscosity measurement using an Ubbelohde viscometer according to a known method.

The polycarbonate resin (A) is used alone,
Alternatively, two or more kinds are used in combination. When two or more kinds are used in combination, the combination is not limited. For example, those having different monomer units, different copolymerization molar ratios, different molecular weights, and the like can be arbitrarily combined.

The component (B) used in the present invention (hereinafter referred to as the component (B))
"Borosiloxane polymer") is a polymer composed of silicon, boron and oxygen and having a skeleton substantially formed of silicon-oxygen bonds and boron-oxygen bonds. That is, silicon-oxygen bonds and boron-oxygen bonds occupy 80% or more, preferably 90% or more, of the bonds forming the skeleton of the polymer. Bond, oxygen-
Oxygen bond, bond between silicon and divalent organic group, boron and 2
It may contain a bond with a valent organic group. In this specification, regarding the component (B), when a skeleton is referred to, a bond between silicon or boron and a monovalent organic group is excluded from a bond forming the skeleton.

Preferably, the borosiloxane polymer (B)
Has a skeleton in which a silicon atom and a boron atom are bonded to another silicon atom and / or a boron atom via an oxygen atom. In this case, the skeleton of the polymer is substantially Si—O
-Si bonds, Si-OB bonds, and B-OB bonds. That is, the skeleton of the polymer is Si-OB
It may be formed only from a bond, or may be substantially Si
It may be formed from an -OB bond and contain a slight amount of a Si-O-Si bond and / or a B-OB bond. Further, a Si-O-Si bond, a Si-OB bond, and a B-
A skeleton containing OB bonds at random may be used. Further, a skeleton substantially consisting of a Si—O—Si bond and a B—O—B bond and containing a slight amount of a Si—O—B bond may be used. In this case, the polymer has a skeleton in which a portion consisting essentially of silicon and a portion consisting essentially of boron are divided in the molecule. The skeleton of the polymer may be a linear skeleton or a three-dimensional crosslinked skeleton, but a three-dimensional crosslinked structure is preferable from the viewpoint of flame retardancy.

The borosiloxane polymer (B) has an organic group in the molecule. Here, the organic group refers to a monovalent or higher valent substituent composed of a carbon atom and any one of a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a halogen atom, and the like. Typically, it is a hydrocarbon group, having 1 to 1 carbon atoms.
Twenty are preferred.

The borosiloxane polymer (B) has an aromatic ring among organic groups. The aromatic ring may be monovalent, divalent, trivalent, or the like, but is preferably monovalent because of ease of synthesis. The aromatic ring in the molecule may be bonded in any form, may be directly bonded to a silicon atom and / or a boron atom, or may be bonded via a divalent organic group such as a methylene group or an ethylene group. (Ie, the aromatic ring may be included as an aralkyl group such as a benzyl group or a phenylethyl group). In order to further improve the flame retardancy, it is preferable that the aromatic ring in the molecule is directly bonded to a silicon atom. The method for introducing an aromatic ring into a molecule is not particularly limited.

The term "aromatic ring" as used herein refers to a general term for aromatic rings, and is not particularly limited. Preferred aromatic rings include a phenyl group, a cresyl group, a xylenyl group, a naphthyl group, and an anthracenyl group. More preferably, it is a monovalent benzene-based or condensed benzene-based aromatic group having 6 to 20 carbon atoms, and further preferably, 6 to 10 carbon atoms.
belongs to. Further, it may be an aromatic ring substituted with halogen, oxygen, nitrogen, or another element.

The borosiloxane polymer (B) may further have an organic group containing no aromatic ring. The organic group containing no aromatic ring may be monovalent, divalent, trivalent, or the like, but is preferably a monovalent organic group because of ease of synthesis. Examples of the organic group containing no aromatic ring include a monovalent linear or cyclic alkyl group, and among them, those having 1 to 12 carbon atoms are preferable. In order to obtain more excellent flame retardancy, an alkyl group having a small number of carbon atoms, specifically having 1 to 4 carbon atoms, is preferred.
Are preferred. A particularly preferred alkyl group is a methyl group.

