JP2001335704A - Flame retardant material, injection molding method and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant molding material which realizes higher flame retardancy than ever and which has excellent recycling properties in a system which uses a combination of a low-cost resin with good moldability such as a polystyrene-based resin and a flame retardant resin such as a polycarbonate-based resin, to provide an injection molding method and a molded article. SOLUTION: The flame retardant molding material contains a flame retardant thermoplastic resin (A) and a thermoplastic resin (B), wherein the components (A) and (B) undergo phase separation, when molded, to form a molded article outer layer containing the component (A) as a main component and a molded article inner layer containing the component (B) as a main component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for imparting flame retardancy to a thermoplastic resin.
The present invention relates to a technique for imparting high flame retardancy to thermoplastic resin molded products used in various fields such as electric parts, electronic parts, mechanical parts, and automobile parts.

[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.

In general, a method of blending a halogen-based flame retardant such as a bromine compound having a high flame-retarding efficiency and an antimony compound as a flame-retardant auxiliary with a resin to make the resin flame-retardant is 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 order to avoid these problems, phosphorus-based flame retardants such as red phosphorus and phosphate esters have begun to be used, but their safety is not sufficient, and furthermore, resins using them have been used. The composition had problems such as poor moisture resistance and heat resistance.

Therefore, in recent years, in order to overcome the drawbacks of the halogen-based and phosphorus-based flame retardants, a flame-retardant resin containing no halogen or phosphorus has been strongly desired.

On the other hand, silicone compounds have high heat resistance, are unlikely to generate harmful gases during combustion, and have high safety per se. Therefore, many attempts have been made to use them as flame retardants.

The silicone compound as a flame retardant is a polymer obtained by polymerizing at least one of the following four siloxane units (M unit, D unit, T unit and Q unit).

[0009] M unit

[0010]

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Here, R represents a functional group.

D unit

[0013]

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Here, R represents an organic functional group.

T unit

[0016]

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Here, R represents an organic functional group.

[0018] Q unit

[0019]

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Of these, a branched structure is obtained particularly when a T unit and / or a Q unit are contained.

In order to use a silicone compound as a flame retardant, various silicone compounds having various organic functional groups, such as those described in JP-A-1-318069 and JP-B-62-60421, have been tried. Was.

However, very few of these have a significant flame retardant effect when added alone, and even if relatively effective, a large amount must be added to satisfy the strict flame retardant standards for electrical and electronic equipment. As a result, the moldability, kneadability and other necessary properties of plastics are adversely affected, and the cost is disadvantageous, which is not practical.

On the other hand, a method of using a silicone compound and a metal salt in combination has been reported as an attempt to improve the flame retardant effect of the silicone compound and to reduce the amount of addition. For this purpose, a combination of polydimethylsilicone, a metal hydroxide and a zinc compound (JP-A-2-150436), a combination of polydimethylsilicone and a group IIa metal salt of an organic acid (JP-A-56-100853) and the like are used. However, there is a fundamental problem that each of them is inferior in terms of flame retardancy and it is difficult to greatly reduce the amount of addition.

Further, a composition comprising a combination of a polycarbonate-organopolysiloxane copolymer and various flame retardants (for example, JP-A-1-210462 and JP-A-4-202)
465, JP-A-11-152398, etc.)
However, the flame retardancy of the polycarbonate-organopolysiloxane copolymer alone was insufficient.

Japanese Unexamined Patent Publication No. 11-217494 discloses that a metal salt of a specific silicone compound and an aromatic sulfur compound or a metal salt of perfluoroalkanesulfonic acid and / or a fiber-forming type fluorine-containing polymer is used to provide a high degree of flame retardancy. Disclosed are polycarbonate resins having properties.

However, polycarbonate resin is an expensive material and its moldability is not very good. For this reason,
Practical merits are greater when other resins that are inexpensive and have excellent moldability, such as polystyrene resins, are used in combination, rather than using polycarbonate resins alone.

[0027]

However, the present inventors have studied that when a polycarbonate resin and a polystyrene resin are used in combination, the decrease in flame retardancy due to the addition of the polystyrene resin becomes larger than expected. Was revealed. For example, when these resins are mixed in equal amounts and injection-molded, the flame retardancy of the resulting molded product is not the average of the flame retardancy of the two resins, and the flame retardancy of a polystyrene resin with poor flame retardancy It was confirmed that it was close to flammability.

The reason is considered as follows. When a mixture of a polycarbonate resin and a polystyrene-based resin is injection-molded, the polystyrene-based resin having excellent fluidity at the time of melting flows into the mold before the polycarbonate resin. Therefore, polystyrene-based resin having poor flame retardance segregates in the outer layer of the molded article, and polycarbonate-based resin segregates in the inner layer. For this reason, the decrease in flame retardancy due to the addition of the polystyrene resin is considered to be greater than expected from the mixing amount.

The present invention has been made in view of the above circumstances, and uses a low-cost resin having good moldability, such as a polystyrene resin, and a resin having excellent flame retardancy, such as a polycarbonate resin, in combination. It is an object of the present invention to provide a flame-retardant molding material, an injection molding method, and a molded product which realize high unprecedented flame retardancy and have excellent recyclability.

[0030]

Means for Solving the Problems As a method for preventing the surface segregation of inferior flame-retardant resin such as polystyrene resin, for example, a multilayer molding technique used in a field different from that of flame-retardant resin is used. It is possible. First, after injecting the flame-retardant resin constituting the outer layer, the resin constituting the inner layer may be injected with a time difference so that the flame-retardant resin is exposed to the outer layer of the molded article. However, in such a molding method, there are problems that a restriction on a mold is increased and a molding cycle is likely to be long. Furthermore, when a molded product is collected, recycled, and molded again, each resin raw material is in a mixed state, so that the above method cannot be adopted.

Accordingly, the present invention has studied the prevention of surface segregation of a resin having low flame retardancy by improving the molding material, and has arrived at the present invention.

According to the present invention, there is provided a flame-retardant molding material containing a flame-retardant thermoplastic resin (A) and a thermoplastic resin (B), wherein the components (A) and (B) A flame-retardant molding material characterized in that the components are phase-separated to form an outer layer of a molded article mainly composed of the component (A) and an inner layer of a molded article mainly composed of the component (B). Is done.

