JP2001335638A - Copolymer containing polysiloxane and flame resisting composition by applying the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copolymer containing silicone which can give such a high flame resisting that has not been before, to a system which uses a resin which is low in cost and excellent in molding, such as a polystyrene and a resin which is excellent in flame resisting such as a polycarbonate resin, together. SOLUTION: The copolymer contain a polysiloxane is obtained by copolymerizing a polycarbonate resin and a silicone compound having a base skeleton shown by formula (1) (R13SiO0.5)a(R22SiO)b(R3SiO1.5)c(SiO2)d (in the formula, each of R1, R2 or R3 shows an aromatic residue or a 1 to 6C hydrocarbon group, the relation of (a+b+c+d)=1 is filled) and it is characterized in that an aromatic residue, and the content of aromatic residue is 30 to 95%, and it satisfys 0<c+d.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polysiloxane-containing copolymer and, more particularly, to a thermoplastic resin used in various fields such as electric parts, electronic parts, mechanical parts and automobile parts. The present invention relates to a polysiloxane-containing copolymer which imparts flame retardancy to a copolymer.

[0002]

2. Description of the Related Art Thermoplastic resins are used for various purposes because of their excellent moldability, mechanical properties and electrical properties. Above all, impact-resistant polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene (AB
S) Styrene resins such as resins have excellent properties,
Due to its low cost, it is widely used in various applications including home appliances and OA equipment housings, indoor and outdoor decorations, building materials, automobile parts and the like.

However, these thermoplastic resins are:
In general, because it is flammable, the burning of organic matter may be a cause of disasters that threaten people's safety, and measures to make the thermoplastic resin flame-retardant are required. , UL regulations and other various regulations have been strengthened and obliged. In the electric, electronic and OA fields, to meet safety requirements, higher flame retardancy equivalent to UL94V-0 and 94V-1 is required. I have.

[0004] As a means for imparting flame retardancy, generally, a method of blending a resin with a halogen-based flame retardant such as a bromine compound having a high flame retardancy efficiency and an antimony compound as a flame retardant aid is used. Has been adopted. However, this method has problems such as a large amount of smoke generated during combustion and generation of a harmful gas containing the halogen during combustion. In addition, a method using a phosphorus-based flame retardant such as red phosphorus or a phosphoric acid ester is sometimes used, but the safety of the phosphorus-based flame retardant itself is not sufficient, and further, a resin material using these materials has a moisture resistance and There was a problem that heat resistance was poor.

As a means for imparting flame retardancy without using halogen or phosphorus, a method using an organopolysiloxane-polycarbonate resin copolymer is known. Polycarbonate resins have high flame retardancy among various thermoplastic resins, and higher flame retardancy can be obtained by copolymerizing this with an organopolysiloxane.

Japanese Patent Application Laid-Open No. 8-81620 discloses a copolymer obtained by copolymerizing polydimethylsiloxane and polycarbonate. This copolymer can be used by mixing it with a polycarbonate resin. Describe that the flame retardancy is improved.

Japanese Patent Application Laid-Open No. 8-176427 discloses a relatively low molecular weight (molecular weight of 1000) having a specific structure.
A copolymer obtained by copolymerizing an organopolysiloxane and a polycarbonate is disclosed. It is described that flame retardancy is improved by using this copolymer.

Further, various studies have been made on compositions in which a polycarbonate-organopolysiloxane copolymer and various flame retardants are used in combination (for example, JP-A No. 1-2).
10462, JP-A-4-202465, JP-A-11-152398, etc.).

[0009]

However, it has been difficult for the above-mentioned polycarbonate-organopolysiloxane copolymer to achieve a high level of flame retardancy as currently desired.

In addition, it has been difficult for conventional polycarbonate-organopolysiloxane copolymers to impart sufficient flame retardancy when applied to a system that also uses flame retardancy, such as a polystyrene resin. Polycarbonate resin is an expensive material and its moldability is not so good. Therefore, it is often used in combination with other inexpensive resins having excellent moldability such as polystyrene resins. However, in this case,
Since a resin component such as a polystyrene resin having low flame retardancy tends to precipitate on the surface, it is particularly difficult to improve the flame retardancy.

The present inventors have conducted various studies on a method of imparting flame retardancy to such a system, and as a result, segregating a highly flame retardant component on the surface of a molded article;
It has been found that it is important to uniformly distribute the highly flame-retardant components on the surface of the molded article for imparting a high degree of flame retardancy.

However, there have been few examples of conventional polycarbonate-organopolysiloxane copolymers designed in consideration of the form present in the molded article. In particular, the uniformity of the distribution of the organopolysiloxane on the surface of the molded article is low. There were no examples designed to be good.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a polysiloxane-containing copolymer having an unprecedented high flame retardancy. Provided is a polysiloxane-containing copolymer that can impart unprecedented high flame retardancy to a system using a combination of a good resin and a resin having excellent flame retardancy such as a polycarbonate resin. Things.

[0014]

According to the present invention SUMMARY OF], the following formula _{^{(I) (R 1 3 SiO}} 0.5) a (R 2 2 SiO) b (R 3 SiO 1.5) c (SiO 2) d ... (I (Wherein, R ¹ , R ^2, and R ³ each represent an aromatic residue or a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different. A, b , C and d satisfy the relationship of (a + b + c + d) = 1.) A polysiloxane-containing copolymer obtained by copolymerizing a silicone resin having an aromatic residue with an organopolysiloxane as a basic skeleton and a polycarbonate resin. A polymer having an aromatic residue content of 30 to 95% based on the entire functional groups of the silicone compound, and having the formula (I)
And a polysiloxane-containing copolymer characterized by satisfying 0 <c + d.

Here, in the formula (I), 0.2 <c +
Preferably, d <0.95 is satisfied, and 0.5 <c + d
It is more preferable to satisfy <0.95.

The weight average molecular weight of the silicone compound is preferably from 300 to 100,000.

Further, the above copolymer comprises 0.5 to 80% by weight of a silicone compound and 20 to 80% of a polycarbonate resin.
Preferably, the copolymer is obtained by copolymerizing 99.5% by weight.

Further, according to the present invention, there is provided a polysiloxane obtained by copolymerizing a liquid crystal polyester with a silicone compound having an organopolysiloxane represented by the following formula (I) as a basic skeleton and having an aromatic residue. A containing copolymer is provided. ^{_{(R 1 3 SiO 0.5) a}} (R 2 2 SiO) b (R 3 SiO 1.5) c (SiO 2) d ... (I) ( wherein, R ^1, R ² and R ³ are aromatic residues, respectively Or a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and a, b, c and d satisfy the relationship of (a + b + c + d) = 1 and c + d> 0. According to the present invention, there is provided a polysiloxane-containing resin obtained by copolymerizing a silicone compound having an aromatic residue with an organopolysiloxane represented by the following formula (I) as a basic skeleton and a polystyrene resin. A copolymer is provided. ^{_{(R 1 3 SiO 0.5) a}} (R 2 2 SiO) b (R 3 SiO 1.5) c (SiO 2) d ... (I) ( wherein, R ^1, R ² and R ³ are aromatic residues, respectively Or a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and a, b, c and d satisfy the relationship of (a + b + c + d) = 1 and c + d> 0. ) According to the present invention, the following formula _{^{(I) (R 1 3 SiO}} 0.5) a (R 2 2 SiO) b (R 3 SiO 1.5) c (SiO 2) d ... (I) ( in the formula, R ¹ , R ² and R ³ each represent an aromatic residue or a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and a, b, c and d are represented by ( a + b + c + d) = 1.) A silicone having an organopolysiloxane as a basic skeleton and having an aromatic residue Unit derived from a compound (A)
And a structural unit (B) containing an aromatic residue in the main chain skeleton or in the side chain, and the content of the aromatic residue relative to the entire functional group of the silicone compound is 30 to 95%, A polysiloxane-containing copolymer characterized by satisfying 0 <c + d in the above formula (I) is provided.

Each R ^{1 of the} silicone moiety represented by the above formula may be the same or different. Similarly, each R ² of the silicone moiety may be the same or different, and each R 2
³ may be the same or different. In each of the above formulas, the aromatic residue refers to a functional group having an aromatic ring, and the aromatic ring is bonded to the main chain skeleton or the side chain directly or via a bonding group.

As the structural unit (B), polystyrene,
Examples include a repeating unit such as acrylonitrile-styrene and polycarbonate, and a liquid crystal polyester unit.

According to the present invention, there is also provided a polysiloxane-containing copolymer according to any one of the above, in an amount of from 0.5 to 80% by weight,
The present invention provides a flame-retardant resin composition comprising 20 to 99.5% by weight of one or more resins selected from the group consisting of a polycarbonate resin, a liquid crystal polyester, and a polystyrene resin.

The polysiloxane-containing copolymer of the present invention comprises:
When injection molding is used as a resin molding material in combination with other resins, segregation on the surface of the molded article is highly caused. For this reason, a highly flame-retardant copolymer component is present at a high concentration on the outer surface of the molded article, so that it is difficult to ignite and a structure having high flame retardancy is obtained.

Here, since the polysiloxane-containing copolymer of the present invention has the above-mentioned specific structure,
In addition to being highly segregated on the surface of the molded article, the distribution of the copolymer component on the surface of the molded article becomes uniform. Therefore, even when the copolymer of the present invention is blended in a system in which a resin having low flame retardancy such as a polystyrene resin and a polycarbonate resin are used in combination, sufficient flame retardancy can be obtained.

Further, the polysiloxane-containing copolymer of the present invention has an advantage of being excellent in recyclability. In the copolymer of the present invention, when a molding material obtained by mixing with another resin is injection-molded, phase separation occurs and segregates on the surface of the molded article.This phase separation is caused by the properties of the copolymer component. It is caused by this. Unlike multi-layer molding, in which different resins are injected separately with a time lag, the layer structure is not formed by devising the molding method, so even if the molded product is collected and used again for molding, Similarly, surface segregation of the copolymer can occur. Therefore, a molded article having high flame retardancy can be obtained even when recycled.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer according to the present invention is obtained by copolymerizing a silicone compound and a thermoplastic resin. The copolymer is produced by the reaction between the reactive functional group of the silicone compound and the reactive functional group of the thermoplastic resin. In the copolymer of the present invention, the structural unit derived from the silicone compound lowers the melt viscosity and surface tension of the copolymer, and thus such copolymerization is remarkably precipitated on the surface of a molded article. The structural unit derived from the silicone compound in the copolymer has a high flame-retardant function and segregates on the surface, so that it is possible to realize an unprecedented high flame-retardant property.

