JP2000327781A - Additive flame-retardant to aromatic resin and flame- retardant resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject flame-retardant capable of providing an aromatic resin with excellent flame retardance and optionally with long-term moist heat resistance by making the flame-retardant include a specific straight-chain silicone structure as a constituent unit. SOLUTION: This flame-retardant comprises a straight-chain silicone structure of the formula [R1 is OH, a 1-12C alkoxyl or a 1-12C monofunctional hydrocarbon group; R2 is H or a 1-12C alkyl; R3 is a 6-12C (substituted) aromatic group; (a) is 1-3; X is >=0.1; Y is >=1; Z is a number exceeding 0; and X+Y+Z is 3-100] as a constituent unit. The straight-chain silicone structures are mutually bonded by silicon atoms contained in the Y repeating units through oxygen atoms and the flame-retardant contains at least 0.15 aromatic group per silicon atom. The compound of the formula is obtained by adding an aromatic vinyl- based monomer and a vinyl group-containing silane to a hydrogenpolysiloxane by a hydrosilylation reaction to give a silicone of reaction intermediate and condensing and cross-linking the silicone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame retardant for adding an aromatic resin and a flame retardant resin composition using the same. More specifically, it belongs to a new technical field for improving the flame retardancy of an aromatic resin composition such as a polycarbonate resin.

[0002]

2. Description of the Related Art Aromatic resins (polymer resins having aromatic hydrocarbons in their molecules) are widely used industrially.
Examples thereof include polycarbonate, polyphenylene ether, polyester, polystyrene, acrylonitrile-butadiene-styrene (ABS), polyimide, and compositions obtained by alloying these resins. Among them, the polycarbonate resin has the highest impact resistance among engineering plastics and is known as a resin having good thermal deformation resistance. Further, in order to improve molding processability and the like, which are disadvantages of polycarbonate resins, polycarbonate alloys with thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthalate; styrene resins such as polystyrene and ABS; ing.

[0003] When such an aromatic resin is used industrially, for example, in the field of electric and electronic devices, the resin to be used is UL-94V to ensure safety against fire. In many cases, a high degree of flame retardancy is required so as to meet -0 (U.S. Underwriters Laboratory Standard), and various flame retardants have been developed and studied. In recent years, with increasing interest in environmental issues mainly in Europe, various uses of non-halogen flame retardants such as silicone flame retardants have been studied.

[0004] As a resin composition containing a silicone-based flame retardant, Japanese Patent Publication No. 62-60421 discloses a polysiloxane resin (polysiloxane resin) containing a thermoplastic non-silicone polymer containing at least 80% by weight of a T unit represented by the formula SiO _1.5. A siloxane resin having a molecular weight of 2,000 to 6,000, a phenyl group of 80% or less, and the remainder being a methyl group is described as being preferable for the flame resistance of the polymer composition). Also, JP-A-10-139
No. 964 discloses a flame retardant in which a silicone resin having a unit represented by the formula SiO _1.0 and a unit represented by the formula SiO _1.5 (weight average molecular weight is 10,000 or more and 270000 or less) is blended with a non-silicone resin containing an aromatic ring. Disclosed is a hydrophilic resin composition. On the other hand, JP-A-10-3168
No. 68 discloses flame retardant additives to aromatic-based polymers, including copolymers of aryl-containing silicone compounds and diorganopolysiloxane compounds.

When a conventional silicone-based flame retardant is used to make an aromatic resin flame-retardant, the flame-retardant property is obtained, but it does not reach an industrially practicable level or it is not economical. However, it was not satisfactory because of its relatively high cost. Further, in a resin molded article such as an electric / electronic part using a polycarbonate-based resin composition, when exposed to high temperature and high humidity for a relatively long time during transportation or storage, mechanical properties are deteriorated. There was a problem.

[0006]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention provides a flame retardant for addition which can impart excellent flame retardancy and, in some cases, long-term wet heat resistance to an aromatic resin.
Another object of the present invention is to provide a flame-retardant resin composition excellent in these properties.

[0007]

That is, the present invention comprises a linear silicone structure represented by the following formula (1) as a constitutional unit, and the linear silicone structures are arranged on the side of Y repeating units. A flame retardant for adding an aromatic resin, which is bonded to each other via an oxygen atom by a silicon atom contained in a chain and contains at least 0.15 aromatic groups per silicon atom.

[0008]

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(Wherein R ¹ is the same or different and is a hydroxyl group, an alkoxyl group having 1 to 12 carbon atoms or a C ¹ to C 1
2 represents a monovalent hydrocarbon group. R ² is the same or different and represents a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 12 carbon atoms. R ³ represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms. When there are a plurality of R ³ ,
They may be the same or different. a is 1, 2 or 3. X is a number not less than 0.1, Y is a number not less than 1, Z is a number exceeding 0, and X + Y + Z is 3-100. The arrangement of the X repeating units, the Y repeating units, and the Z repeating units may all be random, or all or some of them may form a block. )

Further, the present invention comprises a linear silicone structure represented by the above formula (1) and a (poly) siloxane structure represented by the following formula (2) as constituent units, and Is bonded to each other via an oxygen atom, and contains at least 0.15 aromatic groups per silicon atom, and is also a flame retardant for adding an aromatic resin.

[0011]

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(In the formula, R ⁴ is the same or different and represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms or a saturated or unsaturated alkyl group having 1 to 12 carbon atoms. Represents an integer of 1 to 5.)

The present invention is also a flame-retardant resin composition comprising 100 parts by weight of an aromatic resin and 0.1 to 30 parts by weight of any of the above-mentioned flame retardants. Hereinafter, the present invention will be described in detail.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The flame retardant of the present invention has the above formula (1)
Is a cross-linked silicone compound having a structure in which a linear silicone structure represented by is a structural unit, and the linear silicone structures are bonded to each other via an oxygen atom at a silicon atom in a side chain. .