Further, according to the present invention, there is provided a flame-retardant molding material used for molding such as injection molding at a predetermined temperature, wherein the melt viscosity and the surface tension have the following specific relationships. A flexible molding material is provided.

That is, according to the present invention, a flame-retardant molding material containing a flame-retardant thermoplastic resin (A) and a thermoplastic resin (B), characterized by satisfying the following formula (1): A flame-retardant molding material is provided. η _a <η _b (1) (η _a indicates the melt viscosity of the component (A) at a shear rate of 300 sec ^-1 at the molding temperature, and η _b indicates the melt viscosity of the component (B) at a shear rate of 300 sec ^-1 at the molding temperature. It shows the melt viscosity.) In the flame-retardant molding material, it is preferable that the following formula (2) is further satisfied. γ _a <γ _b (2) (γ _a indicates the surface tension of the component (A) and γ _b indicates the surface tension of the component (B).) According to the present invention, the flame-retardant thermoplastic resin ( A method for injection-molding a flame-retardant molding material containing A) and a thermoplastic resin (B),
Injection is characterized in that the component (A) and the component (B) are phase-separated to form an outer layer of the molded article mainly composed of the component (A) and an inner layer of the molded article mainly composed of the component (B). A molding method is provided.

Further, according to the present invention, there is provided a method for injection-molding a flame-retardant molding material containing a flame-retardant thermoplastic resin (A) and a thermoplastic resin (B), wherein the following formula (1) is satisfied. An injection molding method is provided. η _a <η _b (1) (η _a indicates the melt viscosity of the component (A) at a shear rate of 300 sec ^-1 at the molding temperature, and η _b indicates the melt viscosity of the component (B) at a shear rate of 300 sec ^-1 at the molding temperature. It shows the melt viscosity.) In this injection molding method, it is preferable that the following formula (2) is further satisfied. γ _a <γ _b (2) (γ _a indicates the surface tension of the component (A), and γ _b indicates the surface tension of the component (B).) According to the present invention, it can be obtained by the above injection molding method. Molded articles are provided. Further, according to the present invention, a molded article having an outer layer of a molded article mainly composed of a flame-retardant thermoplastic resin (A) and an inner layer of a molded article mainly composed of a thermoplastic resin (B), A molded article characterized in that the oxygen index of the component (A) is at least 1.2 times the oxygen index of the component (B).

Further, according to the present invention, there is provided a molded article having a molded article outer layer mainly composed of the flame-retardant thermoplastic resin (A) and an molded article inner layer mainly composed of the thermoplastic resin (B). Wherein the component (A) is one or more resins selected from the group consisting of a polycarbonate resin, a liquid crystal polyester, and a copolymer obtained by copolymerizing a silicone compound (b) and a thermoplastic resin (a). Wherein the component (B) is a polystyrene resin.

In the present invention, the component (A) and the component (B) undergo phase separation by molding such as injection molding, and the molded article outer layer mainly composed of the component (A) and the component (B) are mainly used. A molded article inner layer as a component is formed. For this reason, when a molded article is produced, the outer surface of the molded article is covered with the highly flame-retardant component (A), so that it is difficult to ignite, and the structure has a high degree of flame retardancy. On the other hand, for the component (B), a material having low flame retardancy can be used, so that the range of material selection can be widened, and a material with low cost, a material with good moldability, and mechanical properties can be used. An excellent material can be freely selected.

Further, the present invention has an advantage of being excellent in recyclability. The flame-retardant molding material according to the present invention is in a state where the components (A) and (B) are mixed at a stage before molding, and after molding, the inherent properties of the components (A) and (B) Phase separation. Unlike multi-layer molding, different resin materials are not separately injected, so even if the molded product is collected and used again for molding, it can be phase-separated into the outer layer of the molded product and the inner layer of the molded product. A molded article having flammability can be obtained.

In general, when a molding material composed of a plurality of resins is injection-molded, the distribution of each resin may be non-uniform due to the gathering of the same type of resin. However, such uneven distribution is random and does not separate the outer layer and the inner layer with order. On the other hand, the present invention relates to a molded article outer layer mainly comprising the component (A) and
An inner layer of the molded article containing the component as a main component is formed, and a high degree of flame retardancy is imparted by the outer layer of the molded article.

Heretofore, a technique for segregating a flame retardant such as phosphorus on the surface of a molded article has been known (Japanese Patent Laid-Open No. 8-3112).
No. 80). In contrast, the present invention segregates the highly flame-retardant resin itself on the surface. Specifically, in the flame-retardant molding material containing the flame-retardant thermoplastic resin (A) and the thermoplastic resin (B), the component (A) is highly segregated on the surface. In this case, a higher degree of control is required than when a flame retardant that is easily separated from the base resin is segregated. This is because the component (A) and the component (B) are both thermoplastic resins and have similar molecular structures, so that ordered phase separation hardly occurs. In particular, in order to impart a high degree of flame retardancy by phase separation, phase separation occurs remarkably, and a high flame-retardant molded article outer layer and a low flame-retardant molded article inner layer may be formed. Required. Therefore, to generate phase separation to the extent that sufficient flame retardancy can be obtained, specific means for generating such phase separation will be described below.

The phase separation between the component (A) and the component (B)
Shear rate 300 sec at temperature ^-1Melt viscosity at
It can be realized by making a sharp adjustment.

The shear rate applied to the molten resin at the time of injection molding takes different values depending on the location in the mold, and also takes various values depending on the type of the resin, the shape of the molded body, and the like. Specifically, it usually takes a value of 100 to 10000 sec ^-1 . In the injection molding which can take such a wide range of shear rates, the present inventors particularly select a shear rate of 300 sec ^-1 as a representative value, and (A) and (B) at such shear rates.
By defining the relationship between the melt viscosities of the components, it has been found that a desired multilayer molded article can be obtained. The present invention has been made based on such findings.

Separation of different kinds of resins at the time of molding can occur due to various factors.
In order to separate the outer layer and the inner layer with order, the melt viscosity at a shear rate of 300 sec ^-1 at the molding temperature is a dominant factor. Specific means for adjusting the melt viscosity include means for appropriately selecting the type and molecular weight of the resin constituting each component, and the like. Generally, when a material formed by mixing a polycarbonate resin and a polystyrene resin is molded, the polystyrene resin is more likely to segregate on the surface as described above. However, by adjusting the melt viscosity, it becomes possible to segregate a resin, such as a polycarbonate resin, which easily segregates in the inner layer of the molded article, in the outer layer of the molded article, thereby realizing a high degree of flame retardancy.