Further, when the copolymer of the present invention is used,
Since the distribution of silicone on the surface of the molded article can be made uniform, particularly excellent flame retardancy can be obtained. For example, when the outer layer of a molded article is made of a mixed material of polydimethylsiloxane and a thermoplastic resin, the polydimethylsiloxane is unevenly distributed on the surface of the molded article, and sufficient flame retardancy may not be obtained. On the other hand, when the silicone part (organopolysiloxane unit) is incorporated into a part of the copolymer, it is possible to effectively prevent the silicones from gathering and distributing non-uniformly, and to achieve uniform distribution of the silicone on the surface of the molded article. The properties are extremely good. In particular, the silicone compound having an aromatic residue,
When a resin having an aromatic ring such as a polycarbonate resin, a liquid crystal polyester, or a polystyrene resin is selected as the thermoplastic resin, the uniformity of the distribution of silicone on the surface of the molded product is particularly good.

As the thermoplastic resin used in the copolymer, a resin containing an aromatic ring in the main chain skeleton is preferably used, and a resin having an aromatic residue in a side chain can also be used. By using a resin having such a structure, the heat resistance of the copolymer is further improved. Specifically, polycarbonate, liquid crystal polyester, polystyrene, acrylonitrile-styrene resin, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polyimide, polyamide imide, polyether imide, poly-p-phenylene terephthalamide, poly Butylene terephthalate and derivatives thereof. Of these, polycarbonate, liquid crystal polyester, polystyrene and derivatives thereof are preferably used because of their good flame retardancy and good moldability. These resins may be used alone or as a mixture of two or more.

The polycarbonate resin in the present invention is a resin containing a polycarbonate unit represented by the following general formula, and has a reactive functional group capable of reacting with a silicone compound. The reactive functional group is located, for example, at the terminal of the polycarbonate resin.

[0029]

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Wherein R ⁴ and R ⁵ each have 1 carbon atom
Represents an alkyl group of 6 to 6 or an aryl group of 6 to 12 carbon atoms, which may be the same or different, and m and n are each an integer of 0 to 4. Z is
A single bond, an alkylene or alkyldene group having 1 to 6 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, a cycloalkylidene group, a fluorenylidene group, or -O-, -S
—, —SO—, —SO ₂ — or —CO— bond. The polycarbonate resin is a polymer obtained by a phosgene method of reacting various dihydroxydiaryl compounds with phosgene, or a transesterification method of reacting a dihydroxydiaryl compound with a carbonate such as diphenyl carbonate, and is a typical one. Examples include derivatives of polycarbonate resins produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the dihydroxydiaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) in addition to bisphenol A.
Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4 -Hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5-dichlorophenyl) propane, bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane Cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether; dihydroxy diaryl sulfides such as 4,4'-dihydroxy diphenyl sulfide; 4,4'-dihydroxy diphenyl sulphoxide; 4,4'-dihydroxy-3,3 Dihydroxydiarylsulfoxides such as'-dimethyldiphenylsulfoxide; and dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

These are used singly or as a mixture of two or more kinds. It is preferable that they have no halogen substituent from the viewpoint of preventing the emission of a gas containing the halogen, which is a concern during combustion, to the environment. . In addition to these, piperazine,
Dipiperidyl hydroquinone, resorcinol, 4,4'-
Dihydroxydiphenyl, hydroquinone and the like may be used as a mixture.

Further, the above dihydroxyaryl compound and a phenol compound having a valency of 3 or more as shown below may be mixed and used.

Examples of the trivalent or higher phenol include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, and 2,4,6-dimethyl-2,4,6-triphenol. -(4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4,4-
(4,4'-dihydroxydiphenyl) -cyclohexyl] -propane.

The viscosity average molecular weight of the polycarbonate resin is usually from 10,000 to 100,000, preferably from 15,000 to 35,000. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as required.

The liquid crystal polyester in the present invention is a polyester called a thermotropic liquid crystal polymer and has a reactive functional group capable of reacting with a silicone compound. The reactive functional group is located, for example, at the terminal of the polycarbonate resin. Specifically, (1) those comprising a combination of an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid,
(2) a combination of different kinds of aromatic hydroxycarboxylic acids, (3) a combination of aromatic dicarboxylic acids and a nucleus-substituted aromatic diol, (4) a polyester such as polyethylene terephthalate and an aromatic hydroxycarboxylic acid And an anisotropic melt at a temperature of 400 ° C. or lower. In addition, in place of these aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids, ester-forming derivatives thereof may be used. Examples of the repeating structural unit of the liquid crystal polyester include the following. The flow start temperature of the liquid crystal polyester is defined as a melt viscosity of a liquid crystal polyester heated at a rate of 4 ° C./min when extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 100 kgf / cm ^2. Is 48,000 poise,
Usually measured.

A repeating structural unit derived from an aromatic dicarboxylic acid:

[0038]

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A repeating structural unit derived from an aromatic diol:

[0040]

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A repeating structural unit derived from an aromatic hydroxycarboxylic acid:

[0042]

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A liquid crystal polyester which is particularly preferred in view of the balance among heat resistance, mechanical properties, workability and flame retardancy is

[0044]

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The repeating structural unit is preferably 30 units
Mol% or more, and specifically, combinations of repeating structural units are those of the following (I) to (VI).

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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The production method of the above liquid crystal polyesters (I) to (VI) is described in, for example, JP-B-47-47870.
JP-B-63-3888, JP-B-63-3891, JP-B-56-18016, JP-B2-51
No. 523, etc. Of these, a combination of (I), (II) and (IV) is preferable, and a combination of (I) and (II) is more preferable.

The polystyrene resin is a synthetic resin obtained by polymerizing styrene with other components appropriately added, and has a reactive functional group capable of reacting with a silicone compound. The reactive functional group is located, for example, at the terminal of the polycarbonate resin.

Also included are those obtained by compounding or copolymerizing a rubber component to impart impact resistance. As the rubber component,
Butadiene is generally used, but is not particularly limited. Part of the polystyrene of the rubber-reinforced polystyrene resin can be replaced with another aromatic vinyl compound. As other aromatic vinyl compounds, for example, α-
Examples include methylstyrene, p-methylstyrene, p-hydroxystyrene, vinyltoluene, sodium styrenesulfonate, and the like. Further, in order to improve the properties of the resin, a copolymer with another monomer, such as acrylonitrile, or a graft polymer may be included.

Specific examples include impact-resistant polystyrene, that is, rubber-reinforced polystyrene (HIPS), acrylonitrile-butadiene-styrene (ABS) copolymer resin, styrene / butadiene rubber (SBR), and the like. The rubber-reinforced polystyrene-based resin is produced by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, or a blend of a molten resin.

Next, the silicone compound in the present invention will be described. The silicone compound in the present invention has an organopolysiloxane skeleton represented by the following formula, and has a reactive functional group capable of reacting with a thermoplastic resin to be copolymerized in the present invention. ^{_{(R 1 3 SiO 0.5) a}} (R 2 2 SiO) b (R 3 SiO 1.5) c (SiO 2) d ... (I) ( wherein, R ^1, R ² and R ³ are aromatic residues, respectively Or a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and a, b, c and d satisfy the relationship of (a + b + c + d) = 1 and c + d> 0. The reactive functional group is a functional group in which R in the basic skeleton is substituted, and is usually located at the terminal of the organopolysiloxane.

The silicone compound in the present invention is represented by (R
³ preferably contains SiO _1.5) T units and represented by (SiO ₂₎ at a certain level or more Q units represented. Specifically, it is preferable that the branch unit content α represented by α = (c + d) be equal to or more than a predetermined value. If the value of α is too low, the heat resistance of the silicone compound may decrease, and sufficient flame retardancy may not be obtained.

In the copolymer of the organopolysiloxane and the polycarbonate resin, preferably 0.2 <
α, more preferably 0.5 <α, most preferably 0.6
<Α.

In the copolymer of the organopolysiloxane and the liquid crystal polyester, α is preferably 0.1 or more, more preferably 0.2 or more. Since the heat resistance of the liquid crystal polyester itself is good, a higher flame retardancy can be obtained even if α is smaller than in the case of the polycarbonate resin.

In the copolymer of organopolysiloxane and polystyrene resin, α is preferably 0.1 or more, more preferably 0.2 or more. A copolymer with a polystyrene-based resin is excellent in moldability, so that a molding material can be used alone or in a form in which a small amount of another resin is used in combination. For this reason, the content of the copolymer with respect to the entire molding material can be set high, so that even when α is smaller than that of the polycarbonate resin, sufficient flame retardancy can be obtained.

The upper limit of α in each of the above copolymers is preferably 0.95 or less. 0.9
If it exceeds 5, the degree of freedom of the main chain of the silicone decreases, so that the condensation of aromatic residues during combustion becomes less likely to occur, and the flame retardancy may be rather reduced.

In the silicone compound of the present invention, it is preferable that the content of the aromatic residue with respect to the whole organic functional group contained in the compound is a certain value or more. This is because the condensation of aromatic residues proceeds more efficiently during combustion, and the dispersibility of the silicone compound in the thermoplastic resin is greatly improved, so that an extremely good flame retardant effect can be exhibited. If the content is too low, condensation of aromatic residues hardly occurs during combustion, and the flame retardant effect may decrease. here,
The organic functional group contained in the silicone compound refers to an organic functional group bonded to a main chain or a branched side chain.

The aromatic residue contained in the silicone compound is a functional group derived from an aromatic, and the aromatic is a benzene ring, a condensed benzene ring, a polyaromatic ring, or a non-benzene-based aromatic ring. A compound having an aromatic ring such as a ring or a heteroaromatic ring. Examples of aromatics include benzene, naphthalene, anthracene, biphenyl, diphenyl ether, biphenylene, pyrrole, and derivatives thereof. Examples of the derivative include those obtained by adding an alkyl group having 1 to 10 carbon atoms to the above compound. A preferred embodiment of the aromatic residue is a phenyl group. This is because it is excellent in the effect of improving the flame retardancy.

Specifically, the content of the aromatic residue is preferably as follows.

In the copolymer of the organopolysiloxane and the polycarbonate resin, the aromatic residue content is preferably at least 30%, more preferably at least 40%.

In the copolymer of organopolysiloxane and liquid crystal polyester, the content of aromatic residues is preferably at least 10%, more preferably at least 30%. Because the heat resistance of the liquid crystal polyester itself is good,
Higher flame retardancy can be obtained even if the content of aromatic residues is lower than in the case of a polycarbonate resin.

In the copolymer of organopolysiloxane and polystyrene resin, the content of aromatic residues is preferably at least 10%, more preferably at least 30%. A copolymer with a polystyrene-based resin is excellent in moldability, so that a molding material can be used alone or in a form in which a small amount of another resin is used in combination. For this reason, since the content of the copolymer with respect to the whole molding material can be set high, sufficient flame retardancy can be obtained even when the content of aromatic residues is smaller than that of the polycarbonate resin.