In the formula (1), R ¹ represents a hydroxyl group, an alkoxyl group having 1 to 12 carbon atoms or a monovalent hydrocarbon group having 1 to 12 carbon atoms. A plurality of R ¹ may be the same or different. Among them, a hydrocarbon group having 1 to 12 carbon atoms is preferable, for example, a methyl group, an ethyl group,
And a phenyl group.

R ² is a hydrogen atom or a group having 1 to 12 carbon atoms.
Represents a saturated or unsaturated alkyl group. Multiple R
² may be the same or different. Preferred are a methyl group, an ethyl group and a vinyl group.

R ³ represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms. When there are a plurality of R ^{3 s} , they may be the same or different. Carbon number 6
Specific examples of the substituted or unsubstituted aromatic group of ~ 12,
Examples include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an alkyl-substituted derivative thereof, and a halogen-substituted derivative thereof. It is preferably a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, and among them, a phenyl group or a tolyl group is preferred.

In the formula (1), a represents the number of oxygen atoms directly bonded to the silicon atom in the side chain (however, excluding the hydroxyl group of R ¹ and the oxygen atom of the alkoxyl group);
Or 3. However, when Y is 2 or more, a in each side chain independently represents any one of 1, 2 or 3. In particular, from the viewpoints of economy, workability of the composition when the flame retardant is added, and the like, the mixture of 1 and 3 is preferable.

On the other hand, in the formula (1), X, Y and Z are
Indicates the number of each repeating unit. X is a number greater than or equal to 0.1, Y is a number greater than or equal to 1, and Z is a number greater than zero.
Note that Z may be 0 in each constituent unit. X + Y + Z is 3 to 100. Preferably it is 5-80. If it is less than 3, the workability at the time of processing the composition at the time of adding the flame retardant may be poor, or the mechanical strength of the molded article may be reduced. If it exceeds 100, the effect of improving the flame retardancy is obtained. There is a problem that there may not be. Of these, Y
The number of repeating units is preferably 2 or more.

The linear silicone structure (1) is composed of three types of repeating units (X repeating units, Y repeating units, and Z repeating units). The sequence is not particularly limited, and all of them may be random, or
All or some of these repeating units may form a block.

Each of a plurality of structural units (1) (linear silicone structure) present in the crosslinked silicone compound which is a flame retardant of the present invention may be the same,
It may be different. That is, the substituents R ¹ , R ² and / or R ³ may be different for each structural unit (1), or the number X, Y and / or Z or a of the repeating units may be different. They may be different, or the order of the repeating units may be different.

In the crosslinked silicone compound which is a flame retardant of the present invention, the above-mentioned linear silicone structures (1) are bonded to each other via an oxygen atom via a silicon atom contained in the side chain of Y repeating units. It has a structure that is bonded to each other. That is, it has a structure in which silicon atoms in the side chains are bonded to each other via an oxygen atom, and linear silicone is crosslinked.

In one structural unit (1), if Y is fixed to 1, there is a possibility that the structural unit is combined with a different structural units. On the other hand, if a is fixed to 1, there is a possibility that Y different structural units are combined with one structural unit. Thus, each constituent unit may combine with at most Y × a other constituent units. However, there may be a silicon atom which does not participate in the bonding between the structural units (1), and this silicon atom may be bonded to another side chain in one structural unit via an oxygen atom. Alternatively, it may be sealed with a triorganosiloxy group (for example, a trimethylsiloxy group or the like).

A flame retardant according to another embodiment of the present invention is a compound having the above-mentioned linear silicone structure (1) and the (poly) siloxane structure represented by the above formula (2) as constitutional units. In this embodiment, the mechanical properties and surface properties of the resin composition to which the flame retardant of the present invention has been added can be made higher depending on the properties of the aromatic resin.

In the equation (2), R^Four Has 6 or more carbon atoms
12 substituted or unsubstituted aromatic groups, or 1 carbon atom
Represents up to 12 saturated or unsaturated alkyl groups. Multiple
Some R ^Four May be the same or different
No. Specifically, for example, a methyl group, an ethyl group,
Group, phenyl group, tolyl group, xylyl group, naphthyl group
And the like. Among them, phenyl
Groups or methyl groups are preferred. N is an integer of 1 to 5
You.

The flame retardant of the present invention in this embodiment is a compound having a structure in which at least the above-mentioned linear silicone structure (1) and the above-mentioned (poly) siloxane structure (2) are bonded and silicone is crosslinked. . In this structure, silicon atoms contained in the side chains of the Y repeating units in the linear silicone structure (1) are bonded to each other via the (poly) siloxane structure (2).

However, the flame retardant of the present invention in this embodiment is characterized in that, in addition to the bond between the linear silicone structure (1) and the (poly) siloxane structure (2), the bond between the linear silicone structures (1) And (poly) siloxane structure (2) may have a bond. When the linear silicone structures (1) are bonded to each other, they are bonded to each other via an oxygen atom as described above.

The crosslinked silicone compound as a flame retardant of the present invention has an average of at least 0.1 per silicon atom.
It has 15 aromatic groups. In order to obtain an excellent flame retardant effect, it is preferable to have 0.20 to 1.5 aromatic groups. When the number of aromatic groups is less than 0.15, there is a problem that the effect of improving the flame retardancy cannot be sufficiently obtained or the surface appearance of a molded article obtained from the composition containing the flame retardant is deteriorated. There are cases.

In producing such a crosslinked silicone compound, various methods known to those skilled in the art can be used. Useful documents include, for example, JP-A-10-316868.

