JP2002138204A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant resin composition that is inexpensive and has excellent flame retardancy. SOLUTION: This flame retardant resin composition comprises 100 pts.wt. resin and 0.1-50 pts.wt. organic silicone, wherein the organic silicone is synthesized from a silicate and an organosilane compound and has a unit represented by structural formula (1) and a unit represented by structural formula (2) and/or (3): (SiO4/2) (1), (RSiO3/2) (2), (R2SiO2/2) (3), (wherein R is a 1-16C modified alkyl group modified with a reactive group selected from the group consisting of an epoxy group, a hydroxyl group, a vinyl group, an acrylic group and a methacrylic group or a 1-10C monovalent hydrocarbon group, and R may be each independently the same or different).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition flame-retarded with an organically modified silicone.

[0002]

2. Description of the Related Art Flame-retardant resin compositions are used in various fields such as electric and electronic fields and building materials in order to ensure fire safety. These resin compositions generally used halogen-based compounds such as chlorine-based and bromine-based compounds as flame retardants.In recent years, however, interest in environmental issues, mainly in Europe, has increased, and halogens such as phosphorus-based flame retardants have been used. Various studies have been made on the use of a flame retardant that does not contain such a flame retardant.

[0003] However, when a flame retardant is produced by using a phosphoric ester compound, red phosphorus or the like as a phosphorus flame retardant, an odor is generated at the time of extrusion / molding, and the mechanical properties and thermal properties are adversely affected. Therefore, various flame retardants have been studied in place of halogen compounds and phosphorus compounds.

[0004] Silicone compounds are known as flame retardants containing no halogen or phosphorus. JP-A-54-3
No. 6365 discloses that a non-silicone polymer is RSiO
A resin composition flame-retarded with a silsesquioxane resin mainly composed of _3/2 units is disclosed in JP-A-58-5007.
No. 80, JP-A-4-226159, JP-A-7
In JP-A-33971 and JP-B-3-48947, a flame-retarding technique using MQ silicone composed of R ₃ SiO _1/2 units and SiO _4/2 units is disclosed. Japanese Patent Application Laid-Open No. Hei 10-139964 discloses that a non-silicone resin containing an aromatic ring is made of RSiO _3/2 units and R ₂
A resin composition flame-retarded with silicone having SiO _2/2 units is disclosed.

[0005] If the organic silicones are used in these conventional resin composition contains a Q unit (SiO _4/2), the organic silicones, silicon tetrahalides such as silicon tetrachloride; tetraethoxysilane , And tetramethoxysilane, and alkoxysilanes such as silicate stabilized by an alkoxyl group.

However, when the organosilicone is synthesized by a condensation reaction following the hydrolysis of silicon halides such as silicon tetrachloride, the conventional method is extremely difficult because the reaction rate is extremely fast and gels. Organized silicone having a burning effect cannot be obtained. Also, when synthesized by a condensation reaction following hydrolysis of alkoxysilanes such as tetraethoxysilane, tetramethoxysilane, and silicate stabilized by an alkoxyl group, the reaction control is easy, but the alkoxyl group remains. As a result, an organically modified silicone having an excellent flame retarding effect cannot be obtained.

[0007] In general, when the silicone obtained by the above-mentioned production method is used, it is necessary to add a large amount of the silicone because the flame retarding effect is insufficient. Further, since silicone flame retardants are relatively expensive, they have few merit of being used industrially in spite of the merit that they have a smaller burden on the global environment than halogen compounds and phosphorus compounds.

[0008]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a flame-retardant resin composition which is inexpensive and has excellent flame retardancy.

[0009]

Therefore, the present inventors have proposed S
As a result of conducting various studies on an organosilicone having a unit structure of iO _4/2 , the flame retardant effect is reduced when an alkoxyl group remains in the organosilicone, but the silicate and organosilane compound It has been found that the organosilicone having a specific structure synthesized according to the present invention exhibits excellent flame retardancy with a small amount of residual alkoxyl group, and has reached the present invention.

That is, the present invention is a flame-retardant resin composition containing 100 parts by weight of a resin and 0.1 to 50 parts by weight of an organically modified silicone, wherein the organically modified silicone is composed of a silicate and an organosilane compound. A flame-retardant resin composition which is synthesized and has a unit represented by the following structural formula (1) and a unit represented by the following structural formulas (2) and / or (3). (SiO _4/2 ) (1) (RSiO _3/2 ) (2) (R ₂ SiO _2/2 ) (3) (In each formula, R represents 1 carbon atom modified with a reactive group selected from the group consisting of an epoxy group, a hydroxyl group, a vinyl group, an acryl group and a methacryl group. Represents up to 16 modified alkyl groups or monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R may be the same or different.) Hereinafter, the present invention will be described in detail.

The organosilicon used in the present invention is synthesized from a silicate and an organosilane compound.
For these production methods, various known methods can be used. For example, sodium silicate is decomposed with hydrochloric acid in a water-insoluble organic solvent, and then organosilylated using trimethylchlorosilane. A method described in JP-B-49-40639; sodium silicate is neutralized by acid treatment in an aqueous solution. After obtaining siloxysilanol, it is added to a water-soluble organic solvent, and further reacted with an organosilylating agent.
No. 73; an acidic aqueous solution, a water-soluble organic solvent,
A method described in JP-B-60-34574 in which sodium silicate is gradually added to a mixed solution of an organosilylating agent; sodium silicate is added to a mixed solution of an acidic aqueous solution and a water-soluble organic solvent. After the addition, the method described in JP-A-8-151444, in which an organosilylating agent is added, can be used, and it can be obtained by adding and mixing an organosilane compound at an arbitrary stage of the reaction.