The ratio of the organic group having an aromatic ring to the total organic group is not particularly limited, but in order to obtain more excellent flame retardancy, 10 mol% or more of the organic group has an organic group having an aromatic ring. It is more preferable that 30 mol% or more of the organic group is an organic group having an aromatic ring,
More preferably, 50 mol% or more of the organic groups are organic groups having an aromatic ring.

The silicon atom in a borosiloxane polymer _{(B), SiO 4/2} units, SiRO _3/2 units, SiR
₂ O _2/2 units and SiR ₃ O _1/2 units (wherein R
Represents a monovalent substituent capable of bonding to a silicon atom, a plurality of Rs may be the same or different, and at least one of a plurality of Rs in the polymer is a monovalent organic group having an aromatic ring Is preferable to be contained as at least one of the following. Examples of the monovalent substituent capable of bonding to a silicon atom include the above-described aromatic ring and the organic group containing no aromatic ring, a hydroxyl group, an alkoxyl group, and a halogen atom. The monovalent organic group having an aromatic ring may be a monovalent aromatic ring itself or a monovalent organic group containing an aromatic ring.

The ratio of these units is not particularly limited.
Preferably, among all silicon atoms, SiRO_3/2unit
At least 10 mol%, more preferably SiRO_3/2unit
At least 30 mol%, more preferably SiRO_3/2unit
At least 50 mol%. SiRO
_3/2If the unit is less than 10 mol%, the resulting flame-retardant poly
In some cases, the flame retardancy of the carbonate resin composition is not sufficient.
is there. Preferably, among all the silicon atoms, SiO 2
_4/2The unit is less than 50 mol%, more preferably SiO
_4/2The unit is less than 30 mol%, more preferably SiO
_4/2The unit is less than 10 mol%. SiO_4/2unit
Is more than 50 mol%, the resulting flame-retardant polycarbonate
Flame retardancy of impact resin composition and impact strength decrease
Or tend to. Further, preferably all silicon atoms
Of the numbers, SiR₂O_2/2Less than 80 mol% unit
More preferably SiR₂O_2/2The unit is less than 50 mol%,
More preferably, SiR₂O_2/2Unit less than 20 mol%
It is. SiR₂O_2/2Unit exceeds 80 mol%
And the flame retardancy of the resulting flame retardant polycarbonate resin composition
Properties tend to decrease.

The boron atom in the borosiloxane polymer (B) is represented by BO _3/2 units, BR'O _2/2 units and BR ' ₂ O _1/2 units (wherein R' is a boron atom A plurality of R's may be the same or different, and at least one of the plurality of R's in the polymer is a monovalent organic group having an aromatic ring ) Is preferably contained as at least one of them. Examples of the monovalent substituent capable of bonding to a boron atom include the above-described aromatic ring, an organic group not containing the aromatic ring, a hydroxyl group, an alkoxyl group, and a halogen atom. Of the above units, from the viewpoint of stability, BO
_3/2 units are preferred.

The borosiloxane polymer (B) contains _3/2 units of SiRO (where R is the same as above) and BO
A three-dimensional crosslinked polymer containing _3/2 units is preferred because more excellent flame retardancy can be obtained. In this case, Si
It may contain silicon-containing units other than RO _3/2 units, or may contain boron-containing units other than BO _3/2 units. In particular, those containing SiR ₃ O _1/2 units (where R is the same as above) in addition to the SiRO _3/2 units and the BO _3/2 units are more preferable.

The borosiloxane polymer (B) is also a three-dimensional crosslinked polymer containing SiR ₃ O _1/2 unit (where R is the same as above) and BO _3/2 unit in the skeleton. It is preferable because excellent flame retardancy can be obtained. In this case, Si
It may contain a silicon-containing unit other than R ₃ O _1/2 unit, or may contain a boron-containing unit other than BO _3/2 unit.