Specifically, by adjusting the melt viscosity so as to satisfy the following formula (1), the component (A) can be highly segregated in the outer layer of the molded article. η _a <η _b (1) (η _a indicates the melt viscosity of the component (A) at a shear rate of 300 sec ^-1 at the molding temperature, and η _b indicates the melt viscosity of the component (B) at a shear rate of 300 sec ^-1 at the molding temperature. (The melt viscosity is shown.) Furthermore, if not only the melt viscosity but also the surface tension is adjusted so that the following formula (2) is satisfied, the component (A) can be more remarkably segregated in the outer layer of the molded article. γ _a <γ _b (2) (γ _a indicates the surface tension of the component (A), and γ _b indicates the surface tension of the component (B).) The melt viscosity satisfies the following expression (3). By doing so, more remarkable flame retardancy can be obtained. η _a ≦ 0.90 × η _b (3) On the other hand, regarding the surface tension, if the following expression (4) is satisfied, more remarkable flame retardancy can be obtained. γ _a ≦ 0.90 × γ _b (4) As described above, according to the present invention, a material having high flame retardancy and low flame retardancy but low cost, excellent moldability, and high strength In a system in which a material having such features as described above is used in combination, excellent unprecedented flame retardancy can be realized. For this reason, it is possible to obtain a molded product that is low in cost, has excellent moldability, and has high flame retardancy. Moreover, even when the obtained molded article is recycled, excellent flame retardancy can be obtained. In addition, since it is not necessary to use a large amount of the halogen-based flame retardant, there is no fear of generating a harmful gas containing halogen due to the halogen-based flame retardant during combustion.
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.

The molding temperature of the flame-retardant resin molding material of the present invention is appropriately selected according to its components.
20 ° C to 340 ° C, preferably 240 ° C to 32
0 ° C or less. Within this temperature range, good moldability can be obtained.

[0046]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, phase separation occurs during molding, and an outer layer of a molded article mainly composed of the component (A) and an inner layer of a molded article mainly composed of the component (B) are formed. .
The phrase “having the component (A) as a main component” means that, for example, the content of the component (A) is at least 70 wt-%, preferably at least 80 wt-%, in the material constituting the outer layer of the molded article. on the other hand,
The phrase “having the component (B) as a main component” means that, for example, in the material constituting the inner layer of the molded article, the abundance of the component (B) is at least 60 wt-%, preferably at least 70 wt-%.

Here, the outer layer of the molded article refers to a layer near the outer surface of the molded article, for example, a layer including at least a region from the surface of the molded article to a depth of 100 μm. On the other hand, the inner layer of the molded article refers to a layer constituting the inside of the molded article, and refers to a layer located at an arbitrary position inside the outer layer of the molded article. For example, when the thickness of the molded article is d, the layer is located at a depth of about 0.5 × d from the surface of the molded article. In a preferred embodiment, assuming that the thickness of the molded article is d, the concentration of the component (A) is higher than the concentration of the component (B) in the region extending from the surface of the molded article to a depth of 0.1 × d, and the depth of the component is 0.1 mm. 4 × d
In the region ranging from 0.5 to 0.5 × d, the concentration of the component (B) is higher than the concentration of the component (A), and a molded article outer layer mainly containing the component (A) is formed near the surface of the molded article. An embodiment in which an inner layer of a molded article mainly containing the component (B) is formed near the center of the molded article.

The flame-retardant thermoplastic resin (A) in the present invention
Is to segregate on the surface of a molded article to give a high degree of flame retardancy. Usually, a resin material having higher flame retardancy than the thermoplastic resin (B) is used. For example, it is preferable that the oxygen index of the flame-retardant thermoplastic resin (A) is larger than that of the thermoplastic resin (B), and the oxygen index of the flame-retardant thermoplastic resin (A) is greater than that of the thermoplastic resin (B). It is more preferably larger than 1.2 times the oxygen index of

As the flame-retardant thermoplastic resin (A), a resin having 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 resin itself is improved. In addition, when a silicone compound having an aromatic residue is used in combination, since the compatibility with the silicone compound is good, the distribution of the silicone compound on the surface of the molded article becomes uniform, and from this point the effect of improving the flame retardancy is also obtained. Is obtained. As such a resin, specifically, polycarbonate, liquid crystal polyester, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polyimide, polyamide imide, polyether imide, poly-p-phenylene terephthalamide, polybutylene Examples include terephthalate, polycarbonate-containing copolymers, and derivatives thereof. Among them, polycarbonate, liquid crystal polyester, polycarbonate-containing copolymer, and derivatives thereof are particularly preferable because higher flame retardancy can be obtained.

The component (A) may be configured to include a copolymer obtained by copolymerizing the silicone compound (b) and the thermoplastic resin (a). This copolymer 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 such copolymerization, the structural unit derived from the silicone compound (b) lowers the melt viscosity and surface tension of the copolymer, so that it is remarkably precipitated on the surface of the molded article. The structural unit derived from the silicone compound (b) in the copolymer has a high flame-retardant function, and since it segregates on the surface, it is possible to realize an unprecedented high flame-retardant property. Furthermore, when the above copolymer is used, the distribution of silicone on the surface of the molded article can be made uniform, so that 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 unevenly, and to reduce the distribution of the silicone on the surface of the molded article. Very good uniformity. In particular, the silicone compound (b) has 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 (a), the distribution of silicone on the surface of the molded product is particularly good.

In addition, even when the flame-retardant molding material of the present invention further contains a silicone compound (a) having an aromatic residue, the uniformity of the distribution of silicone on the surface of the molded article is improved. Can be.

As the thermoplastic resin (a) used in the above copolymer, a resin containing an aromatic ring in the main chain skeleton is preferably used, and a resin having an aromatic residue in the 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, acrylonitrile-butadiene-styrene resin, polyphenylene sulfide, polysulfone, polyether sulfone, polyetheretherketone, polyimide, polyamideimide, polyetherimide, poly- Examples include p-phenylene terephthalamide, polybutylene terephthalate, and derivatives thereof. Of these, polycarbonate, liquid crystal polyester, polybutylene terephthalate, polystyrene and derivatives thereof are preferably used because of their good flame retardancy and good moldability.