[0030] The flame retardant of the present invention can be suitably produced by the following method. First, as the first step,
An aromatic vinyl monomer (for example, styrene) and a silane containing a vinyl group are added to the hydrogen polysiloxane according to a known hydrosilylation reaction. Examples of the vinyl group-containing silanes used herein include vinyl group-containing alkoxyl silanes (for example, trimethoxyvinyl silane) and vinyl group-containing chlorosilanes. In the hydrosilylation reaction, a known hydrosilylation catalyst such as a platinum compound can be used. By this hydrosilylation reaction, a silicone represented by the following formula (3) is obtained as a reaction intermediate common to the two flame retardants according to the present invention.

[0031]

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(Wherein, R ² , R ³ , a, X, Y and Z are the same as above. R ⁵ is the same or different and represents a hydroxyl group, an alkoxyl group having 1 to 12 carbon atoms or a chlorine atom. R ⁶
Represents the same or different and represents a monovalent hydrocarbon group having 1 to 12 carbon atoms. )

In order to produce a crosslinked silicone compound comprising only the linear silicone structure (1), which is one embodiment of the flame retardant of the present invention, as a second step, a reactive hydroxylsilyl group as described above, The reaction intermediate having an alkoxylsilyl group or a chlorosilyl group is subjected to condensation crosslinking using a known reaction such as a dehydration-condensation reaction of silanol, hydrolysis of alkoxysilane or chlorosilane, followed by a dehydration-condensation reaction. At the time of the dehydration condensation reaction, it is preferable to use a known tin catalyst or the like in order to accelerate the reaction.

On the other hand, a cross-linked silicone compound comprising a linear silicone structure (1) and a (poly) siloxane structure (2), which is another embodiment of the flame retardant of the present invention, is a bifunctional compound having a bifunctional property. It can be produced by carrying out in the presence of a silicon-containing compound. Examples of the bifunctional silicon-containing compound include a polysiloxane compound having a reactive group such as a silanol group at a terminal obtained by a ring-opening reaction of a cyclic siloxane such as octamethylcyclotetrasiloxane; diphenyldimethoxysilane, dimethyldimethoxy Silane and the like can be mentioned.

In order to control the molecular weight of the cross-linked silicone compound, a monofunctional silicon-containing compound such as trimethylmethoxysilane or trimethylchlorosilane is further reacted during or after the above-mentioned dehydration condensation reaction, whereby the side chain silicon Atoms can also be sealed.

The shape when the flame retardant of the present invention is used is not particularly limited, and may be any shape such as oil, gum, varnish, powder, and pellet. When the flame retardant of the present invention is used, only one type may be used alone or two or more types may be used in combination.
The combination of two or more types is not particularly limited, and those having different polymerization components and molar ratios, those having different molecular weights, and the like can be used in any combination.

The desired purpose can be achieved by adding 0.1 to 30 parts by weight of the flame retardant of the present invention to 100 parts by weight of the aromatic resin. If the amount is less than 0.1 part by weight, the effect of improving the flame retardancy may not be obtained, and if the amount exceeds 30 parts by weight, the surface properties, moldability and the like tend to deteriorate. Preferably it is 0.3 to 25 parts by weight, more preferably 0.5 to 20 parts by weight. In addition, what is mentioned later can be used as an aromatic resin.

The second aspect of the present invention is a flame-retardant resin composition containing 100 parts by weight of an aromatic resin and 0.1 to 30 parts by weight of the additive flame retardant.

The aromatic resin (polymer resin having an aromatic hydrocarbon in the molecule) used in the resin composition of the present invention is not particularly limited, and examples thereof include a polycarbonate resin, a polyphenylene ether resin, and a thermoplastic resin. Polyester resin, aromatic vinyl resin (specifically, polystyrene, acrylonitrile-butadiene-styrene (A
BS)) and thermoplastic resins such as polyimide resins. The aromatic resin preferred in the present invention is at least one selected from the group consisting of a polycarbonate resin, a thermoplastic polyester resin, a polyphenylene ether resin, and an aromatic vinyl resin.

The polycarbonate resin among the aromatic resins is a polycarbonate obtained by polymerizing a phenol compound having a valency of 2 or more and phosgene or a carbonic acid diester by a known method.

The dihydric phenol compound is not particularly restricted but includes, for example, 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A] and 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, 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
Dihydroxydiarylalkanes such as -bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl)
Dihydroxydiarylcycloalkanes such as cyclodecane; dihydroxydiarylsulfones such as bis (4-hydroxyphenyl) sulfone and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; bis (4-
Dihydroxydiaryl ethers such as hydroxyphenyl) ether and bis (3,5-dimethyl-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, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide and the like Dihydroxydiaryl sulfides; dihydroxy diaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide;
Dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl; dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene; dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone; 1,5-dihydroxy Dihydroxynaphthalenes such as naphthalene and 2,6-dihydroxynaphthalene; and the like. These may be used alone or in combination of two or more. Among them, bisphenol A is preferred.

The diester carbonate is not particularly limited.
For example, diaryl carbonates such as diphenyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; These may be used alone or in combination of two or more.

Preferred polycarbonate resins are 2,2 from the viewpoint of balance between mechanical strength and moldability.
A polycarbonate resin obtained by reacting -bis (4-hydroxyphenyl) propane with diphenyl carbonate, a polycarbonate resin obtained by reacting 2,2-bis (4-hydroxyphenyl) propane and dimethyl carbonate, 2 Bis (4-hydroxyphenyl) propane and diethyl carbonate, a polycarbonate resin obtained by reacting bis (4-hydroxyphenyl) methane with diphenyl carbonate, a bis (4 (Hydroxyphenyl) phenylmethane and polycarbonate resin obtained by reacting diphenyl carbonate.