The borosiloxane polymer (B) can be produced by a known method, for example, as described in JP-A-53-5029.
No. 9, JP-A-54-83100, JP-A-57
It can be produced by the methods described in JP-A-23629, JP-A-58-201821, and the like.

Specifically, for example, boric acid, boron oxide,
One or more boron compounds selected from a metal borate, a boron halide, a borate, and the like, and SiR ″ X ₃
(In the formula, R ″ represents a monovalent organic group. X is at least one selected from a halogen, a hydroxyl group, and a dehydration condensate of a hydroxyl group (for example, an alkoxyl group). Can be synthesized by mixing with at least one silicon compound represented by the formula (1) in the presence or absence of a solvent, if necessary, while heating. by using part of the compound having an aromatic ring as "R among the compounds represented by _{X 3"} SiR, _SiRO in _3/2 units (wherein in the backbone,
R represents a monovalent substituent capable of bonding to a silicon atom, a plurality of Rs may be the same or different, and at least one of the plurality of Rs is a monovalent organic group having an aromatic ring ) And BO _3/2 units can be obtained.

Further, "in addition to the compound represented by _{X 3, SiX 4, SiR"} SiR 2 X 2, SiR "3 X ( wherein R" and X are as defined above) at least one silicon compound represented by the Are mixed and reacted to synthesize borosiloxane polymer (B) having various properties. Particularly, SiR ″ ₃ X is used as a terminator for the synthesis reaction.
By using an appropriate amount of the compound represented by the formula, a polymer having a desired molecular weight can be synthesized.

The silicon atom: boron atom ratio contained in the borosiloxane polymer (B) is not particularly limited, but the silicon atom: boron atom ratio is 100: 1 to 1: 4 in molar ratio.
Is preferable, 70: 1 to 1: 3 are more preferable, and 5: 1
0: 1 to 1: 2 is most preferred. If the silicon atom: boron ratio is higher than 100: 1, the resulting flame retardancy may not be sufficient. When the silicon atom: boron atom ratio is higher than 1: 4, the resulting polymer tends to be unstable, such as being easily hydrolyzed.

This ratio depends on the type of starting material, reaction conditions,
It can be arbitrarily changed depending on the charging ratio and the like. In addition, since the proportion of the compound used for blocking the crosslinkable substituent changes depending on the molecular weight of the borosiloxane polymer (B), it is possible to easily synthesize a compound having an arbitrary proportion.

The weight average molecular weight of the borosiloxane polymer (B) is not particularly limited, but is preferably 800 to 10,000,000, more preferably 1200 to 1,000,000, and most preferably 1,000 to 200,000. When the weight average molecular weight is less than 800, the flame retardancy may not be sufficient, and when the weight average molecular weight exceeds 10,000,000, the flame retardancy of the obtained resin composition tends to decrease. The weight average molecular weight is determined by GPC analysis in terms of styrene.

The borosiloxane polymer (B) is used in an amount of 0.01 to 100 parts by weight of the polycarbonate resin (A).
The desired purpose can be achieved by adding 10 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving the flame retardancy may not be obtained, and if the amount exceeds 10 parts by weight, the surface properties, moldability and the like tend to deteriorate. Preferably 0.1
To 5 parts by weight, more preferably 0.5 to 3 parts by weight.

The metal salt (C) of the aromatic sulfur compound used in the present invention includes a metal salt of an aromatic sulfonamide and a metal salt of an aromatic sulfonic acid. As the metal salt of the aromatic sulfonamide, those represented by the following general formula (1) or (2) are preferable. As the metal salt of the aromatic sulfonic acid, those represented by the following general formula (3) are preferable. preferable.

[0041]

Embedded image

(Wherein, R ₁ and R ₂ are the same or different and each represents a monovalent aromatic group, and M ⁺ represents a metal cation.)