It is to be noted that the upper limit of the content is preferably not more than 95 mol% in the copolymer. If it exceeds 95 mol%, steric hindrance between aromatic residues may make it difficult to cause these condensations, and a sufficient flame retardant effect may not be obtained.

There are no particular restrictions on the groups other than the aromatic residues among the organic functional groups, but it is preferred that most of the remaining groups are methyl groups. This is because the dispersibility of the silicone compound in the thermoplastic resin is improved.

The terminal group of the silicone compound may be a methyl group, a phenyl group or a hydroxyl group, and a reactive group capable of reacting with another resin to be copolymerized is appropriately introduced.

The copolymer of the present invention is obtained by copolymerizing a silicone compound with another resin. It is preferable that the amount of the silicone compound to be copolymerized is within a certain range. If the copolymerization amount of the silicone compound is too small, it will be difficult to obtain sufficient flame retardancy. On the other hand, if the copolymerization amount is too large, the moldability may be poor or the cost of the resin material may be high.

In the copolymer of the organopolysiloxane and the polycarbonate resin, 0.5 to 80% by weight of the silicone compound and 20 to
It is preferable to copolymerize with 99.5% by weight.

In the copolymer of the organopolysiloxane and the liquid crystal polyester, 0.5 to 80% by weight of the silicone compound and 20 to 99.
It is preferable to copolymerize with 5% by weight.

Further, in the copolymer of the organopolysiloxane and the polystyrene resin, 0.5 to 80% by weight of the silicone compound and 20 to 9% of the polystyrene resin are used.
It is preferred to copolymerize with 9.5% by weight.

The average molecular weight (weight average) of the silicone compound in the present invention is preferably 300 or more, more preferably 500 or more, and most preferably 1,000 or more. If the molecular weight is too low, it will be difficult to obtain sufficient flame retardancy. On the other hand, the upper limit is preferably 100,000 or less. It is preferable that the molecular weight of the silicone compound is appropriately selected according to the molecular weight of the thermoplastic resin to be copolymerized.

The copolymer of the present invention comprises, for example, a silicone compound having a reactive functional group (a) and a thermoplastic resin having a reactive functional group (b) capable of reacting with the reactive functional group (a). And copolymerizing them. Further, it can also be obtained by introducing a radical polymerizable functional group into a silicone compound and radically polymerizing a radical polymerizable monomer capable of reacting with the functional group in the presence of a polymerization initiator.

The reactive functional group includes, for example, a hydroxyl group, an epoxy group, an amino group, a carboxyl group, an acyl group, a mercapto group, a methacrylo group, an isocyanate group, a ureido group, a vinyl group, an amide group, an imide group, an imino group, and an aldehyde group. , A nitro group, a nitrile group, an oxime group, an azo group, a hydrazone group, an alkoxy group, an alkoxysilyl group, a thiol group, an allyl group, and an SiH group. In the production of a copolymer of a silicone compound and a thermoplastic resin used in the present invention, it is preferable to select a reactive group depending on the resin to be combined and to efficiently copolymerize. As a combination of the above reactive functional groups (a) and (b), one is an epoxy group and the other is an amino group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, a vinyl group, an allyl group, an amide group, an imide group. And a combination having one as a hydroxyl group and the other as an alkoxy group or a mercapto group.

Examples of the radical polymerizable monomer include acrylate and methacrylate derivatives such as phenyl (meth) acrylate and benzyl (meth) acrylate; styrene, α-methylstyrene, p-te
Examples include styrene derivatives such as rt-butylstyrene and the like, vinyl toluene, acrylonitrile, vinyl acetate, vinyl propionate, vinyl versatate and the like.

Further, at the time of radical polymerization, a radical polymerizable monomer is polymerized in the presence of a radical polymerization initiator having a reactive group or a chain transfer agent having a reactive group,
A polymer having a reactive group end can also be obtained. Examples of the radical polymerization initiator containing a carboxyl group in the molecule include 4,4'-azobis (4-cyanovaleric acid) and the like, and include "VA-548", "VA
-558 "," VA-059 "," VA-060 ",
“VA-080”, “VA-082”, “VA-08”
6 "," VA-077 "," V-501 "," VF-0 "
77 "(Wako Pure Chemical Industries, Ltd.). These can be used alone or in combination of two or more, and a polymer having a carboxyl group terminal can be synthesized.

Further, examples of the radical polymerization initiator having a hydroxyl group in the molecule include 2,2'-azobis [N- (4-hydroxyphenyl) -2-methylpropionamidine] dihydrochloride and 2,2 ' -Azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyridin-2-yl) propane ] Dihydrochloride and the like. These can be used alone or in combination of two or more, and a polymer having a hydroxyl group terminal can be synthesized.

Further, the polymer having a carboxyl group or a hydroxyl group at one end can be reacted with a compound having a functional group capable of reacting with these functional groups and a radical polymerizable unsaturated group at the same time to obtain one end of the polymer. May be introduced with a radically polymerizable unsaturated group. In the case of a polymer having a carboxyl group at one end, examples of the unsaturated compound having a functional group capable of reacting with the polymer include glycidyl (meth) acrylate,
Radical polymerizable unsaturated monomers such as 3,4-epoxycyclohexylmethyl (meth) acrylate and 2-methylglycidyl (meth) acrylate can be exemplified.
A polymer having a radically polymerizable unsaturated group at one end by reacting these radically polymerizable unsaturated monomers in an equimolar amount to 5 times the molar amount with respect to the carboxyl group of the above polymer. Can be.

In the case of a polymer having a hydroxyl group at one end, examples of the unsaturated compound having a functional group capable of reacting with the polymer include acid chloride compounds such as (meth) acrylic acid chloride; diisocyanate compounds An equimolar reaction product of isocyanate ethyl (meth) acrylate and isocyanatopropyl (meth) acrylate with 2-hydroxyethyl (meth) acrylate,
Isocyanate butyl (meth) acrylate, isocyanate hexyl (meth) acrylate, m-isopropenyl-α, α'-dimethylbenzyl isocyanate, m
Compounds having both isocyanate groups and unsaturated groups such as -ethylenyl-α, α'-dimethylbenzyl isocyanate; acid anhydride compounds such as itaconic anhydride and maleic anhydride; N-methylol (meth) acrylamide;
n-butoxy (meth) acrylamide and the like can be mentioned. By reacting these compounds in an equimolar amount to a 5-fold molar amount with respect to the hydroxyl groups of the polymer, a polymer having a radically polymerizable unsaturated group at one end can be obtained. The styrene-based polymer having an unsaturated group at one terminal can be separated from unreacted substances by purification and used.

It is also possible to produce a thermoplastic resin-silicone compound copolymer by a hydrosilylation reaction between a polymer having a radically polymerizable unsaturated group at one end produced by the above synthesis method and hydrogenated silane. is there.

The chain transfer agent is, for example, a carboxyl group-containing mercaptan compound such as mercaptoacetic acid, 2-mercaptopropionic acid, or 3-mercaptopropionic acid. By using this, it is possible to have a carboxyl group at the terminal of the molecular main chain. Polymer can be synthesized. Also, as a functional group-containing mercaptan compound-based chain transfer agent, a polymer having a hydroxyl group at one end can be synthesized by using 2-mercaptoethanol, and by using 2-aminoethanethiol hydrochloride, a polymer having a hydroxyl group at one end of the molecular main chain can be obtained. A polymer having an amino group can be synthesized.

The highly flame-retardant thermoplastic resin copolymerized with the silicone compound is a thermoplastic resin containing an aromatic residue in the main chain skeleton or in a side chain. Examples of the copolymer include silicone resin. -Polycarbonate copolymer, silicone-liquid crystal polyester copolymer, silicone-acrylonitrile-styrene copolymer, silicone-polyphenylene sulfide copolymer, silicone-polybutylene terephthalate copolymer, silicone-polyether sulfone copolymer, Silicone-polysulfone copolymer, silicone-polyetheretherketone copolymer, silicone-polyimide copolymer, silicone-polyamideimide copolymer, silicone-polyetherimide copolymer, silicone-poly-p-phenyleneterephthalamide It is a copolymer etc.

When designing a resin molding material containing the copolymer of the present invention, the amount of the copolymer is preferably from 0.5 to 150 parts by weight per 100 parts by weight of the resin molding material. If the amount is less than 0.5 part by weight, the flame retardant effect may be insufficient, and if it exceeds 150 parts by weight, no economic merit can be found. More preferably, it is in the range of 1 part by weight to 60 parts by weight, and still more preferably in the range of 3 parts by weight to 30 parts by weight. Within this range, the balance between flame retardancy and moldability, impact strength, and economy is further improved.

The resin molding material may contain a metal salt of an aromatic sulfur compound or a metal salt of perfluoroalkanesulfonic acid.

As the metal salt of the aromatic sulfur compound, a metal salt of an aromatic sulfonamide, a metal salt of an aromatic sulfonic acid and the like are used.

Preferred examples of the metal salt of an aromatic sulfonamide include a metal salt of saccharin, a metal salt of N- (p-tolylsulfonyl) -p-toluenesulfonimide, and a metal salt of N- (p-tolylsulfonyl).
A metal salt of (N'-benzylaminocarbonyl) sulfanylimide and a metal salt of N- (phenylcarboxyl) -sulfanylimide. Further, as the metal salt of the aromatic sulfonic acid, diphenyl sulfone-3-
Metal salt of sulfonic acid, diphenylsulfone-3,3'-
Metal salt of disulfonic acid and diphenyl sulfone
Metal salts of 3,4'-disulfonic acid are mentioned. These may be used alone or in combination of two or more.

Suitable metals include Group I metals (alkali metals) such as sodium and potassium, or Group II metals, and copper and aluminum, with alkali metals being particularly preferred.

Among these, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfonimide, potassium salt of N- (N'-benzylaminocarbonyl) sulfanylimide or diphenylsulfone-3
-Potassium salt of sulfonic acid is suitably used, and more preferably, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfonimide or potassium salt of N- (N'-benzylaminocarbonyl) sulfanylimide is there.

The amount of the metal salt of the aromatic sulfur compound is preferably from 0.03 to 5 parts by weight based on 100 parts by weight of the flame-retardant resin composition. 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. Especially in this range,
The balance between flame retardancy, moldability and impact strength is further improved.

The metal salt of perfluoroalkanesulfonic acid is a metal salt of perfluoroalkanesulfonic acid.