The polycarbonate resin is not limited to a straight polycarbonate, but may be a branched polycarbonate. The branching agent used to obtain the branched polycarbonate is not particularly limited, and includes, for example, phloroglucin, melitic acid, trimellitic acid, trimellitic chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic Acid, pyromellitic dianhydride, α-resorcinic acid, β-resorcinic acid, resorcinaldehyde, isatin bis (o-cresol), benzophenonetetracarboxylic acid, 2,4,
4'-trihydroxybenzophenone, 2,2 ', 4
4'-tetrahydroxybenzophenone, 2,4,4 '
-Trihydroxyphenyl ether, 2,2 ', 4
4'-tetrahydroxyphenyl ether, 2,4
4'-trihydroxydiphenyl-2-propane, 2,
2'-bis (2,4-dihydroxyphenyl) propane, 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) -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, tris (4'-hydroxyphenyl) -amyl-s-triazine and the like.

In some cases, the polycarbonate resin may be a polycarbonate-polyorganosiloxane copolymer composed of a polycarbonate part and a polyorganosiloxane part. At this time, the degree of polymerization of the polyorganosiloxane part is preferably 5 or more.

Further, the polycarbonate resin is a polycarbonate resin obtained by copolymerizing a linear aliphatic dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and the like. It may be united. Further, in order to enhance the weather resistance, a polycarbonate copolymer with a dihydric phenol having a benzotriazole group may be used.

As the terminal terminator used for polymerizing the polycarbonate resin, various known terminators can be used. Specifically, monohydric phenols such as phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol and nonylphenol are exemplified.

The polycarbonate resin preferably has a viscosity average molecular weight of 10,000 to 60,000. 1
When it is less than 0000, the strength and heat resistance of the obtained resin composition are often insufficient. On the other hand, when it exceeds 60,000, molding processability is often insufficient. It is more preferably 15,000 to 45,000, and still more preferably 18,000 to 35,000.

As the polycarbonate resin, 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, the combination is not particularly limited. For example, those having different monomer units, different copolymerization molar ratios, different molecular weights, and the like can be arbitrarily combined.

Among the aromatic resins used in the resin composition of the present invention, the thermoplastic polyester resins include a divalent or higher valent aromatic carboxylic acid compound and a divalent or higher valent alcohol and / or phenol compound. Is a thermoplastic polyester obtained by polycondensation according to the above method. Specifically, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like,
It is not limited to these. Among these thermoplastic polyesters, polyethylene terephthalate, polypropylene terephthalate or polybutylene terephthalate is preferred from the viewpoint of heat resistance and moldability.

The divalent or higher valent aromatic carboxylic acid compound is not particularly limited, and examples thereof include divalent or higher valent aromatic carboxylic acids having 8 to 22 carbon atoms, and ester-forming derivatives thereof. Specifically, for example, phthalic acid such as terephthalic acid and isophthalic acid; naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4-4′-diphenyldicarboxylic acid,
2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, diphenylsulfonedicarboxylic acid, trimesic acid,
Examples thereof include carboxylic acids such as trimellitic acid and pyromellitic acid, and derivatives thereof having an ester forming ability. These may be used alone or in combination of two or more. Above all, terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid is preferred from the viewpoints of ease of handling, ease of reaction, and properties of the obtained resin composition.

The dihydric or higher alcohol and / or phenol compound is not particularly limited.
15 aliphatic compounds, an alicyclic compound having 6 to 20 carbon atoms,
Examples thereof include aromatic compounds having 6 to 40 carbon atoms and having two or more hydroxyl groups in a molecule, and ester-forming derivatives thereof. Specifically, for example, ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2'-bis (4-hydroxyphenyl) propane, 2,2 '-Bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, derivatives thereof having an ester-forming ability, and the like. These may be used alone or in combination of two or more. Among them, ethylene glycol, butanediol or cyclohexane dimethanol is preferred from the viewpoints of ease of handling, ease of reaction, and properties of the obtained resin composition.

The thermoplastic polyester resin can be obtained by copolymerizing a known copolymerizable compound in addition to the aromatic carboxylic acid compound and the alcohol and / or phenol compound as long as the desired properties are not impaired. May be obtained. Such copolymerizable compounds are not particularly limited, and include, for example, 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, Ester-forming derivatives and the like. Specifically, for example, dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid, and derivatives having an ester-forming ability thereof And the like. Other examples include oxyacids such as p-oxybenzoic acid and p-hydroxybenzoic acid or ester-forming derivatives thereof, and cyclic esters such as ε-caprolactone.

The thermoplastic polyester resin may be a thermoplastic polyester resin obtained by partially copolymerizing a polyalkylene glycol unit in a polymer chain. The polyalkylene glycol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, bisphenol A copolymerized polyethylene oxide addition polymer, and propylene copolymer. Oxide addition polymer,
The same tetrahydrofuran addition polymer, polytetramethylene glycol and the like can be mentioned.

The use amount of the above-mentioned copolymer component in the thermoplastic polyester resin is usually 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less.

The thermoplastic polyester resin is preferably a polyalkylene terephthalate containing an alkylene terephthalate unit in an amount of 80% by weight or more, since the resulting resin composition has an excellent balance of physical properties (eg, moldability and mechanical properties). . More preferably, the same unit is 85
It is a polyalkylene terephthalate containing at least 90% by weight, more preferably at least 90% by weight.

The thermoplastic polyester resin has a logarithmic viscosity (IV) of 0.3 when measured at 25 ° C. in a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solvent.
It is preferably 0 to 2.00 dl / g or more. If the logarithmic viscosity is less than 0.30, the mechanical strength of the molded product is often insufficient, and if it exceeds 2.00 dl / g, the moldability tends to decrease. More preferably 0.40
1.80 dl / g, more preferably 0.50 to
1.60 dl / g.