The examples of the resin used as the flame-retardant thermoplastic resin (A) have been described above, but these resins may be used alone or in combination of two or more.

In the present invention, the thermoplastic resin (B) segregates in the inner layer of the molded product. Although there is no particular limitation on the material, materials having low cost, good moldability, and high mechanical strength are preferably used. Specifically, polystyrene resin, rubber-reinforced polystyrene, acrylonitrile-styrene resin, and their modified acrylic rubber, acrylonitrile-butadiene-styrene resin, acrylonitrile-ethylene-propylene-diene rubber (EPDM) -styrene copolymer, etc. Polystyrene resins; polyesters such as polyethylene terephthalate and polybutylene terephthalate; and polypropylene. These may be used alone or as a mixture of two or more.

Preferred examples of the combination of the flame-retardant thermoplastic resin (A) and the thermoplastic resin (B) include a polycarbonate resin and a liquid crystal polyester as the component (A).
Component (B) is a combination of a polystyrene resin, or component (A) is a copolymer obtained by copolymerizing silicone compound (b) and thermoplastic resin (a), and component (B) is polystyrene. Examples of the combination include a base resin. For example, the component (A) may be a polycarbonate resin, a liquid crystal polyester and derivatives thereof, a mixture of a polycarbonate resin and a liquid crystal polyester, a copolymer of a polycarbonate resin and a silicone compound (b), a liquid crystal polyester and a silicone compound (b), and a polycarbonate. And one or more resin materials selected from the group consisting of copolymers obtained by copolymerizing a liquid crystal polyester and a silicone compound (b), while (B) is polystyrene, rubber-reinforced polystyrene, acrylonitrile-styrene Resin, one or more resin materials selected from the group consisting of acrylonitrile-butadiene-styrene resin and derivatives thereof.

The flame-retardant thermoplastic resin (A) and the thermoplastic resin (B) may contain the same component in the resin skeleton (structure). For example, (A) is a copolymer obtained by copolymerizing a silicone compound (b) and an acrylonitrile-styrene resin, and (B) is acrylonitrile-
It is also possible to use styrene resins. further,
It is also possible to use (A) a copolymer obtained by copolymerizing a silicone compound (b) and a polycarbonate resin, and (B) a polycarbonate resin.

The polycarbonate resin in the present invention is a resin containing a polycarbonate unit represented by the following general formula.

[0059]

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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-based 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 representative. Examples include polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the above 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 at the time of combustion, into 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. Specifically, (1) a combination of an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid, (2) a combination of different aromatic hydroxycarboxylic acids, and (3) an aromatic hydroxycarboxylic acid Examples thereof include a combination of a dicarboxylic acid and a nucleus-substituted aromatic diol, and (4) a product obtained by reacting an aromatic hydroxycarboxylic acid with a polyester such as polyethylene terephthalate. It forms a melt. 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 100 kgf / c of the liquid crystal polyester heated at a heating rate of 4 ° C./min.
It is usually measured as the temperature at which the melt viscosity shows 48,000 poise when extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of m ² .

A repeating structural unit derived from an aromatic dicarboxylic acid:

[0068]

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A repeating structural unit derived from an aromatic diol:

[0070]

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A repeating structural unit derived from an aromatic hydroxycarboxylic acid:

[0072]

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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

[0074]

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

[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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The production method of the liquid crystal polyesters (I) to (VI) is described in, for example, Japanese Patent Publication No. 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-based resin and the rubber-reinforced polystyrene-based resin are obtained by mixing other components as appropriate with a synthetic resin obtained by polymerization of styrene. It also includes 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. Examples of other aromatic vinyl compounds include α-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 of the present invention will be described.

In the present invention, the silicone compound (a) having an aromatic residue may be contained as the component (C). The silicone compound (a) improves flame retardancy by being used in combination with the flame retardant thermoplastic resin (A), and is preferably a compound having a main chain having a branched structure.

The silicone compound (a) has, for example, an organopolysiloxane skeleton represented by the following formula.

[0088]

Embedded image

(Wherein R ¹ , R ² and R ³ each represent an aromatic residue or an aliphatic derivative group having 1 to 6 carbon atoms;
Each may be the same or different.
a, b, c and d satisfy the relationship of (a + b + c + d) = 1. In addition, 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 can be the same or different, and each R ³ can be
Each 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. Where c
When + d> 0, the flame retardancy is further improved.

The silicone compound (a) is represented by (R ³ SiO
_1.5 ) T unit represented by) and Q unit represented by (SiO ₂ )
It is preferable to contain a certain amount or more of units. In particular,
The branch unit content α represented by the following formula α = c + d is preferably 0.2 or more, more preferably 0.5 or more.

By doing so, the flame retardancy is further improved. If the value of α is too low, the heat resistance of the silicone compound may be reduced and its flame-retardant effect may be reduced. In addition, the viscosity of the silicone compound (a) itself is too low and the kneadability with the thermoplastic resin may be reduced. And adversely affect moldability. On the other hand, the upper limit of α is preferably set to 0.95 or less. If α is too large, the degree of freedom of the main chain of the silicone is reduced, so that condensation of aromatic residues during combustion may be difficult to occur, and it may be difficult to exhibit remarkable flame retardancy.

The silicone compound (a) has a content of an aromatic residue with respect to the whole organic functional group contained in the compound.
Preferably 20 mol% or more, more preferably 40 mol%
1% or more, most preferably 60 mol% or more. By doing so, the condensation of the aromatic residue proceeds more efficiently during combustion, and the dispersibility of the silicone compound in the thermoplastic resin is significantly improved, and a very 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. In addition, regarding the upper limit of the content rate,
It is preferable that the content be 95 mol% or less. 95 mol%
When the number exceeds 3, the steric hindrance between aromatic residues may make it difficult to cause these condensations, and the flame retardant effect may not be sufficiently obtained.

The organic functional group contained in the silicone compound (a) refers to an organic functional group bonded to a main chain or a branched side chain.

The aromatic residue contained in the silicone compound (a) is a functional group derived from an aromatic, and the aromatic is a benzene ring, a condensed benzene ring, a polyaromatic ring,
A compound having an aromatic ring such as a non-benzene-based aromatic ring and 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.