Preferred examples of the metal salt of perfluoroalkanesulfonic acid include a metal salt of perfluoromethanesulfonic acid, a metal salt of perfluoroethanesulfonic acid, a metal salt of perfluoropropanesulfonic acid, and a metal salt of perfluorobutanesulfonic acid. Metal salts, metal salts of perfluoromethylbutanesulfonic acid, metal salts of perfluorohexanesulfonic acid, metal salts of perfluoroheptanesulfonic acid,
Metal salts of perfluorooctanesulfonic acid. These may be used alone or in combination of two or more. Further, the metal salt of perfluoroalkanesulfonic acid may be used in combination with the metal salt of the aromatic sulfur compound described above.

Suitable metals used for the metal salt of perfluoroalkanesulfonic acid include Group I metals (alkali metals) such as sodium and potassium, or Group II metals, and copper and aluminum. Metals are preferred. Among them, potassium salt of perfluorobutanesulfonic acid is particularly preferably used.

The amount of the metal salt of perfluoroalkanesulfonic acid is 0.1 to 100 parts by weight of the flame-retardant resin composition.
The content is preferably from 01 to 5 parts by weight. The blending amount is 0.
If the amount is less than 01 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 at the time of injection molding may be inferior. The impact strength may be adversely affected. More preferably, it is in the range of 0.02 to 2 parts by weight, and still more preferably in the range of 0.03 to 0.2 parts by weight. Particularly in this range, the balance between flame retardancy, moldability and impact strength is further improved.

Further, when a fiber-forming type fluoropolymer which is considered to have an effect of preventing drip is added to the above-mentioned flame-retardant resin composition, a higher degree of flame-retardant effect can be obtained. As the fiber-forming type fluorine-containing polymer, those which form a fiber structure (fibril-like structure) in a thermoplastic resin are preferable, and polytetrafluoroethylene, tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoro Propylene copolymer).

The compounding amount of the fiber-forming type fluorine-containing polymer is 0.05 to 5 parts by weight based on 100 parts by weight of the flame-retardant resin composition. If the compounding amount is less than 0.05 part by weight, the effect of preventing dripping during combustion may be poor, and if it exceeds 5 parts by weight, granulation becomes difficult, which may hinder stable production. More preferably,
0.05 part by weight or more and 1 part by weight or less, more preferably 0.1 part by weight
It is in the range of not less than 0.5 parts by weight and not more than parts by weight. Within this range, the balance between flame retardancy, moldability and impact strength will be even better.

Further, as long as the effects of the present invention are not impaired,
Various heat stabilizers, antioxidants,
Additives such as a coloring agent, a fluorescent whitening agent, a filler, a release agent, a softening agent, an antistatic agent, and the like, an impact modifier, and the like may be blended.
Further, other flame retardants may be blended, and in the case of the present invention, the addition amount can be greatly reduced.

Examples of the heat stabilizer include metal hydrogen sulfates such as sodium hydrogen sulfate, potassium hydrogen sulfate and lithium hydrogen sulfate, and metal sulfates such as aluminum sulfate. These are generally used in a range of 0 part by weight to 0.5 part by weight based on 100 parts by weight of the flame-retardant resin composition.

Examples of the filler include glass fibers, glass beads, glass flakes, carbon fibers, talc powder, clay powder, mica, potassium titanate whisker, wollastonite powder, and silica powder.

Examples of impact modifiers include acrylic elastomers, polyester elastomers, core-shell type methyl methacrylate / butadiene / styrene copolymers, methyl methacrylate / acrylonitrile / styrene copolymers, ethylene / propylene rubbers, and ethylene / propylene rubbers. And propylene-diene rubber.

Other flame retardants can be added as required, and examples thereof include phosphorus-based flame retardants, metal hydroxides, nitrogen compounds such as melamines, and halogen-based flame retardants. It is possible to reduce to.

The method of mixing the various components in the flame-retardant resin composition of the present invention is not particularly limited, and includes a known mixer such as a tumbler, a ribbon blender or the like, and a melt-kneading using an extruder. .

As a method for molding the flame-retardant resin composition of the present invention, a known injection molding method, injection / compression molding method or the like can be used, but injection molding is preferred. Injection molding allows more efficient phase separation and highly segregated highly flame-retardant components in the outer layer, greatly improving the flame retardancy of molded products. .

As the preferred combinations of the resins constituting the flame-retardant resin composition according to the present invention, NO. 1 to
And three. In addition, a silicone component (C), a metal salt, a fiber-forming type fluoropolymer, or the like can be appropriately added to the component (A).

[0107]

[Table 1]

In the table, NO. The copolymers contained in the components (A) 1 and 2 and other resins have good compatibility. For this reason, the organopolysiloxane unit derived from silicone is uniformly distributed in the outer layer of the molded article, and particularly high flame retardancy is obtained.

[0109] In addition, NO. The copolymer (3) is excellent in moldability, and thus is used alone (A) without being used in combination with other resins.
Can be used as a component.

[0110]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “parts” are based on weight.

Example 1 In the following examples, the molecular weight was measured by GPC (gel permeation chromatography).

The details of the raw materials used in the examples and comparative examples are as follows. 1. Acrylonitrile-styrene resin (AS): AS
(Weight average molecular weight 80,000) 2. Carboxyl group-terminated acrylonitrile-styrene resin: AS-2 (weight average molecular weight 80,000) was produced according to a general production method. That is, as a polymerization initiator having a carboxyl group, 4,4'-azobis (4-
It was obtained by radical polymerization of acrylonitrile and styrene using cyanovaleric acid). 3. 3. Polycarbonate resin (PC): PC (weight average molecular weight 19,000) Hydroxyl-terminated polycarbonate resin (PC-3): P
C-3 (weight average molecular weight 15,600) was produced according to a general production method. That is, bisphenol-A
And diphenyl carbonate by melt polycondensation. The phenolic terminal group concentration of the polycarbonate can be adjusted by changing the molar ratio between the aromatic dihydroxy compound and the carbonic acid diester, or by changing the reflux conditions of the volatile components in the reaction system. For example,
The lower the molar ratio of carbonate diester to aromatic dihydroxy compound, the higher the phenolic end group concentration of the resulting polycarbonate. 5. Polystyrene resin: Nippon Steel Chemical's G-10 was used as the polystyrene resin (PS). 6. Hydroxyl terminated polycarbonate resin (PC-4): P
C-4 (weight average molecular weight 25,000) was produced according to the same production method as in 3. 7. Liquid crystal polyester (LCP):
According to a general manufacturing method, the following two types were manufactured.

LCP-1 An appropriate amount of p-
Acetoxybenzoic acid and 2-acetoxy-6-naphthoic acid (p-acetoxybenzoic acid and 2-acetoxy-6
-Naphthoic acid is mixed at a molar ratio of 60/40), polycondensed while heating at a predetermined temperature, and then heat-treated under a high vacuum for a predetermined time to obtain a flow start temperature of 250
A liquid crystal polyester (LCP-1) having a temperature of 18000C (Mw 18000) was produced.

LCP-2 In the same manner as above, p-acetoxybenzoic acid, terephthalic acid, isophthalic acid and 4,4′-diacetoxydiphenyl (p-acetoxybenzoic acid, terephthalic acid, isophthalic acid) And 4,4′-diacetoxydiphenyl in a molar ratio of 60/15/5 / 20.2),
After polycondensation while heating at a predetermined temperature, the mixture is subjected to a heat treatment under a high vacuum for a predetermined time so that the flow start temperature becomes 256 ° C.
9000) of a liquid crystal polyester (LCP-2). 8. Silicone compounds (a) and (b): Silicone compounds (a) and (b) were produced according to a general production method. That is, an appropriate amount of diorganodichlorosilane, monoorganotrichlorosilane and tetrachlorosilane, or a partial hydrolyzate thereof, depending on the molecular weight of the silicone compound component and the ratio of M unit, D unit, T unit and Q unit constituting the silicone compound. By dissolving the decomposition condensate in an organic solvent, adding water and hydrolyzing to form a partially condensed silicone compound, and further reacting by adding triorganochlorosilane,
The polymerization was terminated, and then the solvent was separated by distillation or the like. The structural characteristics of various silicone compounds synthesized by the above method are shown in the following table.

[0115]

[Table 2]

[0116]

[Table 3]

* Ratio of (T + Q) in main chain structure including terminal (value of branching unit content α (c + d) described above) ** Phenyl group is regarded as T unit in silicone containing T unit. First included and remaining cases are included in D units. When a phenyl group is attached to the D unit, the addition of one has priority, and when the phenyl group remains, two are attached. Except for the terminal groups, the organic functional groups are all methyl groups except for the phenyl group. *** Significant figures of weight average molecular weight are two digits.

Next, an example of producing a copolymer using the above raw materials will be described. Production Example 1 Production of epoxy-terminated silicone (1) Production of epoxy-terminated silicone SE1 2-Allylphenylglycidyl ether 5 was placed in a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen inlet tube.
0 g and 200 cc of methyl isobutyl ketone as a solvent were added and dissolved by heating under stirring. To this solution, 0.32 g of a 2% by weight solution of chloroplatinic acid in 2-ethylhexanol was added as a catalyst. Thereafter, while confirming that water does not evaporate over about 1 hour while refluxing the solvent at about 120 ° C., the mixture was cooled to 100 ° C., and silicone d, 56.
3 g were charged to the reactor over about 1 hour. After further reacting for 3 hours, the mixture was cooled to room temperature. After washing with water three times to remove a 2-ethylhexanol solution of chloroplatinic acid as a catalyst, the solvent was distilled off and the epoxy-terminated silicone resin SE was removed.
1, 105.8 g were obtained. It was confirmed by infrared absorption spectrum analysis that the Si-H group (absorption wavelength: 2175 cm ^-1 ) had almost disappeared.

(2) Production of epoxy-terminated silicone SE2 In the above (1), 200 cc of methyl isobutyl ketone as a solvent was changed to 250 cc, and a 0.3% solution of 2 wt% chloroplatinic acid in 2-ethylhexanol as a catalyst was changed to 0.32.
g was changed to 0.42 g.
An epoxy-terminated silicone resin SE was prepared in the same manner as (1) except that 6.3 g was changed to silicone e and 87.5 g.
2, 137.1 g were obtained. It was confirmed by infrared absorption spectrum analysis that the Si-H group (absorption wavelength: 2175 cm ^-1 ) had almost disappeared.

(3) Production of epoxy-terminated silicone SE3 In the above (1), 200 cc of methyl isobutyl ketone as a solvent was changed to 400 cc, and a 0.3% solution of 2-wt% chloroplatinic acid in 2-ethylhexanol was used as a catalyst.
g was changed to 0.76 g.
An epoxy-terminated silicone resin SE was prepared in the same manner as in (1) except that 6.3 g was changed to silicone f and 200 g.
3, 248.9 g were obtained. It was confirmed by infrared absorption spectrum analysis that the Si-H group (absorption wavelength: 2175 cm ^-1 ) had almost disappeared.