[0043]

Embedded image

(Wherein R ₃ represents a monovalent aromatic group;
₄ represents a monovalent organic group containing sulfonyl or carbonyl, and M ⁺ represents a metal cation. However, R ₃ and R ₄ may be combined. )

[0045]

Embedded image

(Wherein R ₅ and R ₆ are the same or different and are each a monovalent hydrocarbon group having 1 to 6 carbon atoms, or
Represents a valent aromatic group. X represents an SO ₃ M (M is a metal cation) group; n represents an integer of 0 to 2;
Are the same or different and represent an integer from 0 to 6, except when two are simultaneously 0. )

The metal salts of aromatic sulfonamides include:
For example, a metal salt of saccharin, a metal salt of N- (p-tolylsulfonyl) -p-toluenesulfonimide, N-
Metal salts of (N'-benzylaminocarbonyl) sulfanylimide, metal salts of N- (phenylcarboxyl) -sulfanylimide and the like can be mentioned.

Examples of the metal salt of an aromatic sulfonic acid include, for example, a metal salt of diphenylsulfon-3-sulfonic acid, a metal salt of diphenylsulfone-3,3'-disulfonic acid, and diphenylsulfone-3,4'- Metal salts of disulfonic acid. These may be used alone or in combination of two or more.

The metal for forming the above metal salt is not particularly limited, and examples thereof include Group I metals (alkali metals) such as sodium and potassium, Group II metals, copper and aluminum. Alkali metals are preferred.

Among these, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfonimide, potassium salt of N- (N'-benzylaminocarbonyl) sulfanylimide and diphenylsulfone-3-
The potassium salt of sulfonic acid is preferred. More preferably,
A potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfonimide and a potassium salt of N- (N'-benzylaminocarbonyl) sulfanylimide.

The amount of the metal salt (C) of the aromatic sulfur compound is preferably from 0.03 to 5 parts by weight based on 100 parts by weight of the polycarbonate resin (A). If the amount is less than 0.03 parts by weight, it may be difficult to obtain a remarkable flame retardant effect, and if it exceeds 5 parts by weight, the thermal stability during injection molding may be poor. As a result, moldability and impact strength may be adversely affected. More preferably, the content is in the range of 0.05 to 2 parts by weight, and still more preferably 0.06 to 0.4 parts by weight. In this range, the balance among flame retardancy, moldability and impact strength is further improved.

As the metal salt (D) of perfluoroalkanesulfonic acid used in the present invention, those represented by the following general formula (4) are preferable. _{CF 3 (CF 2) p SO} 3 M (4) ( wherein, M represents a metal cation, p is an integer of 0-7.)

Preferred metal salts (D) of perfluoroalkanesulfonic acid have 1 to 8 carbon atoms. Specifically, metal salts of perfluoromethanesulfonic acid, metal salts of perfluoroethanesulfonic acid, Metal salt of fluoropropanesulfonic acid, metal salt of perfluorobutanesulfonic acid, metal salt of perfluoromethylbutanesulfonic acid, metal salt of perfluorohexanesulfonic acid, metal salt of perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid And the like. They are,
One or more of them may be used in combination. The metal salt (D) of perfluoroalkanesulfonic acid may be used in combination with the metal salt (C) of the aromatic sulfur compound described above.

The metal for forming the metal salt (D) of perfluoroalkanesulfonic acid is not particularly limited.
Examples thereof include Group I metals (alkali metals) such as sodium and potassium, Group II metals, copper, aluminum and the like, with alkali metals being particularly preferred. Among them, potassium salt of perfluorobutanesulfonic acid is particularly preferably used.

The compounding amount of the metal salt (D) of perfluoroalkanesulfonic acid is 100 parts of the polycarbonate resin (A).
It is preferably 0.01 part by weight or more and 5 parts by weight or less based on part by weight. If the amount is less than 0.01 part by weight, it may be difficult to obtain a remarkable flame retardant effect, and if it exceeds 5 parts by weight, the thermal stability during injection molding may be poor. As a result, moldability and impact strength may be adversely affected. More preferably, 0.02 parts by weight or more and 2 parts by weight or less,
More preferably, it is in the range of 0.03 parts by weight or more and 0.2 parts by weight or less. In this range, the balance among flame retardancy, moldability and impact strength is further improved.