As the thermoplastic polyester resin, 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, the combination is not particularly limited. For example, those having different copolymer components and different molar ratios, those having different molecular weights, and the like can be arbitrarily combined.

Among the aromatic resins used in the resin composition of the present invention, the aromatic vinyl resin may be a resin obtained by homopolymerizing an aromatic vinyl compound, or a main vinyl aromatic compound. As a monomer, a resin obtained by copolymerizing at least one vinyl monomer such as an unsaturated nitrile compound, an alkyl (meth) acrylate, an N-substituted maleimide, an unsaturated carboxylic acid and / or an anhydride thereof is used. That means. Further, a copolymerizable monomer other than these may be used.

The aromatic vinyl compound which is a main monomer of the aromatic vinyl resin is not particularly limited.
Styrene, o-methylstyrene, p-methylstyrene,
m-methylstyrene, α-methylstyrene, vinyltoluene, divinylbenzene and the like. These may be used alone or in combination of two or more.

The unsaturated nitrile compound is not particularly restricted but includes, for example, acrylonitrile, methacrylonitrile and the like. The alkyl (meth) acrylate is not particularly limited, and examples thereof include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid. Examples include stearyl, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and the like. The N-substituted maleimide is not particularly limited, and includes, for example, maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof. The unsaturated carboxylic acid and / or anhydride thereof is not particularly limited, and includes, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and the like.

The other copolymerizable monomer is not particularly restricted but includes, for example, vinyl alkyl ether, unsaturated amino compound, di-alkyl maleate, allyl alkyl ether, diene compound, vinyl acetate and the like. .

The vinyl alkyl ether is not particularly restricted but includes, for example, vinyl methyl ether, vinyl ethyl ether, vinyl i-propyl ether, vinyl n-propyl ether, vinyl i-butyl ether, vinyl n
-Amyl ether, vinyl i-amyl ether, vinyl 2-ethylhexyl ether, vinyl octadecyl ether and the like. The unsaturated amino compound is not particularly limited, and includes, for example, acrylamide, methacrylamide and the like. The di-alkyl maleate is not particularly restricted but includes, for example, di-n-amyl maleate, di-i-butyl maleate, dimethyl maleate, di-n-propyl maleate, di-maleate. -Octyl ester, di-nonyl maleate and the like. The allyl alkyl ether is not particularly limited, and includes, for example, allyl ethyl ether, allyl n-octyl ether and the like. The diene compound is not particularly limited, for example,
Dicyclopentadiene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbonadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclohexadiene, 1,3-cyclooctaene Diene and the like.

Preferred aromatic vinyl resins include polystyrene, polymethyl methacrylate, styrene / acrylonitrile copolymer, methyl methacrylate / acrylonitrile copolymer, styrene / N-phenylmaleimide copolymer, and styrene / acrylonitrile / N-phenyl. And maleimide copolymers.

The aromatic vinyl resin is preferred from the viewpoint of processability.
The reduced viscosity is preferably 0.2 to 1.2 dl / g (dimethylformamide solution, 30 ° C., concentration 0.3 g / dl). If the reduced viscosity is less than 0.2 dl / g, the mechanical strength may decrease, and if it exceeds 1.2 dl / g, the fluidity tends to decrease. More preferably, 0.
3 to 0.9 dl / g.

Among the aromatic resins used in the resin composition of the present invention, the polyphenylene ether-based resin is a single monomer having a repeating unit represented by the following general formula (4) and / or (5), It is a copolymer.

[0067]

Embedded image

(Where R⁷ , R⁸ , R⁹ , R^Ten, R¹¹Passing
And R¹²Are the same or different and each represents a hydrogen atom,
Represents an alkyl group or an aryl group having 6 to 10 carbon atoms. However
Then R ^TenAnd R¹¹Represents a hydrogen atom at the same time
Good. )

The polyphenylene ether homopolymer is not particularly limited, and typical examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and
Poly (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.
Copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymer of 2,6-dimethylphenol and o-cresol, 2,6-dimethylphenol and 2,2 And copolymers of 3,6-trimethylphenol and o-cresol.

The aromatic resin used in the resin composition of the present invention may be one using two or more of the above aromatic resins. In particular, when a polycarbonate resin is used as a main aromatic resin, an ABS resin, a polystyrene resin, a modified polystyrene resin; polyethylene terephthalate or a polystyrene resin is used as long as its properties (flame retardancy, long-term wet heat resistance, etc.) are not impaired. It may be alloyed with a thermoplastic polyester resin such as butylene terephthalate; and the like. Further, another thermoplastic resin or thermosetting resin may be further added singly or in combination of two or more. Such a resin is not particularly limited, for example, a liquid crystal polyester resin, a polyester ester elastomer resin, a polyester ether elastomer resin, a polyolefin resin, a polyamide resin,
Examples include polyphenylene sulfide-based resin, polyphenylene ether-based resin, polyacetal-based resin, and polysulfone-based resin.

Particularly, in the present invention, when the aromatic resin is a polycarbonate resin or a combination of the polycarbonate resin and at least one of a thermoplastic polyester resin and an aromatic vinyl resin. Thus, a resin composition having not only flame retardancy but also excellent long-term wet heat resistance can be obtained.

In the flame retardant resin composition of the present invention, 0.1 to 30 parts by weight of a flame retardant is used based on 100 parts by weight of the aromatic resin. If the amount is less than 0.1 part by weight, the effect of improving the flame retardancy may not be obtained.
Surface properties and moldability tend to deteriorate. Preferably it is 0.3 to 25 parts by weight, more preferably 0.5 to 25 parts by weight.
20 parts by weight.

In the flame-retardant resin composition of the present invention, only one type of the flame retardant of the present invention may be used alone, or two or more types may be used in combination. In addition, the shape is not particularly limited, oil-like, gum-like, varnish-like,
Any shape such as a powder or a pellet can be used.