(4) Production of epoxy-terminated silicone SE4 In the above (1), 200 cc of methyl isobutyl ketone as a solvent was changed to 1200 cc, and 2 cc as a catalyst was used.
0.3 wt% chloroplatinic acid solution in 2-ethylhexanol
2 g was changed to 2.3 g, and silicone d, 5
An epoxy-terminated silicone resin SE was prepared in the same manner as in (1) except that 6.3 g was changed to silicone g and 625 g.
4,673.2 g were obtained. It was confirmed by infrared absorption spectrum analysis that the Si-H group (absorption wavelength: 2175 cm ^-1 ) had almost disappeared.

(5) Production of epoxy-terminated silicone SE5 In the above (1), 200 cc of methyl isobutyl ketone as a solvent was changed to 400 cc, and a 0.3% solution of 2-wt% chloroplatinic acid in 2-ethylhexanol was used as a catalyst.
g was changed to 0.76 g.
An epoxy-terminated silicone resin SE was prepared in the same manner as in (1) except that 6.3 g was changed to silicone h and 200 g.
5, 249.2 g were obtained. It was confirmed by infrared absorption spectrum analysis that the Si-H group (absorption wavelength: 2175 cm ^-1 ) had almost disappeared.

(6) Production of epoxy-terminated silicone SE6 In the above (1), 200 cc of methyl isobutyl ketone as a solvent was changed to 400 cc, and a 0.3% solution of 2 wt% chloroplatinic acid in 2-ethylhexanol as a catalyst was used.
g was changed to 0.76 g.
An epoxy-terminated silicone resin SE was prepared in the same manner as (1) except that 6.3 g was changed to silicone i and 200 g.
6, 249.1 g were obtained. It was confirmed by infrared absorption spectrum analysis that the Si-H group (absorption wavelength: 2175 cm ^-1 ) had almost disappeared.

(7) Production of epoxy-terminated silicone SE7 In the above (1), 200 cc of methyl isobutyl ketone as a solvent was changed to 400 cc, and a 0.3% solution of 2-wt% chloroplatinic acid in 2-ethylhexanol was used as a catalyst.
g was changed to 0.76 g.
An epoxy-terminated silicone resin SE was prepared in the same manner as in (1) except that 6.3 g was changed to silicone j and 200 g.
7, 249.3 g were obtained. It was confirmed by infrared absorption spectrum analysis that the Si-H group (absorption wavelength: 2175 cm ^-1 ) had almost disappeared.

(8) Epoxy-terminated silicone SE8-3
Preparation of 2 Same as (1) except that methyl isobutyl ketone as a solvent, 2-wt% chloroplatinic acid solution in 2-ethylhexanol as a catalyst and silicone were changed as shown in the following table in (1) above. Thus, epoxy-terminated silicone resins SE8 to SE32 were obtained. It was confirmed by infrared absorption spectrum analysis that the Si-H group (absorption wavelength: 2175 cm ^-1 ) had almost disappeared.

[0126]

[Table 4]

The general formulas of the epoxy-terminated silicone resins of SE1 to SE32 are shown below.

[0128]

Embedded image

Next, a method for producing a copolymer of the silicone compound and various resins will be described.

Production Example 2 Production of Silicone Compound-Polycarbonate Resin Copolymer Epoxy-modified silicone resins SE1 to SE7 obtained according to the general method of Production Example 1 and a hydroxyl-terminated polycarbonate (PC-3) were each copolymerized. Thus, a copolymer having a structure represented by the following formula was obtained.

[0131]

Embedded image

The details of the manufacturing method will be described below.

According to the general method of Production Example 1- (1),
4.6 g of the obtained epoxy-modified silicone resin SE1
Was dissolved in 400 g of methylene chloride, and 312.0 g of a polycarbonate having a hydroxyl group terminal (PC-3) was added and dissolved. Then, 1.0 g of triphenylphosphine was added, and the mixture was reacted under reflux for 5 hours. And the solvent is distilled off under reduced pressure while heating.
-1 and 316.3 g were obtained (the above formula).

According to the general method of Production Example 1- (2),
7.2 g of the obtained epoxy-modified silicone resin SE2
Was dissolved in 400 g of methylene chloride, and 312.0 g of a polycarbonate having a hydroxyl group terminal (PC-3) was added and dissolved. Then, 1.0 g of triphenylphosphine was added, and the mixture was reacted under reflux for 5 hours. And the solvent is distilled off under reduced pressure while heating.
-31 and 319.1 g were obtained (the above formula).

According to the general method of Production Example 1- (3),
The obtained epoxy-modified silicone resin SE3, 16.4
g in methylene chloride (400 g) in a solution having a hydroxyl group-terminated polycarbonate (PC-3) in a solution of 312.0 g
Was added and dissolved, 1.0 g of triphenylphosphine was added, and the mixture was reacted under reflux for 5 hours, washed with xylene, and the solvent was distilled off under reduced pressure under heating to remove SiP.
327.5 g of C-3 was obtained (the above formula).

According to the general method of Production Example 1- (4),
The resulting epoxy-modified silicone resin SE4, 25.2
g in methylene chloride (300 g) in a solution having a hydroxyl group-terminated polycarbonate (PC-3) in a solution of 156.0 g.
Was added and dissolved, and 1.1 g of triphenylphosphine was added. The mixture was reacted under reflux for 5 hours, washed with water, and the solvent was distilled off under reduced pressure while heating to obtain SiPC-4, 1.
80.8 g was obtained (the above formula).

According to the general method of Production Example 1- (5),
The obtained epoxy-modified silicone resin SE5, 16.4
g in methylene chloride (400 g) in a solution having a hydroxyl group-terminated polycarbonate (PC-3) in a solution of 312.0 g
Was added and dissolved, 1.0 g of triphenylphosphine was added, and the mixture was reacted under reflux for 5 hours, washed with water, and the solvent was distilled off under reduced pressure while heating to obtain SiPC-5,3.
27.8 g were obtained (the above formula).

According to the general method of Production Example 1- (6),
The obtained epoxy-modified silicone resin SE6, 16.4
g in methylene chloride (400 g) in a solution having a hydroxyl group-terminated polycarbonate (PC-3) in a solution of 312.0 g
Was added and dissolved, and 1.0 g of triphenylphosphine was added. The mixture was reacted under reflux for 5 hours, washed with water, and the solvent was distilled off under reduced pressure while heating to obtain SiPC-6,3.
28.0 g were obtained (the above formula).

According to the general method of Production Example 1- (7),
The obtained epoxy-modified silicone resin SE7, 16.4
g in methylene chloride (400 g) in a solution having a hydroxyl group-terminated polycarbonate (PC-3) in a solution of 312.0 g
Was added and dissolved, 1.0 g of triphenylphosphine was added, and the mixture was reacted under reflux for 5 hours, washed with water, and the solvent was distilled off under reduced pressure while heating to obtain SiPC-7,3.
27.9 g were obtained (the above formula).

After heating the obtained resin SiPC-1 with sulfuric acid, adding sodium carbonate and calcium carbonate, and heating in an electric furnace, ICP (Inductively Coupled) was used.
When the content of silicon (Si) atoms was quantified by plasma emission spectroscopy, the content of silicon (Si) atoms was 0.32%. In addition, the weight average molecular weight of SiPC-1 was 31,400, and the peak of the polymer of Production Example 2 was shifted to the high molecular weight side as a whole with respect to the peak of the polymer. Further, it was confirmed by infrared absorption spectrum analysis that the epoxy group (absorption wavelength: 918 cm ^-1 ) had almost disappeared. From the above, it was confirmed that a block copolymer was produced. The same analysis was performed for Si polycarbonate resins 2 to 7. Table 3 below shows the silicon (Si) atom content, weight average molecular weight, and siloxane copolymerization amount of SiPC-1 to SiPC-7.

[0141]

[Table 5]

The type in the parentheses indicates the type of silicone used for the copolymerization.

(Production of Silicone Compound-Polycarbonate Resin Copolymer (SiPC-8)) A hydroxyl-terminated polycarbonate (PC-3) was placed in a reactor equipped with a stirrer, a reflux condenser, N2 gas and a raw material polymer inlet. )
After melting 312.0 g at 260 ° C., 1.04 g of triphenylphosphine was added and mixed. Further, 35.0 g of the obtained epoxy-modified silicone SE8 was added and reacted for 30 minutes to obtain SiPC-8 ( o), 346.8
g (above formula).

Production Example Production of Silicone Compound-Polycarbonate Resin Copolymer (SiPC-9) A hydroxyl-terminated polycarbonate (PC-4) was placed in a reactor equipped with a stirrer, a reflux condenser, N 2 gas and a raw material polymer inlet. ) After melting 250 g at 260 ° C, 0.80 g of triphenylphosphine was added and mixed, and 18.0 g of the obtained epoxy-modified silicone SE9 was added and reacted for 30 minutes to obtain SiPC-9 (p). ), 26
7.8 g was obtained (the following formula).

(Production of Silicone Compound-Polycarbonate Resin Copolymer (SiPC-10-31))
In the production example of iPC-9, in the same manner as in the production example of SiPC-9, except that the hydroxyl-terminated polycarbonate (PC-4), epoxy-modified silicone, and triphenylphosphine as a catalyst were changed as shown in the following table. , Si polycarbonate resin SiPC-10 to 31
Was obtained (the following formula).

[0146]

[Table 6]

The SiPC-10 to 31 have the following structure.

[0148]

Embedded image

After heating the obtained resin SiPC-8 with sulfuric acid, adding sodium carbonate and calcium carbonate, and heating in an electric furnace, the ICP (Inductively Coupled) was used.
The content of silicon (Si) atoms was quantified by (d Plasma) emission spectroscopy. As a result, the content of silicon (Si) atoms was 2.00%. In addition, the weight average molecular weight of SiPC-1 was 34,000, and the peak of the polymer of this Production Example was shifted to the high molecular weight side as a whole with respect to the peak of the polymer. Further, it was confirmed by infrared absorption spectrum analysis that the epoxy group (absorption wavelength: 918 cm ^-1 ) had almost disappeared. From the above, it was confirmed that a block copolymer was produced.