The fluororesin (E) used in the present invention is a resin having a fluorine atom. Specifically, polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene,
Examples thereof include a fluorinated polyolefin resin such as a tetrafluoroethylene / hexafluoropropylene copolymer and a polyvinylidene fluoride resin. Further, a copolymer obtained by polymerizing a monomer used for producing the fluororesin in combination with a copolymerizable monomer may be used.

The fluorinated resin (E) is preferably a fluorinated polyolefin resin, and more preferably a fluorinated polyolefin resin having an average particle diameter of 700 μm or less. Here, the average particle size refers to an average particle size of secondary particles formed by aggregation of primary particles of a fluorinated polyolefin resin.

Further, the fluorinated polyolefin resin preferably has a ratio of density to bulk density (density / bulk density) of 6.0.
The following fluorinated polyolefin resin: Here, the density and the bulk density are measured by the method described in JIS-K6891.

The fluorine resin (E) 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, different types are arbitrarily used.

The amount of the fluororesin (E) used is 0.005 to 100 parts by weight of the polycarbonate resin (A).
1 part by weight is preferable, and 0.01 to 0.7 is more preferable.
5 parts by weight, more preferably 0.02 to 0.6 parts by weight. If the amount is less than 0.005 parts by weight, the effect of improving the flame retardancy is small, and if it exceeds 1 part by weight, the molding fluidity of the flame-retardant polycarbonate resin composition of the present invention and the surface appearance of the molded article decrease. This is not preferred because of the tendency.

The flame-retardant polycarbonate resin composition of the present invention is used in order to further improve the molding fluidity and the flame retardancy, as long as the properties (flame retardancy, etc.) of the present invention are not impaired. Compounds and the like can be added.

The silicone compound refers to a polyorganosiloxane in a broad sense, and specifically includes (poly) diorganosiloxane compounds such as dimethylsiloxane and phenylmethylsiloxane; methylsilsesquioxane, phenylsilsesquioxane (Poly) organosyl sesquioxane compounds such as trimethylsilhemioxane, triphenylsilhemioxane, etc .; (poly) triorganosylhemioxane compounds; copolymers obtained by polymerizing these; polydimethyl Siloxane, polyphenylmethylsiloxane and the like can be mentioned. 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, the flame-retardant polycarbonate resin composition of the present invention can further improve mechanical strength and heat resistance by adding a reinforcing filler within a range not impairing the flame retardancy of the present invention. . Specific examples of the reinforcing filler include, for example, glass fibers, carbon fibers, fibrous fillers such as potassium titanate fibers, glass beads, glass flakes, talc, mica, kaolin, wollastonite, smectite, diatomaceous earth, carbonic acid Calcium, calcium sulfate, barium sulfate and the like can be mentioned. The reinforcing filler is preferably a silicate compound from the viewpoint of flame retardancy.

The silicate compound is a compound having a chemical composition having a shape of powder, granule, needle, plate or the like containing SiO ₂ units. Examples thereof include magnesium silicate, aluminum silicate, and the like. Calcium silicate, talc,
Examples include mica, wollastonite, kaolin, diatomaceous earth, smectite, and the like, which may be natural or synthetic. Among them, talc, mica, kaolin and smectite are preferred, and talc and mica are particularly preferred.

Further, the silicate compound may be treated with a surface treating agent such as a silane coupling agent and a titanate coupling agent. Examples of the silane-based coupling agent include an epoxy-based silane, an amino-based silane, and a vinyl-based silane, and examples of the titanate-based coupling agent include a monoalkoxy type, a chelate type,
Coordinated type and the like can be mentioned.