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

The terminal group of the silicone compound (a) is preferably a methyl group, a phenyl group or a hydroxyl group, particularly preferably a methyl group. Because these functional groups have low reactivity, when kneaded with a thermoplastic resin,
Gelation (cross-linking) of the silicone compound is less likely to occur, a more favorable flame-retardant effect is obtained, dispersibility is further improved, and moldability is improved.

The average molecular weight (weight average) of the silicone compound (a) is preferably from 5,000 to 500,000. If it is less than 5,000, the heat resistance of the silicone compound (a) itself is reduced, and the flame retardant effect and moldability are reduced.
If it exceeds 10,000, the melt viscosity increases and the surface layer precipitation during molding is hindered, so that the flame-retardant effect and moldability may be reduced. More preferably, it is 10,000 or more and 270,000 or less. In this range, the melt viscosity of the silicone compound (a) is optimized and the kneadability with the thermoplastic resin is improved, so that better flame retardancy and moldability can be achieved.

The compounding amount of the silicone compound (a)
Preferably from 0.01 to 8 parts by weight, more preferably from 0.1 to 5 parts by weight, most preferably from 0.5 to 5 parts by weight, per 100 parts by weight of the total of component (A) and component (B).
Not less than 2 parts by weight. Within this range, the balance between flame retardancy, moldability, and impact strength is further improved.
If the amount is too small, the flame retardant effect may be insufficient,
On the other hand, if the compounding amount is too large, surface layer peeling may occur on the surface of the molded product, and the appearance may be deteriorated.

In the present invention, the flame-retardant thermoplastic resin (A) can be a copolymer obtained by copolymerizing the silicone compound (b) and the thermoplastic resin (a).

The silicone compound (b) 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. ^{_{(R 1 3 SiO 0.5) a}} (R 2 2 SiO) b (R 3 SiO 1.5) c
(SiO ₂ ) _d (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 and c + d> 0.) The reactive functional group is a functional group in which R in the above basic skeleton is substituted, and usually, the above-mentioned organopolysiloxane is used. Located at the end of the siloxane. 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 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.

The silicone compound (b) is represented by (R ³ SiO
_1.5 ) T unit represented by) and Q unit represented by (SiO ₂ )
It is preferable to contain a certain amount or more of units. Specifically, it is preferable that the branch unit content rate α represented by α = c + d is 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, α is preferably 0.2 or more, more preferably 0.5 or more.

In the copolymer of organopolysiloxane and 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.

The silicone compound (b) preferably has a content of aromatic residues in the organic functional groups contained in the compound of not less than a certain value. 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 (b) is a functional group derived from an aromatic, and the aromatic is a benzene ring, a condensed benzene ring, a polyaromatic ring,
A compound having an aromatic ring such as a non-benzene-based aromatic ring and 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.

It is preferable that the content of the aromatic residue is specifically 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.

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 is no particular limitation on the groups other than the aromatic residues among the organic functional groups, but it is preferable 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 in the present invention is obtained by copolymerizing a silicone compound with another resin, and 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.

Further, 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.

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 (b) is preferably 300 or more, more preferably 5 or more.
00 or more, most preferably 1,000 or more. 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 groups include, 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, a halogen group, an allyl group, and an SiH group. In the production of the copolymer of the silicone compound (b) and the thermoplastic resin (a) used in the present invention, it is preferred that the reactive group is selected depending on the resin to be combined and the copolymerization is carried out efficiently. As the combination of the 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 hydroxyl group, a carboxyl group, a vinyl group, and an allyl group. , An amide group, an imide group, an imino group, and the like, and a combination having one as a hydroxyl group and the other as an alkoxy group and a mercapto group.

Examples of the radical polymerizable monomer include acrylate derivatives such as phenyl (meth) acrylate and benzyl (meth) acrylate and methacrylate derivatives; 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.

In the 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.

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, a 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, thereby obtaining 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 an acid chloride compound such as (meth) acrylic acid chloride; a diisocyanate compound 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-mentioned 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 such a compound, it has 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 preferably a thermoplastic resin containing an aromatic residue in an organic functional group. Examples of the copolymer include silicone-polycarbonate. Copolymer, silicone-liquid crystalline polyester copolymer, silicone-acrylonitrile-styrene copolymer, silicone-polyphenylene sulfide copolymer, silicone-polybutylene terephthalate copolymer, silicone-polyethersulfone copolymer, silicone- Polysulfone copolymer, silicone-polyetheretherketone copolymer, silicone-polyimide copolymer, silicone-polyamideimide copolymer, silicone-polyetherimide copolymer, silicone-poly-p-phenyleneterephthalamide copolymer Etc.

The amount of the copolymer obtained by copolymerizing the silicone compound (b) and the thermoplastic resin (a) is as follows:
0.1 parts per 100 parts by weight of the total of the components (A) and (B).
It is preferably from 5 parts by weight to 150 parts by weight. If the compounding amount is less than 0.5 parts by weight, the flame retardant effect may be insufficient,
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.

In the present invention, in the case of phase separation during molding,
An intermediate layer in which these are mixed may exist between the outer layer and the inner layer, and the flame retardant thermoplastic resin (A) component may partially exist in the inner layer of the molded article. The thermoplastic resin (B) component may partially exist in the outer layer. Further, other components such as the third component and the fourth component may be present in a part of the outer layer or the inner layer, or in the intermediate layer.

Further, in the present invention, when a metal salt of an aromatic sulfur compound (D) or a metal salt of perfluoroalkanesulfonic acid (E) is blended, even higher flame retardancy can be obtained.

The metal salt (D) of the aromatic sulfur compound is a metal salt of an aromatic sulfonamide or a metal salt of an aromatic sulfonic acid.

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-tolylsulfonimide).
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, and 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 compounding amount of the metal salt (D) of the aromatic sulfur compound is preferably from 0.03 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B). 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. Particularly in this range, the balance between flame retardancy, moldability and impact strength is further improved.

The metal salt of perfluoroalkanesulfonic acid (E) is a metal salt of perfluoroalkanesulfonic acid.

Preferred examples of the metal salt of perfluoroalkanesulfonic acid (E) include metal salts of perfluoromethanesulfonic acid, metal salts of perfluoroethanesulfonic acid, metal salts of perfluoropropanesulfonic acid, and perfluorobutane. Metal salts of sulfonic acid, metal salts of perfluoromethylbutanesulfonic acid, metal salts of perfluorohexanesulfonic acid, metal salts of perfluoroheptanesulfonic acid, and metal salts of perfluorooctanesulfonic acid. These may be used alone or in combination of two or more. The metal salt (E) of perfluoroalkanesulfonic acid may be used in combination with the metal salt (D) of the aromatic sulfur compound.