After dissolving the obtained resin SiPC-9 with hot xylene, diethyl ether was added, unreacted silicone was removed by filtration, heated with sulfuric acid, and sodium carbonate and calcium carbonate were added. After heat treatment in a furnace, the content of silicon (Si) atoms was quantified by ICP (Inductively Coupled Plasma) emission spectroscopy. As a result, the content of silicon (Si) atoms was 2.59%. From the silicon (Si) atom content, it was found that the reaction rate (equimolar reaction) between the epoxy-modified silicone and the hydroxyl-terminated polycarbonate resin was almost 100%.
Further, the weight average molecular weight of SiPC-9 was 26,000, and the peak of the polymer of this Production Example was shifted to the high molecular weight side as a whole with respect to the peak of the polymer. From the above, it was confirmed that a block copolymer was produced. The same analysis was performed for Si polycarbonate-based resins 10 to 31. In the table below, SiPC-8 ~
31 shows the silicon (Si) atom content, weight average molecular weight, and siloxane copolymerization amount of No. 31.

[0151]

[Table 7]

Production Example 3 Production of Silicone Compound-Liquid Crystal Polyester Copolymer Epoxy-modified silicone resin obtained according to the method of Production Example 1 and liquid crystal polyester (LCP-1 and LCP-2) were respectively copolymerized, and 10 was obtained. (1) Production of Silicone Compound-Liquid Crystal Polyester Copolymer (SiLCP-1) 300 g of liquid crystal polyester (LCP-1) was melted at 280 ° C. in a nitrogen atmosphere, and then 180 g of epoxy-modified silicone resin SE29 was added. . Thereafter, 3.0 g of triphenylphosphine was added and reacted for 1 hour. Thereafter, the reaction product was freeze-pulverized, and unreacted silicone was removed with chloroform. Then, impurities such as a solvent were distilled off under reduced pressure under heating to obtain 1,418 g of SiLCP. (2) Production of Silicone Compound-Liquid Crystal Polyester Copolymer (SiLCP-2) 300 g of liquid crystal polyester (LCP-1) was melted at 280 ° C. in a nitrogen atmosphere, and 175 g of epoxy-modified silicone resin SE26 was added. . Thereafter, 3.0 g of triphenylphosphine was added and reacted for 1 hour. Thereafter, the reaction product was freeze-pulverized, and after removing unreacted silicone with chloroform, impurities such as a solvent were distilled off under reduced pressure under heating to obtain 416 g of SiLCP2. (3) Production of Silicone Compound-Liquid Crystal Polyester Copolymer (SiLCP-3) 300 g of liquid crystal polyester (LCP-1) was melted at 280 ° C. in a nitrogen atmosphere, and 110 g of epoxy-modified silicone resin SE32 was added. . Thereafter, 3.0 g of triphenylphosphine was added and reacted for 1 hour. Thereafter, the reaction product was freeze-pulverized, and unreacted silicone was removed with chloroform. Then, impurities such as a solvent were distilled off under reduced pressure under heating to obtain 370 g of SiLCP3. (4) Production of Silicone Compound-Liquid Crystal Polyester Copolymer (SiLCP-4) 300 g of liquid crystal polyester (LCP-1) was melted at 280 ° C. in a nitrogen atmosphere, and then 140 g of epoxy-modified silicone resin SE11 was added. . Thereafter, 3.0 g of triphenylphosphine was added and reacted for 1 hour. Thereafter, the reaction product was freeze-pulverized and unreacted silicone was removed with chloroform, and impurities such as a solvent were distilled off under reduced pressure under heating to obtain 390 g of SiLCP4. (5) Production of Silicone Compound-Liquid Crystal Polyester Copolymer (SiLCP-5) 300 g of liquid crystal polyester (LCP-1) was melted at 280 ° C. in a nitrogen atmosphere, and 176 g of epoxy-modified silicone resin SE13 was added. . Thereafter, 3.0 g of triphenylphosphine was added and reacted for 1 hour. Thereafter, the reaction product was freeze-pulverized, and after removing unreacted silicone with chloroform, impurities such as a solvent were distilled off under heating and reduced pressure to obtain 5,418 g of SiLCP. (6) Production of Silicone Compound-Liquid Crystal Polyester Copolymer (SiLCP-6) 300 g of liquid crystal polyester (LCP-2) was melted at 280 ° C. under a nitrogen atmosphere, and 166 g of epoxy-modified silicone resin SE13 was added. . Thereafter, 3.0 g of triphenylphosphine was added and reacted for 1 hour. Thereafter, the reaction product was freeze-pulverized, and after removing unreacted silicone with chloroform, impurities such as a solvent were distilled off under reduced pressure under heating to obtain 410 g of SiLCP6. (7) Production of Silicone Compound-Liquid Crystal Polyester Copolymer (SiLCP-7) 300 g of liquid crystal polyester (LCP-1) was melted at 280 ° C. under a nitrogen atmosphere, and 225 g of epoxy-modified silicone resin SE15 was added. . Thereafter, 3.0 g of triphenylphosphine was added and reacted for 1 hour. Thereafter, the reaction product was freeze-pulverized, and unreacted silicone was removed with chloroform. Then, impurities such as a solvent were distilled off under reduced pressure under heating to obtain 448 g of SiLCP7. (8) Production of Silicone Compound-Liquid Crystal Polyester Copolymer (SiLCP-8) 300 g of liquid crystal polyester (LCP-1) was melted at 280 ° C. in a nitrogen atmosphere, and 236 g of epoxy-modified silicone resin SE16 was added. . Thereafter, 3.0 g of triphenylphosphine was added and reacted for 1 hour. Thereafter, the reaction product was freeze-pulverized, and unreacted silicone was removed with chloroform. Then, impurities such as a solvent were distilled off under reduced pressure under heating to obtain 457 g of SiLCP8. (9) Production of Silicone Compound-Liquid Crystal Polyester Copolymer (SiLCP-9) 300 g of liquid crystal polyester (LCP-1) was melted at 280 ° C. under a nitrogen atmosphere, and then 90 g of epoxy-modified silicone resin SE9 was added. . Thereafter, 3.0 g of triphenylphosphine was added and reacted for 1 hour. Thereafter, the reaction product was freeze-pulverized, and unreacted silicone was removed with chloroform. Then, impurities such as a solvent were distilled off under reduced pressure under heating to obtain 358 g of SiLCP9. (10) Production of Silicone Compound-Liquid Crystal Polyester Copolymer (SiLCP-10) 300 g of liquid crystal polyester (LCP-1) was melted at 280 ° C. in a nitrogen atmosphere, and 176 g of epoxy-modified silicone resin SE310 was added. . Thereafter, 3.0 g of triphenylphosphine was added and reacted for 1 hour.
Thereafter, the reaction product was freeze-pulverized, and unreacted silicone was removed with chloroform. Then, impurities such as a solvent were distilled off under reduced pressure under heating to obtain 10,418 g of SiLCP.

After heating the obtained resin SiLCP-1 with sulfuric acid, adding sodium carbonate and calcium carbonate, and heating in an electric furnace, ICP (Inductively Coupled) was used.
The content of silicon (Si) atoms was quantified by (d Plasma) emission spectroscopy. As a result, the content of silicon (Si) atoms was 5.6%. Further, it was confirmed by infrared absorption spectrum analysis that the epoxy group (absorption wavelength: 918 cm ^-1 ) had almost disappeared. The same analysis was performed for SiLCP resins 2 to 10. In the table below, SiLCP-
The molecular weight, silicon (Si) atom content, and siloxane copolymerization amount of 1 to 10 are shown.

[0154]

[Table 8]

Note: The weight average molecular weight was calculated from the amount of reacted silicone.

Production Example 4 Production of Silicone Compound-Acrylonitrile-Styrene Resin Copolymer (1) Production of Silicone Compound-Acrylonitrile-Styrene Resin Copolymer (SiAS-1) Stirrer, reflux condenser, dropping funnel, N ₂ A solution prepared by dissolving 2.21 g of triphenylphosphine in 50 ml of 1,2-dichloroethane is added to a reactor equipped with a gas and raw material polymer solution inlet. Next, 2.36 g of hexachloroethane was added to 1,2-dichloroethane 50 from the dropping funnel.
The solution dissolved in ml is dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. An acrylonitrile-styrene copolymer having one end of a carboxyl group (AS)
-2), a solution in which 152 g was dissolved in 2000 ml of 1,2-dichloroethane was added to the reactor. Then 30
The mixture was heated under reflux using an oil bath for minutes. After removing the oil bath and allowing it to cool for 10 minutes,
3.0 g of the silicone compound k in 50 ml of 1,2-
1.6 ml of a solution dissolved in dichloroethane and triethylamine as an acid scavenger are added to the reactor. Then, the mixture was heated and refluxed again by an oil bath for 20 minutes.
After allowing the reaction solution to cool to room temperature, it was poured into 8 liters of methanol, and the precipitate was purified. Thereafter, the polymer was separated by filtration, washed,
Degassing was performed at 70 ° C. in mmHg to remove evaporated components. The weight of the obtained silicone compound (b) -acrylonitrile-styrene resin copolymer (SiAS-1) was 154.6 g.
Met. The weight average molecular weight of the obtained SiAS-1 was 81,200, and the peak of the polymer of this example was shifted to the high molecular weight side as a whole with respect to the peak of the polymer. In addition, it was confirmed by infrared absorption spectrum analysis that the carboxyl group (absorption wavelength: 3550 cm ^-1 ) had almost disappeared. From the above, it was confirmed that a block copolymer was produced.

(2) Production of silicone compound-acrylonitrile-styrene resin copolymer (SiAS-2) In the same manner as in Production Example 4- (1), 2.21 g of triphenylphosphine was added to 50 ml of 1,2-dichloroethane. Add the dissolved one. Next, 2.36 g of hexachloroethane was added to 1,2-dichloroethane 50 from the dropping funnel.
The solution dissolved in ml is dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. An acrylonitrile-styrene copolymer having one end of a carboxyl group (AS)
-2) A solution in which 152 g was dissolved in 2000 ml of 1,2-dichloroethane was added to the reactor. Thereafter, the mixture was heated under reflux for 30 minutes. And, Table 2 having a hydroxyl terminal
30.5 g of the silicone compound 1 in 700 ml of 1,
A solution of 2-dichloroethane and 1.6 ml of triethylamine are added to the reactor. Then, heating and refluxing were performed again for 25 minutes. After allowing the reaction solution to cool to room temperature, it was poured into 12 liters of methanol for precipitation purification. afterwards,
The polymer was separated by filtration, washed, degassed at 1 mmHg and 70 ° C,
The evaporation was removed. The obtained silicone compound (b)-
Acrylonitrile-styrene resin copolymer (SiAS-
The weight of 2) was 182.0 g. In addition, the obtained S
The weight average molecular weight of iAS-3 is 96,000,
With respect to the polymer peak, the peak of the polymer of this example was shifted to the higher molecular weight side as a whole. In addition, a carboxyl group (absorption wavelength 3
It was confirmed that 550 cm ^-1 ) had almost disappeared. From the above, it was confirmed that a block copolymer was produced.