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.

[0075] Of the preferred rubber-like elastic bodies, the term "graft rubber" refers to a rubber obtained by graft copolymerizing a vinyl-based monomer with a general rubber-like elastic body. 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 to 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 rubber-like elastic material and the vinyl-based 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 aromatic resin tends to decrease.

Among the preferred rubber-like elastic materials, olefin-based resins include, in addition to polyolefins in a narrow sense, polydienes and copolymers composed of two or more thereof, copolymers composed of olefin monomers and two or more diene monomers, and olefins. 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 for 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 long 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 according to the present invention means a polyorganosiloxane in a broad sense excluding the flame retardant for addition according to the present invention. Specifically, (silicon) such as dimethylsiloxane and phenylmethylsiloxane (Poly) diorganosiloxane compounds; (poly) organosilsesquioxane compounds such as methylsilsesquioxane and phenylsilsesquioxane; (poly) triorganosils such as trimethylsilhemioxane and triphenylsilhemioxane Hemioxane compounds; copolymers obtained by polymerizing these; polydimethylsiloxane, polyphenylmethylsiloxane and the like. 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. There is no particular limitation on the shape of the silicone, oil-like, gum-like, varnish-like,
Any material such as powder and pellets can be used.

Further, the flame-retardant resin composition of the present invention may be used as a reinforcing material by combining a reinforcing filler within a range that does not impair the properties (flame retardancy and the like) of the present invention. That is, heat resistance, mechanical strength, etc. can be further improved by adding a reinforcing filler. Such a reinforcing filler is not particularly limited, and examples thereof include fibrous fillers such as glass fiber, carbon fiber, and potassium titanate fiber; glass beads, glass flakes; talc, mica, kaolin,
Silicate compounds such as wollastonite, smectite, and diatomaceous earth; and 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 and having a shape such as powder, granule, needle, and plate 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.
It is 1 to 50 μm, more preferably 0.3 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 treatment 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 includes, for example, glass fiber, carbon fiber, potassium titanate fiber and the like. 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 fiber is 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 to be added is not limited as long as the properties (flame retardancy and the like) of the present invention are not impaired, but is preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the resin composition. Preferably 1 to 60 parts by weight, more preferably 2 parts by weight
４０40 parts by weight. If the amount is less than 0.5 part by weight, the effect of improving mechanical strength may be small, and if it exceeds 100 parts by weight, properties such as workability and impact resistance tend to be impaired.

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-based antioxidant; a heat stabilizer such as a phosphorus-based stabilizer; And the like are preferably used alone or in combination of two or more. Further, if necessary, usually well-known, lubricants, release agents, plasticizers, flame retardants such as phosphorus compounds,
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 can be suitably used for various uses. Preferred uses include injection molded products such as home appliances, OA equipment parts, automobile parts,
Blow molded articles, extruded molded articles, foam molded articles and the like can be mentioned.

[0096]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, "parts"
Means parts by weight, and "%" means% by weight.

[0097]Production Example 1 of resin-added flame retardant (S-1)
Manufacture  Platinum divinyl siloxane 31.2 × 10^-3mmol
In a hexane solution of 800 ml, molecules with a polymerization degree of 35-45
Trimethylsiloxy group-blocked methyl hydrogen
Mixture of polysiloxanes (of silicon-bonded hydrogen atoms)
Content: 1.0 wt%) 250 g and trimethoxyvinyl
190 g of silane was added and stirred for 1 hour under reflux. Continued
After adding 150 g of styrene and reacting similarly, the solvent was removed.
This was removed to obtain a liquid modified polysiloxane. Then visua
Add 40 g of dibutyltin cetylacetonate and stir,
After curing at 50 ° C for 10 hours, excess trimethylmeth
Toxisilane (300 g) was added to block the end,
Cured for 10 hours. The reaction mixture is solvent and
And low-molecular substances such as unreacted silane
A flame retardant for addition (S-1) was obtained. X made by Varian
The NMR spectrum was measured using the L-300 apparatus.
As a result, 0.36 phenyl groups were confirmed per silicon atom.
It has been certified.

[0098]Production Example 2 of resin-added flame retardant (S-2)
Manufacture  Platinum divinyl siloxane 31.2 × 10^-3mmol
In a hexane solution of 800 ml, molecules with a polymerization degree of 35-45
Trimethylsiloxy group-blocked methyl hydrogen
Mixture of polysiloxanes (of silicon-bonded hydrogen atoms)
280 g and 0.5% by weight of trimethoxyvinyl
75 g of silane was added and stirred for 1 hour under reflux. continue
100 g of styrene was added and reacted similarly. Then gif
244 g of phenyldimethoxysilane and bisacetylacetate
Add 40 g of toner todibutyltin, stir and at 50 ° C
After curing for 10 hours, excess trimethylmethoxy
Runs (300 g) were added to seal the ends and an additional 10 hours
Cured. Solvent and unreacted reaction mixture in vacuum
Removes low molecular substances such as silane, and is used for adding solid resin
A flame retardant (S-2) was obtained. XL-3 made by Varian
As a result of measuring the NMR spectrum using the
0.6 phenyl groups were confirmed per elementary atom.

[0099]Production Example 3 of flame retardant for resin addition (S-3)
Manufacture  Platinum divinyl siloxane 31.2 × 10^-3mmol
In a hexane solution of 800 ml, molecules with a polymerization degree of 35-45
Trimethylsiloxy group-blocked methyl hydrogen
Mixture of polysiloxanes (of silicon-bonded hydrogen atoms)
Content: 1 wt%) 250 g and trimethoxyvinylsila
120 g was added, and the mixture was stirred under reflux for 1 hour. Then
200 g of styrene was added and reacted similarly. Next, Jife
245 g of nildimethoxysilane and bisacetylacetate
Add 40 g of sodium dibutyltin, stir and add 10 g at 50 ° C.
After curing for an hour, excess trimethylmethoxysilane
(300 g) was added to seal the end, and then cured for 10 hours.
I let it. The reaction mixture is evaporated in vacuo with solvent and unreacted silica.
Removes low molecular substances such as
Agent (S-3) was obtained. XL-300 made by Varian
The NMR spectrum was measured using the
0.8 phenyl groups were confirmed per child.