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

The amount of the metal salt of perfluoroalkanesulfonic acid (E) is 10% in total of the components (A) and (B).
It is preferably 0.01 part by weight or more and 5 parts by weight or less based on 0 part by weight. If the amount is less than 0.01 part by weight, it may be difficult to obtain a remarkable flame retardant effect, and if it exceeds 5 parts by weight, the thermal stability during injection molding may be poor. As a result, moldability and impact strength may be adversely affected. More preferably, 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, by adding a fiber-forming type fluoropolymer (F), which is considered to have a drip prevention effect, to the flame-retardant molding material according to the present invention, an even higher flame-retardant effect can be obtained. As the fiber-forming fluoropolymer (F),
Those which form a fiber structure (fibril-like structure) in a thermoplastic resin are preferable, and examples thereof include polytetrafluoroethylene, tetrafluoroethylene-based copolymers (eg, tetrafluoroethylene / hexafluoropropylene copolymer, etc.). Can be

The compounding amount of the fiber-forming fluoropolymer (F) is 0.05 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B). 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, the content is in the range of 0.05 to 1 part by weight, and even more preferably 0.1 to 0.5 part 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, colorants, optical brighteners, fillers, release agents, softeners,
Additives such as antistatic agents, impact modifiers 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 a total of 1 (A) component and (B) component.
It is usually used in a range of 0 part by weight to 0.5 part by weight based on 00 parts by weight.

Examples of the filler include glass fiber, glass beads, glass flake, carbon fiber, 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.

If necessary, other flame retardants can be added, 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 thermoplastic resin composition of the present invention is not particularly limited, and mixing by a known mixer such as a tumbler or a ribbon blender or melt-kneading by an extruder is possible. No.

As a method for molding the flame-retardant thermoplastic 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 molding material of the present invention, NO. 1 to
5 are mentioned. In addition, the silicone component (C), the metal salts (D) and (E), the fiber-forming fluoropolymer (F), and the like can be appropriately added to the component (A).

[0152]

[Table 1]

In the table, NO. The copolymers contained in the components (A) and (3) have good compatibility with other resins. For this reason, the organopolysiloxane unit derived from silicone (b) is uniformly distributed in the outer layer of the molded article, and particularly high flame retardancy is obtained.

In addition, NO. The copolymer No. 5 is excellent in moldability, and thus is used alone (A) without being used in combination with other resins.
Can be used as a component.

[0155]

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.

In the following Examples and Comparative Examples, the molecular weight was measured by GPC (gel permeation chromatography).
Was measured by

The details of the raw materials used in the examples and comparative examples are as follows. 1. Acrylonitrile-styrene resin (AS-1 and A
S-2): AS-1 (weight average molecular weight 330,00
0), AS-2 (weight average molecular weight 60,000) Carboxy group-terminated acrylonitrile-styrene resin: AS-3 (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. Polycarbonate resin (PC-1 and PC-2):
PC-1 (weight average molecular weight 15,600), PC-2
(Weight average molecular weight 19,000) 4. 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. Hydroxyl-terminated polycarbonate resin (PC-4): PC-
No. 4 (weight average molecular weight 25,000) was produced according to the same production method as above. 5. Polystyrene resin: Nippon Steel Chemical's G-10 was used as the polystyrene resin (PS). 6. 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 described above, an appropriate amount of 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). 7. 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. Table 2 shows the structural characteristics of the 14 silicone compounds synthesized by the above method.

[0160]

[Table 2]

[0161]

[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. The relationship between the type of silicone compound used and the copolymer produced is shown in FIGS. 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 wt.
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 0.32% solution of 2-wt% chloroplatinic acid in 2-ethylhexanol as a catalyst was 0.32.
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 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 (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.
6, 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 in (1) above, methyl isobutyl ketone as a solvent, a 2 wt% solution of chloroplatinic acid in 2-ethylhexanol as a catalyst, and silicone as shown in the following table were used. Thus, epoxy-terminated silicone resins SE8 to 32 were obtained. It was confirmed by infrared absorption spectrum analysis that the Si-H group (absorption wavelength: 2175 cm ^-1 ) had almost disappeared.

[0170]

[Table 4]

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

[0172]

Embedded image

Production Example 2 Production of Silicone Compound (b) -Polycarbonate Resin Copolymer 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. After adding and dissolving 312.0 g of hydroxyl group-terminated polycarbonate (PC-3) in the solution thus obtained, adding 1.0 g of triphenylphosphine, reacting the mixture under reflux for 5 hours, washing with xylene, and heating. The solvent was distilled off under reduced pressure to obtain SiPC-1, 31.
6.3 g was obtained (following 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 following 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 following 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 following 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 was obtained (the following 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 following 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 following formula).

After heating the obtained resin SiPC-1 with sulfuric acid, adding sodium carbonate and calcium carbonate, and heating in an electric furnace, the ICP (Inductively Coupled) was used.
When the content of silicon (Si) atoms was quantified by (d 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. The following table shows the silicon (Si) atom content, weight average molecular weight, and siloxane copolymerization amount of SiPC-1 to SiPC-7.

[0181]

[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, and the obtained epoxy-modified silicone SE8, 35.0 was further added.
g, and reacted for 30 minutes to obtain SiPC-8.
(o) 346.8 g was obtained (the 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, N2 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 to 31)) In the above-mentioned production example of SiPC-9, polycarbonate having a hydroxyl group terminal (PC-4), epoxy-modified silicone, and a catalyst were used. In the same manner as in the production example of SiPC-9, except that triphenylphosphine was changed as shown in the following table, a Si polycarbonate resin SiPC-1 was produced.
0-31 were obtained.

[0186]

[Table 6]

[0187]

Embedded image SiPC-10 to 31 have the following structure.

After heating the obtained resin SiPC-8 with sulfuric acid, adding sodium carbonate and calcium carbonate, and performing a heat treatment in an electric furnace, an 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.

[0190]

[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 to obtain SiLCP-1 and SiLCP-1. 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 performing heat treatment 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.

[0193]

[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 of SiAS-1 to SiAS-4.