(3) Production of Silicone Compound-Acrylonitrile-Styrene Resin Copolymer (SiAS-3) In the same manner as in Production Example 4- (1), 0.76 g of triphenylphosphine was added to 30 ml of 1,2-dichloroethane. Add the dissolved one. Next, 0.81 g of hexachloroethane was added to 1,2-dichloroethane 30 from the dropping funnel.
The solution dissolved in ml is dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 10 minutes. An acrylonitrile-styrene copolymer having one end of a carboxyl group (AS)
-2) A solution of 36.8 g in 600 ml of 1,2-dichloroethane was added to the reactor. Thereafter, the mixture was heated under reflux for 20 minutes. And, Table 2 having a hydroxyl terminal
23.5 g of the silicone compound m in 800 ml of 1,
A solution of 2-dichloroethane and 0.6 ml of triethylamine are added to the reactor. Then, heating and refluxing were performed again for 25 minutes. After allowing the reaction solution to cool to room temperature, it was poured into 3 liters of methanol for precipitation purification. Thereafter, the polymer was separated by filtration, washed, and degassed at 1 mmHg and 70 ° C. to remove evaporated components. The obtained silicone compound (b) -acrylonitrile-styrene resin copolymer (SiAS-
The weight of 3) was 59.9 g. In addition, the obtained Si
The weight average molecular weight of AS-3 is 130,000,
With respect to the polymer peak, the peak of the polymer of this example was shifted to the higher molecular weight side as a whole. In addition, a carboxyl group (absorption wavelength 3
It was confirmed that 550 cm ^-1 ) had almost disappeared. From the above, it was confirmed that a block copolymer was produced.

(4) Production of Silicone Compound-Acrylonitrile-Styrene Resin Copolymer (SiAS-4) In the same manner as in Production Example 4- (1), 2.21 g of triphenylphosphine was added to 50 ml of 1,2-dichloroethane. Add the dissolved one. Next, 2.36 g of hexachloroethane was added to 1,2-dichloroethane 50 from the dropping funnel.
The solution dissolved in ml is dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. An acrylonitrile-styrene copolymer having one end of a carboxyl group (AS)
-2) A solution in which 152 g was dissolved in 2000 ml of 1,2-dichloroethane was added to the reactor. Thereafter, the mixture was heated under reflux for 30 minutes. And, Table 2 having a hydroxyl terminal
30.5 g of silicone compound n of 700 ml of 1,
A solution of 2-dichloroethane and 1.6 ml of triethylamine are added to the reactor. Then, heating and refluxing were performed again for 25 minutes. After allowing the reaction solution to cool to room temperature, it was poured into 12 liters of methanol for precipitation purification. afterwards,
The polymer was separated by filtration, washed, degassed at 1 mmHg and 70 ° C,
The evaporation was removed. The obtained silicone compound (b)-
Acrylonitrile-styrene resin copolymer (SiAS-
The weight of 4) was 182.0 g. In addition, the obtained S
The weight average molecular weight of iAS-4 is 96,000,
With respect to the polymer peak, the peak of the polymer of this example was shifted to the higher molecular weight side as a whole. In addition, a carboxyl group (absorption wavelength 3
It was confirmed that 550 cm ^-1 ) had almost disappeared. From the above, it was confirmed that a block copolymer was produced. The following table shows the siloxane content and the like of SiAS-1 to SiAS-4.

[0160]

[Table 9]

(5) Production of Silicone Compound-Acrylonitrile-Styrene Resin Copolymer (SiAS-5) A carboxyl group terminal was provided in a reactor equipped with a stirrer, a reflux condenser, N2 gas and a raw material polymer inlet. Acrylonitrile-styrene copolymer (AS-2) 800.
After melting 0 g at 250 ° C., 2.45 g of triphenylphosphine was added and mixed. Further, 2.45 g of the obtained epoxy-modified silicone SE9 was added and reacted for 30 minutes to obtain SiAS-5 (p). , 817.5 g.

(6) In the production example of SiPC-9, the acrylonitrile-styrene copolymer (AS-2) having one end of a carboxyl group, the epoxy-modified silicone, and triphenylphosphine as a catalyst were changed as shown in the following table. In the same manner as in the production example of SiAS-5 except for the above, Si acrylonitrile-styrene resin SiAS-
6-17 were obtained.

[0163]

[Table 10]

The weight average molecular weights of the obtained SiAS-5 to 17 are as shown in the following table. The peak of the polymer of this example is shifted to the higher molecular weight side as a whole with respect to the peak of the polymer. Was. In addition, it was confirmed by infrared absorption spectrum analysis that the carboxyl group (absorption wavelength: 3550 cm ^-1 ) had almost disappeared. From the above, it was confirmed that a block copolymer was produced. The following table shows the siloxane content of SiAS-5 to 17 and the like.

[0165]

[Table 11]

The parentheses indicate the type of silicone used for the copolymerization.

(Properties of Silicone Copolymer) The melt viscosity, surface hearing, and oxygen index of the various silicone copolymers obtained as described above were evaluated.

The thermoplastic resin was dried at 100 ° C. for 5 hours, and then dried at 240 ° C. or 260 ° C. using a flow tester (Shimadzu Flow Tester CFT-500D, manufactured by Shimadzu Corporation).
The melt viscosity at 300 ° C. and a shear rate of 300 sec ⁻¹ was measured. The surface tension was measured using a contact angle measuring device CA-A manufactured by Kyowa Kagaku Co., Ltd. at 20 ° C. and 50% RH. The results are shown in the table below.

(Silicone compound-polycarbonate copolymer)

[0170]

[Table 12]

The parentheses indicate the type of silicone used for the copolymerization. * Melt viscosity is a value measured at 260 ° C. and a shear rate of 300 sec ⁻¹ . *** Surface tension is a value measured at 20 ° C and 50% RH. -The oxygen index is based on JIS-K for a test piece (125 x 6 x 3.2 mm) for flame retardancy evaluation obtained by injection molding.
According to -7201.

[0172]

[Table 13]

The type in the parentheses indicates the type of silicone used for the copolymerization. * Melt viscosity is a value measured at 260 ° C. and a shear rate of 300 sec ⁻¹ . *** Surface tension is a value measured at 20 ° C and 50% RH. -The oxygen index is based on JIS-K for a test piece (125 x 6 x 3.2 mm) for flame retardancy evaluation obtained by injection molding.
According to -7201.

(Silicone compound-liquid crystal polyester copolymer)

[0175]

[Table 14]

Measurement conditions of melt viscosity: 280 ° C. * 300 sec ⁻¹ (silicone compound-polystyrene copolymer)

[0177]

[Table 15]

The parentheses indicate the type of silicone used for the copolymerization. * Melt viscosity 240 ° C, shear rate 300s
Measurements at ec ^-1 . *** Surface tension is a value measured at 20 ° C and 50% RH. -The oxygen index is based on JIS-K for a test piece (125 x 6 x 3.2 mm) for flame retardancy evaluation obtained by injection molding.
According to -7201.

[0179]

[Table 16]

The type in the parentheses indicates the type of silicone used for the copolymerization. * Melt viscosity is a value measured at 240 ° C. and a shear rate of 300 sec ⁻¹ . *** Surface tension is a value measured at 20 ° C and 50% RH. -The oxygen index is based on JIS-K for a test piece (125 x 6 x 3.2 mm) for flame retardancy evaluation obtained by injection molding.
According to -7201.

The production examples and properties of the silicone copolymer have been described above. The following table summarizes the relationship between these copolymers and the silicone used.

[0182]

[Table 17]

[0183]

[Table 18]

[0184]

[Table 19]

Next, the results of evaluating the flame retardancy of the resin composition prepared using the above materials will be described with reference to the following tables.

Among the experimental examples shown in each table, A-1 and A-
... show a silicone compound-polycarbonate resin copolymer, B-1, B-2, ... show a silicone compound-liquid crystal polyester copolymer, and C-1, C-
2,... Indicate a silicone compound-acrylonitrile-styrene resin copolymer.

In the table, the siloxane content indicates the content (% by weight) of the siloxane contained in the composition. The siloxane content with respect to the copolymer amount indicates the content (% by weight) of the siloxane contained in the copolymer with respect to the entire composition. The oxygen index was determined by a test piece (125 × 6 × 3.2 m) for evaluating flame retardancy obtained by injection molding.
m) was measured according to JIS-K-7201. In each of the following tables, the parentheses indicate the type of silicone used for copolymerization.

A measurement sample was prepared as follows.

(Evaluation of Compositions Using Silicone Compound-Polycarbonate Resin Copolymer) Each compound shown in the table was extruded from a 37 mm-diameter twin screw extruder (KTX-3 manufactured by Kobe Steel, Ltd.).
Using 7), the mixture was melt-kneaded at a cylinder temperature of 260 ° C. to obtain various pellets. 10 pellets obtained
After drying at 0 ° C. for 5 hours, an injection molding machine (J100-E-C5 manufactured by Nippon Steel Corporation) was used at 260 ° C. and an injection pressure of 6 ° C.
A test piece for evaluating the flame retardancy at 125 kg / cm ² (125 ×
6 × 3.2 mm). Thereafter, a test piece (125 × 6 × 3.2 m) for evaluating flame retardancy obtained by injection molding.
For m), the oxygen index was measured according to JIS-K-7201.

(Silicone compound -acrylonitrile-
Evaluation of Compositions Using Styrene Resin Copolymer) Various compounds shown in the table were melt-kneaded using a 37 mm diameter twin screw extruder (KTX-37 manufactured by Kobe Steel) at a cylinder temperature of 240 ° C. Then, various pellets were obtained. The obtained various pellets were dried at 80 ° C. for 5 hours, and then used for evaluation of flame retardancy at 240 ° C. and an injection pressure of 600 kg / cm ² using an injection molding machine (J100-E-C5 manufactured by Nippon Steel Corporation). Test piece (1
25 × 6 × 3.2 mm). A test piece (125 × 6 × 3.2 m) for flame retardancy evaluation obtained by injection molding
For m), the oxygen index was measured according to JIS-K-7201.

(Evaluation of Compositions Using Silicone Compound-Liquid Crystal Polyester Copolymer) Each compound shown in the table was subjected to a twin-screw extruder having a diameter of 37 mm (KTX-37 manufactured by Kobe Steel Ltd.).
Was melt-kneaded at a cylinder temperature of 280 ° C. to obtain various pellets.

The obtained pellets were placed at 125 ° C. for 4 hours.
After the drying, the injection molding machine (J100 manufactured by Nippon Steel Corporation)
-E-C5), injection pressure 1600Kg
/ Cm ^TwoSpecimens for flame retardancy evaluation (125 × 6 × 3.
2 mm).