[0100]Production Example 4 of flame retardant for resin addition (S-4)
Manufacture  Platinum divinyl siloxane 31.2 × 10^-3mmol
In a hexane solution of 800 ml, molecules with a polymerization degree of 35-45
Trimethylsiloxy group-blocked methyl hydrogen
Mixture of polysiloxanes (of silicon-bonded hydrogen atoms)
Content: 1.3 wt%) 290 g and trimethoxyvinyl
75 g of silane was added and stirred for 1 hour under reflux. continue
300 g of styrene was added and reacted similarly. Then gif
360 g of phenyldimethoxysilane and bisacetylacetate
Add 40 g of toner todibutyltin, stir, and add
After curing for 0 hour, excess trimethylmethoxysil
(300 g) was added to block the ends, and the mixture was further cultured for 10 hours.
Alive. The reaction mixture is freed of solvent and unreacted
Removes low-molecular substances such as orchids, making it difficult to add solid resin
A fuel (S-4) was obtained. XL-30 made by Varian
As a result of measuring the NMR spectrum using the
1.1 phenyl groups were confirmed per atom.

[0101]Example 1 Preparation of resin composition  Bisphenol A type polymer with a viscosity average molecular weight of about 22,000
100 parts by weight of a carbonate resin (A-1), Production Example 1
5 parts by weight of the flame retardant for resin addition (S-1) produced in
Adeka as a phosphorus-based and phenol-based stabilizer
Stub HP-10 and AO-60 (both manufactured by Asahi Denka)
Product name) After dry blending each 0.3 parts by weight in advance,
Vent twin screw press with cylinder temperature set to 280 ° C
Hopper of the launch machine [TEX44 (trade name): manufactured by Japan Steel Works]
And melt extruded to obtain a resin composition.
Was.

[0102]Preparation of test specimen  After drying the obtained pellet at 100 ° C. for 5 hours
(However, when using the following aromatic vinyl resin,
Is not dried), using a 35t injection molding machine,
1.8 m thickness at 280 ° C die temperature and 50 ° C mold temperature
m, 2.3 mm or 2.8 mm bar (width 12 mm, length
ASTM No. 1 with a thickness of 127 mm) and a thickness of 3.2 mm
A dumbbell test piece was prepared and evaluated as follows. result
Are shown in Table 1.

[0103]Evaluation method  -Flame retardancy: 1.8 mm thick according to UL-94 standard
The flame retardancy of 2.3 mm or 2.8 mm bars was evaluated in the V test.
Valued.・ Long term wet heat resistance: ASTM No.1 dumbbell test piece
Leave under the conditions of 85 ° C and 80% humidity for 2000 hours.
Was. Each of the test pieces before and after standing was subjected to ASTM D638.
According to the conditions of a temperature of 23 ° C and a tensile speed of 10 mm / min
A tensile test, and determine the difference in tensile strength between the test pieces before and after standing.
From the tensile strength retention rate [= (
Difference) / tensile strength of test piece before standing × 100 (%)]
Issued. The higher the tensile strength retention, the better the long-term wet heat resistance
To indicate that

[0104]Examples 2 to 13 and Comparative Examples 1 to 17  Except that each component was changed to the composition shown in Tables 1 to 6,
A resin composition was obtained in the same manner as in Example 1. However, implementation
In Examples 7 and 8 and Comparative Examples 7 to 10, the cylinder temperature was set to 24.
The temperature was changed to 0 ° C. and melt extrusion was performed. The pen thus obtained
Each test piece was prepared from the let in the same manner as above. However
In Examples 5 and 6 and Comparative Examples 3 to 6, the mold temperature was 12
At 0 ° C., the cylinders in Examples 7 and 8 and Comparative Examples 7 to 10
A test piece was prepared by changing the temperature to 240 ° C. these
The above evaluation method was carried out using the test pieces of Example 1. Table 1 shows the evaluation results.
6 is shown. The following components are listed in the table.
You.

Dimethyl silicone (S-5): viscosity 2
Dimethylpolysiloxane of 200 centipoise Polyethylene terephthalate (B-1): a polyethylene terephthalate resin having a logarithmic viscosity of about 0.75 dl / g Polybutylene terephthalate (B-2): a polymer having a logarithmic viscosity of 0.8 dl / g Butylene terephthalate resin-ABS resin (C-1): HR-101 (manufactured by Kanegafuchi Chemical Industry)-Polystyrene (C-2): styrene G13 (manufactured by Nippon Steel Chemical Industry)-PPE (D-1): in chloroform Poly (2,6-dimethyl-1,4-phenylene) ether resin having a reduced viscosity of 0.50 dl / g measured at 30 ° C. PTFE (polytetrafluoroethylene) (E-
1): Polyflon FA-500 (manufactured by Daikin) (B-1) to (D-1) are aromatic resins,
(E-1) is an anti-dripping agent.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

Comparative Examples 1 and 3 to which no flame retardant was added
4, 7, 8, 11, 14 and 16 are inferior in flame retardancy, or flame retardancy and long-term wet heat resistance, as compared with Examples to which the flame retardant of the present invention was added. Comparative Examples 2, 5, 6, 9, 10, to which a silicone compound other than the flame retardant of the present invention was added.
12, 13, 15 and 17 could not be evaluated because they were inferior in flame retardancy and long-term wet heat resistance or poor in moldability as compared with the examples. Clearly from the above, the flame retardant for addition of the present invention can impart excellent flame retardancy to an aromatic resin, and the flame retardant composition of the present invention is:
It turns out that it is excellent in flame retardance or flame retardancy and long-term wet heat resistance.