The method for treating the silicate compound with the surface treating agent is not particularly limited, and can be carried out by a usual method. For example, it can be performed by adding the surface treating agent to the layered silicate and stirring or mixing in a solution or while heating.

Any other thermoplastic or thermosetting resin such as a polyester resin, a polyamide resin, a polystyrene resin, and a polyphenylene sulfide resin as long as the properties of the flame retardant polycarbonate resin composition of the present invention are not impaired. Resins, polyphenylene ether-based resins, polyacetal-based resins, polysulfone-based resins, polyolefin-based resins, rubber-like elastic materials, and the like may be added alone or in combination of two or more.

In order to make the flame-retardant polycarbonate resin composition of the present invention higher in performance, an antioxidant such as a phenolic antioxidant, a thioether antioxidant, etc.
It is preferable to use heat stabilizers such as phosphorus-based stabilizers alone or in combination of two or more. If necessary,
Well-known stabilizers, lubricants, release agents, plasticizers, ultraviolet absorbers, light stabilizers, pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizers, antibacterial agents, etc. Can be used alone or in combination of two or more.

The method of molding the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, for example, injection molding, blow molding, extrusion molding, vacuum molding , Press molding, calendar molding, etc. can be applied.

[0070]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the following, “parts” means parts by weight and “%” means% by weight, unless otherwise specified.

[0071]Production Example 1 of resin-added flame retardant (S-1)
Manufacture  A pyridine solution containing boric acid (100 g, 1.62 mol)
The solution (1 L) was added to phenyltrichlorosilane (3
42.7 g, 1.62 mol) was added dropwise.
The mixture was heated for a period of time to perform a reflux reaction. Then trimethyl
Add chlorosilane (176 g, 1.62 mol)
The reaction was further refluxed for 3 hours to complete the reaction. The reaction mixture is 2N
-Neutralize with hydrochloric acid and extract with diethyl ether (500 mL)
Issued. The resulting solution is dried over anhydrous sodium sulfate,
The target compound was obtained by distilling off the solvent under vacuum.
As a result of GPC analysis, the molecular weight was Mn = 2484, Mw = 3.
273 (polystyrene equivalent, UV detector). Profit
The obtained compound had a result of IR analysis of 1360 cm.^-1near
Shows a peak derived from the BO bond at 1430 cm^-1Attached
A peak derived from a Si—Ph bond was shown nearby. By NMR
Of the total number of silicon atoms, Me₃-Si-O
_1/213 mol% bonding, Ph-Si-O_3/2Join
It was 87 mol%.

[0072]Production Example 2 of resin-added flame retardant (S-2)
Manufacture  A pyridine solution containing boric acid (100 g, 1.62 mol)
The solution (1 L) was added to phenyltrichlorosilane (1
62.4 g, 0.81 mol) and diphenyldichloro
Silane (205.1 g, 0.81 mol) was added dropwise, and 5
The reaction was carried out under reflux for a period of time. Then trimethylchloro
Add silane (176 g, 1.62 mol) and add 3 more
The reaction was completed by refluxing for an hour. The reaction mixture was 2N-hydrochloric acid
And extracted with diethyl ether (500 mL).
Was. The resulting solution is dried over anhydrous sodium sulfate and vacuum
The target compound was obtained by distilling off the lower solvent. molecule
The amounts were determined by GPC analysis, Mn = 6450, Mw = 892.
5 (polystyrene equivalent, UV detector). NMR
Of the total number of silicon atoms, Me₃-Si-
O_1/214 mol% bonding, Ph-Si-O_3/2Join
Is 51 mol%, Ph₂-Si-O_2/235 mol bond
%,Met.