Further, various pellets were added at 125 ° C. for 4 hours.
After the drying, the injection molding machine (J100 manufactured by Nippon Steel Corporation)
-E-C5), injection pressure 1600Kg
/ Cm ^Two1mm thickness, 10mm width spiral
The low value was measured to evaluate the fluidity.

[0194]

[Table 20]

The total PC: all AS in the system was mixed so as to be 50:50 (weight ratio).

[0196]

[Table 21]

The total PC: all AS in the system was mixed so as to be 50:50 (weight ratio).

[0198]

[Table 22]

The total PC: all AS in the system was mixed so that the ratio became 50:50 (weight ratio).

[0200]

[Table 23]

A-17 and A-18 are all PCs in the system: all AS
Is 30:70 (weight ratio).
Nos. 19 and 20 are such that the total PC: AS in the system becomes 70:30 (weight ratio).

[0202]

[Table 24]

A-21 to 25 were blended so that the ratio of total PC to total AS in the system was 30:70 (weight ratio). A-2
Nos. 6 to 31 were blended such that the ratio of all PC: all AS in the system was 50:50 (weight ratio).

[0204]

[Table 25]

The total PC: all AS in the system was adjusted to be 70:30 (weight ratio).

[0206]

[Table 26]

The total PC: all AS in the system was mixed so as to be 50:50 (weight ratio).

[0208]

[Table 27]

The composition was such that all PC: all AS in the system was 50:50 (weight ratio).

[0210]

[Table 28]

The composition was such that all PC: all AS in the system was 50:50 (weight ratio).

[0212]

[Table 29]

The composition was such that all PC: all AS in the system was 50:50 (weight ratio).

[0214]

[Table 30]

The composition was such that all PC: all AS in the system was 50:50 (weight ratio).

[0216]

[Table 31]

The composition was such that all PC: all AS in the system was 50:50 (weight ratio).

[0218]

[Table 32]

The composition was such that all PC: all AS in the system was 50:50 (weight ratio).

[0220]

[Table 33]

The composition was such that all PC: all AS in the system was 50:50 (weight ratio).

[0222]

[Table 34]

The composition was such that all PC: all AS in the system was 50:50 (weight ratio).

[0224]

[Table 35]

The composition was such that all PC: all AS in the system was 50:50 (weight ratio).

[0226]

[Table 36]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

[0228]

[Table 37]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

[0230]

[Table 38]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

[0232]

[Table 39]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

[0234]

[Table 40]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

[0236]

[Table 41]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

[0238]

[Table 42]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

[0240]

[Table 43]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

[0242]

[Table 44]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

[0244]

[Table 45]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

[0246]

[Table 46]

[0247]

[Table 47]

[0248]

[Table 48]

In the above example, the total amount of AS in the system is other than the siloxane content (% by weight).

As can be seen from the above results, the flame retardancy is greatly improved by incorporating the copolymer of the present invention into the composition. This improvement effect is more remarkable than the case where a silicone compound is used in combination. In addition, it can be seen that the silicone compound to be copolymerized is more preferably one having a branched main chain and containing an aromatic residue as an organic functional group, because the flame retardant effect is higher. In the case of a copolymer having a low content of an aromatic residue as an organic functional group,
It can be seen that a system in which a silicone compound having a structure other than that of the present invention is added in combination cannot provide a sufficient flame retardant effect.

FIGS. 1 and 2 show A-10 and A-38 to
For A-59 and B-18 to B-29 and B-34, the relationship between the content of aromatic residues in the silicone compound to be copolymerized and the flame retardancy of the resin composition is shown.

From the figure, it can be seen that the silicone compound having an aromatic residue content of 30% or more as the organic functional group of the copolymerized compound has higher flame-retardant effect and is more preferable.

(Measurement of silicone distribution in molded article)
SiPC in a molded article of the composition of Example A-2 above
-3 was analyzed for the distribution of silicone.

With respect to the distribution in the depth direction, the molded product (12
A cross section of a 10 mm portion from the tip of (5 × 13 × 3.2 mm) was sliced, and the slice surface was subjected to Si elemental analysis by EDS analysis (energy dispersive X-ray elemental analysis). It was confirmed that the Si element concentration was very high in the outer layer of the molded article and low in the inner layer.

In addition, EDS was applied to a plurality of points on the surface of the molded article.
When the Si elemental analysis was performed, the Si elemental concentration showed a substantially uniform value.

Next, the distribution of dimethylsiloxane-derived silicone in the molded article using A-27 was analyzed. The analysis method is the same as A-2.

Regarding the distribution in the depth direction, it was confirmed that the Si element concentration was extremely high in the outer layer of the molded article and low in the inner layer.

On the other hand, for a plurality of points on the surface of the molded article, EDS
Was performed, it was confirmed that the variation in the Si element concentration was large and the distribution of silicone was non-uniform.

(Dispersion Particle Size of Silicone on Molded Product Surface) The dispersed particle size of the component containing Si element was measured by EDS analysis of the molded product surface. The results are shown in the table below.

[0260]

[Table 49]

[0261]

As described above, since the copolymer according to the present invention uses a silicone compound having a specific structure as a copolymer component, it has an unprecedented excellent flame retardancy. When used in a mixture with a resin such as a polycarbonate resin, a high degree of flame retardancy is obtained. Moreover, high flame retardancy is maintained even when used in combination with low flame retardant resin,
An excellent resin composition having high flame retardancy, low cost, and good moldability can be realized. Further, even when the obtained molded article is recycled, excellent flame retardancy can be obtained. Further, since it is not necessary to use a large amount of the halogen-based flame retardant, there is no concern about generation of harmful gas containing halogen caused by the halogen-based flame retardant at the time of combustion, and it is excellent in environmental protection. Furthermore, since it is not necessary to use a large amount of a phosphorus-based flame retardant, it is excellent in moisture resistance and heat resistance.

[Brief description of the drawings]

FIG. 1 is a diagram showing the relationship between the content of aromatic residues in a silicone compound to be copolymerized and the flame retardancy of a resin composition.

FIG. 2 is a graph showing the relationship between the content of aromatic residues in a silicone compound to be copolymerized and the flame retardancy of a resin composition.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 67/00 C08L 67/00 69/00 69/00 83/10 83/10 F-term (reference) 4-7002 Shiba 5-chome, Minato-ku, Tokyo 4J002 AC08W BC03W BC04W BC08W BC09W BC12W BN14W BN15W CF16W CF18W CG01W CG02W CP17X CP18X FD010 FD060 FD13X FD130 GM00 BA00GQ03 CA072 CA092 CA102 CA112 CA132 CA142 CA182 CA192 CA202 CA212 CA262 GA02 GA03 GA04 GA06 GA08 GA10 GB01 GB02 GB03 LA03 LB20

Claims (12)

[Claims] 1. A formula _{^{(I) (R 1 3 SiO}} 0.5) a (R 2 2 SiO) b (R 3 SiO 1.5) c (SiO 2) d ... (I) ( wherein, R ^1, R ² And R ³ each represent an aromatic residue or a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and a, b, c and d are (a + b + c + d) = 1. A polysiloxane-containing copolymer obtained by copolymerizing a silicone resin having an aromatic residue with an organopolysiloxane as a basic skeleton shown in (1) and a polycarbonate resin, wherein the silicone compound The aromatic residue content of the entire functional group is 30 to 95%, and the above formula (I)
A polysiloxane-containing copolymer, wherein 0 <c + d is satisfied. 2. In the formula (I), 0.2 <c + d
The polysiloxane-containing copolymer according to claim 1, wherein <0.95 is satisfied. 3. In the formula (I), 0.5 <c + d
3. The polysiloxane-containing copolymer according to claim 2, wherein <0.95 is satisfied. 4. The polysiloxane-containing copolymer according to claim 1, wherein the weight average molecular weight of the silicone compound is 300 to 100,000. 5. The composition according to claim 1, wherein said silicone compound is copolymerized with 0.5 to 80% by weight of said polycarbonate resin and 20 to 99.5% by weight of said polycarbonate resin.
The polysiloxane-containing copolymer according to any one of the above. 6. A polysiloxane-containing copolymer obtained by copolymerizing a liquid crystal polyester with a silicone compound having an aromatic residue and an organopolysiloxane represented by the following formula (I) as a basic skeleton. ^{_{(R 1 3 SiO 0.5) a}} (R 2 2 SiO) b (R 3 SiO 1.5) c (SiO 2) d ... (I) ( wherein, R ^1, R ² and R ³ are aromatic residues, respectively Or a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and a, b, c and d satisfy the relationship of (a + b + c + d) = 1 and c + d> 0. ) 7. The polysiloxane-containing copolymer according to claim 6, wherein 0.5 to 80% by weight of the silicone compound is copolymerized with 20 to 99.5% by weight of the liquid crystal polyester. Coalescing. 8. A polysiloxane-containing copolymer obtained by copolymerizing a silicone compound having an aromatic residue with an organopolysiloxane represented by the following formula (I) as a basic skeleton and a polystyrene resin: . ^{_{(R 1 3 SiO 0.5) a}} (R 2 2 SiO) b (R 3 SiO 1.5) c (SiO 2) d ... (I) ( wherein, R ^1, R ² and R ³ are aromatic residues, respectively Or a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and a, b, c and d satisfy the relationship of (a + b + c + d) = 1 and c + d> 0. ) 9. The polysiloxane-containing copolymer according to claim 8, wherein 0.5 to 80% by weight of the silicone compound is copolymerized with 20 to 99.5% by weight of the polystyrene resin. Polymer. 10. A formula _{^{(I) (R 1 3 SiO}} 0.5) a (R 2 2 SiO) b (R 3 SiO 1.5) c (SiO 2) d ... (I) ( wherein, R ^1, R ² And R ³ each represent an aromatic residue or a hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different, and a, b, c and d are (a + b + c + d) = The structural unit (A) is derived from a silicone compound having an organopolysiloxane as a basic skeleton and having an aromatic residue.
And a structural unit (B) containing an aromatic residue in the main chain skeleton or in the side chain, and the content of the aromatic residue relative to the entire functional group of the silicone compound is 30 to 95%, A polysiloxane-containing copolymer characterized by satisfying 0 <c + d in the above formula (I). 11. The structural unit (A) is contained in an amount of 0.5 to 80% by weight.
11. The polysiloxane-containing copolymer according to claim 10, comprising 20 to 99.5% by weight of the structural unit (B). 12. A polysiloxane-containing copolymer according to claim 1 in an amount of 0.5 to 80% by weight, and one or two selected from the group consisting of a polycarbonate resin, a liquid crystal polyester and a polystyrene resin. A flame-retardant resin composition comprising 20 to 99.5% by weight of the above resin.