[0199]

[Table 9]

(5) Production of Silicone Compound-Acrylonitrile-Styrene Resin Copolymer (SiAS-5) One end of a carboxyl group was placed in a reactor equipped with a stirrer, a reflux condenser, N ₂ 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, an 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.

[0202]

[Table 10]

The weight average molecular weights of the obtained SiAS-5 to 17 are as shown in the table below. The peak of the polymer of this example is shifted to the higher molecular weight side 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.

[0204]

[Table 11]

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

(Properties of Silicone Copolymer) The silicone copolymer obtained as described above was evaluated for melt viscosity, surface tension and oxygen index.

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)

[0209]

[Table 12]

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.

[0211]

[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)

[0214]

[Table 14]

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

[0216]

[Table 15]

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.

[0218]

[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 shows the relationship between these copolymers and the silicones used.

[0221]

[Table 17]

[0222]

[Table 18]

[0223]

[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.

Of 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 subjected to 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 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.

[0231] The various pellets obtained 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.

[0233]

[Table 20]

Each example in the above table is formulated such that the ratio of total PC: all AS in the system is 50:50 (weight ratio).

[0235]

[Table 21]

The examples in the above table are based on all the PCs in the system:
The composition is such that the total AS is 50:50 (weight ratio).

[0237]

[Table 22]

The examples in the above table are based on all PCs in the system:
The composition is such that the total AS is 50:50 (weight ratio).

[0239]

[Table 23]

A-22 to A-24 represent all PCs in the system:
The composition is such that the total AS is 30:70 (weight ratio), and the composition of A-25 to A-27 is such that the total PC: all AS in the system is 70:30 (weight ratio). .

[0241]

[Table 24]

[0242]

[Table 25]

[0243]

[Table 26]

[0244]

[Table 27]

[0245]

[Table 28]

[0246]

[Table 29]

[0247]

[Table 30]

[0248]

[Table 31]

[0249]

[Table 32]

[0250]

[Table 33]

[0251]

[Table 34]

[0252]

[Table 35]

[0253]

[Table 36]

[0254]

[Table 37]

[0255]

[Table 38]

[0256]

[Table 39]

[0257]

[Table 40]

[0258]

[Table 41]

[0259]

[Table 42]

[0260]

[Table 43]

[0261]

[Table 44]

[0262]

[Table 45]

[0263]

[Table 46]

[0264]

[Table 47]

FIGS. 1 and 2 show the content of aromatic residues in the silicone compound to be copolymerized and the flame retardancy of the resin composition for A-41 to A-62 and B-20 to B-31. Shows the relationship.

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

Next, the analysis result of a molded article using the flame-retardant molding material according to the present invention will be described.

(Layer Structure of Molded Article) Examples A-1 and A-3
A cross section of 10 mm from the tip of the injection molded product (125 × 13 × 3.2 mm) was sliced and measured by micro FT-IR. Absorption (1780c) attributed to carbonic acid ester C = O stretching vibration of polycarbonate resin in surface layer
m ^-1 ) and the absorption ratio (2245 cm ^-1 ) attributed to the C≡N stretching vibration of the acrylonitrile-styrene resin were calculated by the following equation (1). The results are shown in FIG.

Formula (1) I _PC / I _AS = (absorption rate at 1780 cm ⁻¹ ) / (2
(Absorptance at 245 cm ^-1 ) In A-1, it can be seen that the concentration of the polycarbonate resin is high in the outer layer and the concentration of the acrylonitrile styrene resin is high in the inner layer. On the contrary, it can be seen that the concentration of acrylonitrile styrene resin in the outer layer and that of the polycarbonate resin in the inner layer are high in A-31.

Further, A-4, A-8, A-32, A-3
The cross section (slice surface) of the injection molded product of No. 3 was subjected to EDS analysis (energy dispersive X-ray
Elemental analysis revealed that the outer layer had a very high Si element concentration and the inner layer had a low concentration. (Both methylsilicone and methylphenylsilicone segregate on the surface of each copolymer, but differ in flame retardancy.) (Dispersion particle size of silicone on the surface of molded product) A component containing Si element by EDS analysis of the molded product surface Was measured. The results are shown in the table below.

[0271]

[Table 48]

[0272]

As described above, according to the present invention, when a molded article is produced, the outer layer of the molded article mainly composed of the component (A) and the inner layer of the molded article mainly composed of the component (B) are formed. Therefore, when the molded article is manufactured, the outer surface of the molded article is covered with the highly flame-retardant component (A), so that it is difficult to ignite and the structure has high flame retardancy. On the other hand, for the component (B), a material having low flame retardancy can be used.
The range of material selection can be widened, and cost reduction and the like can be achieved.

Further, even when the molded article is collected and used again for molding, the phase can be separated into the outer layer of the molded article and the inner layer of the molded article, so that the molded article having high flame retardancy even when used for recycling. Can be obtained.

[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.

FIG. 3 is a conceptual diagram of a cross section of the flame-retardant thermoplastic resin composition of the present invention and a molded product thereof.

──────────────────────────────────────────────────続 き 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 83/04 83/04 // B29K 55:02 B29K 55:02 67:00 67:00 69:00 69:00 83:00 83:00 (72) Inventor Shin Serizawa 5-7-1 Shiba, Minato-ku, Tokyo F-term in NEC Corporation (Reference) 4F071 AA22 AA22X AA34X AA43 AA50 AA67 AA76 AF47 AH07 AH12 AH17 BA01 BB05 BC01 4F206 AA13 AA24 AA28 AA33 AB05 AG03 AR17 JA07 JB22 JL02 JM04 JN12 4J002 BB12X BB15X BC03X BC05X BC06X BN15X BP01X CF03W CF06X CF07W CF07X CF18W CG00W CG01W CG02W CG03W CH09W CL03W CM04W CN01W CN03W CP03W FD13W GL00 GN00 GQ00

Claims (41)