[0113]

Since the present invention has the above-mentioned constitution, it has excellent flame retardancy, or an additive flame retardant capable of imparting flame retardancy and long-term wet heat resistance, and excellent in these properties. A flame-retardant resin composition can be obtained, which is industrially very useful.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BC001 CF041 CG001 CH061 CP032 CP172 FD132 GN00 GQ00 4J035 BA04 CA01M CA02U CA06U CA30M GA01 GB03 GB05 HA01 HA02 HB01 HB03 LA03 LB20

Claims (6)

[Claims] 1. A linear silicone structure represented by the following formula (1) as a constituent unit, wherein said linear silicone structures are composed of an oxygen atom and a silicon atom contained in a side chain of Y repeating units. Are connected to each other through
A flame retardant for adding an aromatic resin, comprising at least 0.15 aromatic groups per silicon atom. Embedded image (Wherein, R ¹ is the same or different and is a hydroxyl group, a carbon atom 1
Represents an alkoxyl group having 1 to 12 carbon atoms or a monovalent hydrocarbon group having 1 to 12 carbon atoms. R ² is the same or different and represents a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 12 carbon atoms. R ³ represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms. When there are a plurality of R ³ , they may be the same or different. a is 1, 2 or 3.
X is a number greater than or equal to 0.1; Y is a number greater than or equal to 1;
Is a number exceeding 0, and X + Y + Z is 3 to 100
It is. The arrangement of the X repeating units, the Y repeating units, and the Z repeating units may all be random, or all or some of them may form a block. ) 2. A composition comprising a linear silicone structure represented by the following formula (1) and a (poly) siloxane structure represented by the following formula (2) as structural units, and the linear silicone structures are bonded to each other. Are bonded to each other via oxygen atoms and at least 0.15 per silicon atom
A flame retardant for adding an aromatic resin, comprising a plurality of aromatic groups. Embedded image (Wherein, R ¹ is the same or different and is a hydroxyl group, a carbon atom 1
Represents an alkoxyl group having 1 to 12 carbon atoms or a monovalent hydrocarbon group having 1 to 12 carbon atoms. R ² is the same or different and represents a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 12 carbon atoms. R ³ represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms. When there are a plurality of R ³ , they may be the same or different. a is 1, 2 or 3.
X is a number greater than or equal to 0.1; Y is a number greater than or equal to 1;
Is a number exceeding 0, and X + Y + Z is 3 to 100
It is. The arrangement of the X repeating units, the Y repeating units, and the Z repeating units may all be random, or all or some of them may form a block. ) (Wherein, R ⁴ is the same or different and is a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or 1 to 12 carbon atoms.
Represents a saturated or unsaturated alkyl group. n is 1 to 5
Represents an integer. ) 3. A resin composition comprising 100 parts by weight of an aromatic resin and a linear silicone structure represented by the following formula (1) as a constituent unit. Flame retardant which is bonded to each other via an oxygen atom by a silicon atom contained in a side chain and contains at least 0.15 aromatic groups per silicon atom.
A flame-retardant resin composition comprising 1 to 30 parts by weight. Embedded image (Wherein, R ¹ is the same or different and is a hydroxyl group, a carbon atom 1
Represents an alkoxyl group having 1 to 12 carbon atoms or a monovalent hydrocarbon group having 1 to 12 carbon atoms. R ² is the same or different and represents a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 12 carbon atoms. R ³ represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms. When there are a plurality of R ³ , they may be the same or different. a is 1, 2 or 3.
X is a number greater than or equal to 0.1; Y is a number greater than or equal to 1;
Is a number exceeding 0, and X + Y + Z is 3 to 100
It is. The arrangement of the X repeating units, the Y repeating units, and the Z repeating units may all be random, or all or some of them may form a block. ) 4. A structural unit comprising 100 parts by weight of an aromatic resin, a linear silicone structure represented by the following formula (1) and a (poly) siloxane structure represented by the following formula (2): When the linear silicone structures are bonded to each other via an oxygen atom, the flame retardant is 0.1 to 30 parts by weight containing at least 0.15 aromatic groups per silicon atom. A flame-retardant resin composition comprising: Embedded image (Wherein, R ¹ is the same or different and is a hydroxyl group, a carbon atom 1
Represents an alkoxyl group having 1 to 12 carbon atoms or a monovalent hydrocarbon group having 1 to 12 carbon atoms. R ² is the same or different and represents a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 12 carbon atoms. R ³ represents a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms. When there are a plurality of R ³ , they may be the same or different. a is 1, 2 or 3.
X is a number greater than or equal to 0.1; Y is a number greater than or equal to 1;
Is a number exceeding 0, and X + Y + Z is 3 to 100
It is. The arrangement of the X repeating units, the Y repeating units, and the Z repeating units may all be random, or all or some of them may form a block. ) (In the formula, R ⁴ is the same or different and is a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or 1 to 12 carbon atoms.
Represents a saturated or unsaturated alkyl group. n is 1 to 5
Represents an integer. ) 5. The aromatic resin according to claim 3, wherein the aromatic resin is at least one selected from the group consisting of a polycarbonate resin, a thermoplastic polyester resin, a polyphenylene ether resin, and an aromatic vinyl resin. Flame retardant resin composition. 6. The aromatic resin is a polycarbonate resin or a combination of a polycarbonate resin and at least one of a thermoplastic polyester resin and an aromatic vinyl resin. 4 or 5
The flame-retardant resin composition according to the above.