[0073]Reference Production Example 1 Silicone compound (Si-
Production of 1)  Phenyltriethyl in methyl isobutyl ketone solution (1 L)
Dissolve chlorosilane (342.7 g, 1.62 mol)
Then, 250 ml of pure water was added dropwise under ice cooling, and then refluxed for 5 hours.
The following reaction was performed. Then, trimethylchlorosilane (1
76 g, 1.62 mol) and reflux for another 3 hours.
To complete the reaction. After finishing, clean until the washing water becomes neutral.
Washing with water was repeated. To remove the solvent under vacuum
Thus, a silsesquioxane compound was obtained. Molecular weight is GPC
As a result of analysis, Mn = 9650, Mw = 11700 (poly
(Styrene equivalent, UV detector). Minutes by NMR
As a result of the analysis, Me₃-Si-O_1/2
8 mol% bonding, Ph-Si-O_3/292 mol bond
%Met.

[0074]Reference Production Example 2 Flame retardant for resin addition (S-
X) Manufacturing  Pyridine solution containing boric acid (50 g, 0.81 mol)
(1 L) was added to dimethyldichlorosilane (20
9.1 g, 1.62 mol) was added dropwise and refluxed for 5 hours.
The reaction was performed. Then, trimethylchlorosilane (1
(7.6 g, 0.16 mol) and reflux for another 3 hours
The reaction was terminated. The reaction mixture is neutralized with 2N hydrochloric acid
And extracted with diethyl ether (500 mL). Get
The solution was dried over anhydrous sodium sulfate and the solvent was removed under vacuum.
The compound was obtained by distilling off. GPC analysis for molecular weight
As a result, Mn = 2480, Mw = 3650 (polystyrene
Conversion, UV detector). Analysis results by NMR
Of the total number of silicon atoms, Me₂-Si-O_2/2Join
91 mol%, Me₃-Si-O_1/29 mol% of bonds,
Met.

The following raw materials were used. Polycarbonate resin: viscosity average molecular weight of about 22,000
Bisphenol A type polycarbonate resin Metal salt of aromatic sulfur compound: diphenyl sulfone-3-
Potassium sulfonate (hereinafter abbreviated as M1) Perfluoroalkanesulfonic acid metal salt: potassium perfluorobutanesulfonate (hereinafter abbreviated as M2) Teflon resin: tetrafluoroethylene (Daikin Industries polyflon FA-500) (hereinafter abbreviated as PTFE) Abbreviation)

[0076]Example 1 Preparation of resin composition  100 parts by weight of polycarbonate resin, manufactured in Production Example 1
2 parts by weight of a flame retardant for resin addition (S-1), and phosphorus
Adekastab as a phenolic and phenolic stabilizer
HP-10 and AO-60 (both manufactured by Asahi Denka)
Name) 0.1 parts by weight, PTFE 0.2 parts by weight, diphenyi
0.1 parts by weight of potassium sulfone-3-sulfonate
After the dry blending, raise the cylinder temperature to 270 ° C.
The set twin screw extruder with vent [TEX44 (product
Name): Japan Steel Works] and melt extruded
As a result, a resin composition was obtained.

[0077]Preparation of test specimen  After drying the obtained pellets at 120 ° C. for 5 hours,
Using a 35t injection molding machine, cylinder temperature 310 ° C, gold
At a mold temperature of 50 ° C., a thickness of 1.6 mm and 3.2 mm bar (width
12 mm, 127 mm in length)
Was. Table 1 shows the results.

[0078]Evaluation method  -Flame retardancy: Difficulty of 1.6 mm bar according to UL-94 standard
Flammability was evaluated by the V test. -Impact resistance: 3.2 in thickness according to ASTM D-256
Evaluated by 23 ° C notched Izod impact test for mm bar
did.・ Surface appearance: Determined by visual evaluation according to the following criteria
Was. ：: Good △: Some silver, flash, etc. are generated ×: A lot of silver, flash, etc. are generated

[0079]Examples 2 to 4 and Comparative Examples 1 to 14  Add the amount of flame retardant, metal salt and Teflon (registered trademark) resin
Except for changing the number of copies shown in Table 1, the same as in Example 1
Thus, a resin composition was obtained. The pellets thus obtained
Each test piece was prepared in the same manner as above. These tests
The above evaluation method was performed on a piece. The evaluation results are shown in Tables 1 and 2,
And Table 3.