[Claims] 1. A flame-retardant molding material containing a flame-retardant thermoplastic resin (A) and a thermoplastic resin (B), wherein the component (A) and the component (B) form a phase when molded. A flame-retardant molding material, wherein a molded article outer layer mainly composed of the component (A) and a molded article inner layer mainly composed of the component (B) are formed separately. 2. The flame-retardant molding material according to claim 1, wherein the oxygen index of the component (A) is at least 1.2 times the oxygen index of the component (B). 3. The method according to claim 1, wherein the component (A) contains a polycarbonate resin or a liquid crystal polyester.
Or the flame-retardant molding material according to 2. 4. The flame-retardant molding material according to claim 3, further comprising a silicone compound (a) having an aromatic residue. 5. The method according to claim 1, wherein the component (A) contains a copolymer obtained by copolymerizing the silicone compound (b) and the thermoplastic resin (a). Flammable molding materials. 6. The flame-retardant molding material according to claim 5, wherein the thermoplastic resin (a) is a polycarbonate resin or a liquid crystal polyester. 7. The flame-retardant molding material according to claim 5, wherein the thermoplastic resin (a) is a polystyrene resin. 8. The flame-retardant molding material according to claim 5, wherein the silicone compound (b) has an aromatic residue. 9. The flame-retardant molding material according to claim 1, wherein the component (B) is a polystyrene resin. 10. A flame-retardant molding material containing a flame-retardant thermoplastic resin (A) and a thermoplastic resin (B), characterized by satisfying the following formula (1). . η _a <η _b (1) (η _a represents the melt viscosity of component (A) at a shear rate of 300 sec ^-1 at the molding temperature, and η _b represents the melt viscosity of component (B) at a shear rate of 300 sec ^-1 at the molding temperature. Shows melt viscosity.) 11. The flame-retardant molding material according to claim 10, further satisfying the following expression (2). γ _a <γ _b (2) (γ _a indicates the surface tension of the component (A), and γ _b indicates the surface tension of the component (B).) 12. The flame-retardant molding material according to claim 10, wherein the oxygen index of the component (A) is at least 1.2 times the oxygen index of the component (B). 13. The flame-retardant molding material according to claim 10, wherein the component (A) contains a polycarbonate resin or a liquid crystal polyester. 14. The flame-retardant molding material according to claim 13, further comprising a silicone compound (a) having an aromatic residue. 15. The silicone compound (b) wherein the component (A) is a silicone compound (b)
The flame-retardant molding material according to any one of claims 10 to 14, comprising a copolymer obtained by copolymerizing a thermoplastic resin (a) with a thermoplastic resin (a). 16. The flame-retardant molding material according to claim 15, wherein the thermoplastic resin (a) is a polycarbonate resin or a liquid crystal polyester. 17. The flame-retardant molding material according to claim 15, wherein the thermoplastic resin (a) is a polystyrene resin. 18. The flame-retardant molding material according to claim 10, wherein the component (B) is a polystyrene resin. 19. A method for injection-molding a flame-retardant molding material containing a flame-retardant thermoplastic resin (A) and a thermoplastic resin (B), wherein the components (A) and (B) And b) separating the components from each other to form a molded article outer layer containing the component (A) as a main component and a molded article inner layer containing the component (B) as a main component. 20. The injection molding method according to claim 19, wherein the oxygen index of the component (A) is at least 1.2 times the oxygen index of the component (B). 21. The injection molding method according to claim 19, wherein the component (A) contains a polycarbonate resin or a liquid crystal polyester. 22. The injection molding method according to claim 21, wherein the flame-retardant molding material further contains a silicone compound (a) having an aromatic residue. 23. The composition according to claim 20, wherein the component (A) is a silicone compound (b).
The injection molding method according to any one of claims 19 to 22, comprising a copolymer obtained by copolymerizing a thermoplastic resin (a) with a thermoplastic resin (a). 24. The injection molding method according to claim 23, wherein the thermoplastic resin (a) is a polycarbonate resin or a liquid crystal polyester. 25. The injection molding method according to claim 23, wherein the thermoplastic resin (a) is a polystyrene resin. 26. The injection molding method according to claim 19, wherein the component (B) is a polystyrene resin. 27. A method for injection-molding a flame-retardant molding material containing a flame-retardant thermoplastic resin (A) and a thermoplastic resin (B), wherein the following formula (1) is satisfied. Injection molding method. η _a <η _b (1) (η _a indicates the melt viscosity of the component (A) at a shear rate of 300 sec ^-1 at the molding temperature, and η _b indicates the melt viscosity of the component (B) at a shear rate of 300 sec ^-1 at the molding temperature. Shows melt viscosity.) 28. The injection molding method according to claim 27, further satisfying the following expression (2). γ _a <γ _b (2) (γ _a indicates the surface tension of the component (A), and γ _b indicates the surface tension of the component (B).) 29. The injection molding method according to claim 27, wherein the oxygen index of the component (A) is at least 1.2 times the oxygen index of the component (B). 30. The injection molding method according to claim 27, wherein the component (A) contains a polycarbonate resin or a liquid crystal polyester. 31. The injection molding method according to claim 30, wherein the flame-retardant molding material further contains a silicone compound (a) having an aromatic residue. 32. The silicone compound (b) wherein the component (A) is a silicone compound (b)
The injection molding method according to any one of claims 27 to 31, comprising a copolymer obtained by copolymerizing a thermoplastic resin (a) with a thermoplastic resin (a). 33. The injection molding method according to claim 32, wherein the thermoplastic resin (a) is a polycarbonate resin or a liquid crystal polyester. 34. The injection molding method according to claim 32, wherein the thermoplastic resin (a) is a polystyrene resin. 35. The injection molding method according to claim 27, wherein the component (B) is a polystyrene resin. 36. A molded article obtained by the injection molding method according to claim 19. 37. A molded article having an outer layer of a molded article mainly composed of a flame-retardant thermoplastic resin (A) and an inner layer of a molded article mainly composed of a thermoplastic resin (B), wherein (A) A molded article characterized in that the oxygen index of the component is at least 1.2 times the oxygen index of the component (B). 38. A molded article having an outer layer of a molded article mainly composed of a flame-retardant thermoplastic resin (A) and an inner layer of a molded article mainly composed of a thermoplastic resin (B), wherein (A) The ingredients are
Polycarbonate resin, liquid crystal polyester, and
One or more resins selected from the group consisting of copolymers obtained by copolymerizing a silicone compound (b) and a thermoplastic resin (a), wherein the component (B) is a polystyrene resin. And molded products. 39. The molded article according to claim 38, wherein the thermoplastic resin (a) is a polycarbonate resin or a liquid crystal polyester. 40. The molded article according to claim 38, wherein the thermoplastic resin (a) is a polystyrene resin. 41. The molded article according to claim 37, wherein the flame-retardant thermoplastic resin (A) further contains a silicone compound (a) having an aromatic residue.