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

As shown in Table 1, all the examples show very good flame retardancy and good impact resistance. Further, since the main chain used as a flame retardant has an excellent flame retarding effect of a polymer composed of silicon, boron and oxygen, good flame retardancy is exhibited even with a very small number of added parts. .

As shown in Tables 2 and 3, Comparative Examples 1 and 2 were inferior in flame retardancy because no flame retardant and metal salt were used. In Comparative Examples 3 and 4, dripping occurred because no polymer as a flame retardant was used, and flashes were often observed on the surface of the molded product. In Comparative Example 5, since the amount of the flame retardant polymer added was a small amount outside the range of the present invention, the flame retardancy was insufficient. In Comparative Example 6, since the amount of the flame retardant polymer added was a large amount outside the range of the present invention, molding was difficult. In Comparative Examples 7 and 8, the flame retardancy is insufficient because the amount of the metal salt added is a small amount outside the range of the present invention. In Comparative Examples 9 to 14, since a silicone compound different from that of the present invention was used for the flame retardant, the flame retarding effect was insufficient when the number of added parts was small.

[0085]

As described above, the flame-retardant polycarbonate resin composition of the present invention has the above-mentioned constitution, and thus is very excellent in the addition of a small amount without using a commonly used flame retardant such as chlorine, bromine or phosphorus. It exhibits low flame retardancy and does not impair the inherent characteristics of the resin. And it can be relatively easily synthesized using inexpensive raw materials. Such a flame retardant polycarbonate resin composition is industrially very useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 85/04 C08L 85/04 F-term (Reference) 4J002 CG00W CG01W CG02W CG03W CG04W CP19X CQ02X EV286 FD010 FD136 GC00 GN00 GQ00 4J035 AA05 BA12 BA13 CA281 HA02 HA04 LA05

Claims (6)

[Claims] 1. A composition comprising 100 parts by weight of a polycarbonate resin (A), silicon, boron and oxygen, having a skeleton substantially formed of silicon-oxygen bonds and boron-oxygen bonds, and having an aromatic ring in the molecule. (B) having a polymer
A flame-retardant polycarbonate resin composition comprising from 0.01 to 10 parts by weight, and from 0.03 to 5 parts by weight of a metal salt (C) of an aromatic sulfur compound. 2. A composition comprising 100 parts by weight of a polycarbonate resin (A), silicon, boron and oxygen, having a skeleton substantially formed of silicon-oxygen bonds and boron-oxygen bonds, and having an aromatic ring in the molecule. (B) having a polymer
A flame-retardant polycarbonate resin composition comprising from 0.01 to 10 parts by weight, and from 0.01 to 5 parts by weight of a metal salt (D) of perfluoroalkanesulfonic acid. 3. The fluororesin (E) having a content of from 0.005 to 0.005.
3. The flame-retardant polycarbonate resin composition according to claim 1, comprising 1 part by weight. 4. A polymer (B) comprising silicon, boron and oxygen, having a skeleton substantially formed from silicon-oxygen bonds and boron-oxygen bonds, and having an aromatic ring in the molecule, Substantially Si-O-Si bond, Si-OB
And an aromatic ring in the molecule is directly connected to a silicon atom, and has a weight average molecular weight of 10
Claim 1 which is in the range of 00 to 200,000.
4. The flame-retardant polycarbonate resin composition according to 2 or 3. 5. The flame-retardant polycarbonate resin composition according to claim 1, wherein the metal salt of an aromatic sulfur compound (C) is a metal salt of an aromatic sulfonamide or a metal salt of an aromatic sulfonic acid. . 6. The flame-retardant polycarbonate resin composition according to claim 2, wherein the metal salt of perfluoroalkanesulfonic acid (D) has 1 to 8 carbon atoms.