The silicate used in the production of the organically modified silicone used in the present invention is not particularly limited, and examples thereof include alkali metal silicates such as sodium silicate, potassium silicate, lithium silicate and the like; Kenyaite , Magadiite, Airerite, Macatite, Kanemite,
An aqueous solution of a crystalline layered silicate typified by δ-type sodium disilicate or the like is used. For example, as the sodium silicate, sodium silicate (sodium silicate) Na _{2 according to} JIS K1408 is used.
O · nSiO ₃ · xH water glass expressed as ₂ O (1
No.), water glass (No. 2), water glass (No. 3), sodium orthosilicate, sodium sesquisilicate, sodium metasilicate, powdered sodium silicate, and the like can be preferably used.

The organosilane compound used in the production of the organosilicone used in the present invention includes an organochlorosilane compound and an organoalkoxylsilane compound. From the viewpoint of reducing the residual amount of alkoxyl groups, the organochlorosilane compound is used. It is preferably used.

Examples of the organochlorosilane compound include monoorganotrichlorosilane, diorganodichlorosilane, and triorganomonochlorosilane.
It is not limited to these. Preferred organochlorosilane compounds include methyltrichlorosilane,
Ethyltrichlorosilane, phenyltrichlorosilane,
Examples include dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, phenylmethyldichlorosilane, trimethylchlorosilane, dimethylphenylchlorosilane, and vinyltrichlorosilane. These may be used alone or in combination of two or more.

The organoalkoxyl silane compound is not particularly restricted but includes, for example, methyl trialkoxyl silane, ethyl trialkoxyl silane, phenyl trialkoxyl silane, dimethyl dialkoxyl silane, diethyl dialkoxyl silane, diphenyl dialkoxyl silane, phenyl methyl dialkoxyl Examples include silane, trimethylalkoxyl silane, dimethylphenylalkoxyl silane, vinyl trialkoxyl silane, and the like. These may be used alone or in combination of two or more. Preferred alkoxyl groups have 1 to 1 carbon atoms
4 things.

The organically modified silicone used in the present invention comprises:
It is preferable that the silanol group contained is silylated with a silylating agent. If the silicone is isolated without silylation of the silanol group, a large number of silanol groups will remain in the obtained silicone, which may make the silicone less stable and difficult to handle. The silylation may be carried out by adding a silylating agent to the system to which the silicate and the organosilane compound have been added as it is, or may be carried out after isolating and purifying the silicone once.

The silylating agent is not particularly limited.
For example, hydrides such as trimethylsilane and triethylsilane
Rogen silane; trimethylchlorosilane, triethyl
Chlorosilane, triphenylchlorosilane, CF₃(C
H₂)₂Si (CH₃)₂Chlorosilanes such as Cl;
Silanols such as trimethylsilanol; trimethylmeth
Xysilane, trimethylethoxysilane; (CH₃)₃
SiNHCH₃, (CH ₃)₃SiNHC₂H₅, (C
H₃)₃SiN (CH₃)₂, (CH₃)₃SiN (C
₂H₅)₂, Such as aminosilane; (CH₃)₃SiOC
OCH₃And acyloxysilanes; hexamethyldisila
Zan, 1,3-divinyltetramethyldisilazane,
[(CH₃)₃Si]₃Silazane such as N;
It is. Among these, control of the reaction and removal of unreacted substances
Silazanes and chlorosilanes are preferred because of their ease.
No.

The structure of the organically modified silicone used in the present invention has a Q unit (SiO _4/2 ) and a T unit (RSiO _3/2 ) and / or a D unit (R ₂ SiO ₂ ).
_2/2 ) (in each formula, R is a modified alkyl group having 1 to 16 carbon atoms modified with a reactive group selected from the group consisting of an epoxy group, a hydroxyl group, a vinyl group, an acryl group and a methacryl group, or Represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R may be the same or different), but is preferably a substantially curable reaction by the silylation described above. A structure having no group is preferred.
This is because a flame-retarding effect and mechanical properties may be reduced, for example, a condensation reaction may occur during processing, resulting in gelation.

The organically modified silicone used in the present invention comprises:
80% by weight or more is soluble in methyl isobutyl ketone at 23 ° C., and the number average molecular weight is preferably 1000 or more, more preferably 85% by weight or more, and the number average molecular weight is 1500 or more. 2
If the composition contains an insoluble component exceeding 0% by weight or has a number average molecular weight of less than 1,000, the flame retarding effect and processability may be reduced. The number average molecular weight is a value measured by gel permeation chromatography and calculated in terms of styrene.

The organically modified silicone used in the present invention comprises:
From an economic viewpoint, it is preferable that 80 mol% or more of all the organic groups are phenyl groups and methyl groups, and more preferably 85 mol% or more. Here, the “organic group”
A monovalent group directly bonded to a silicon atom, and includes the above-mentioned modified alkyl group, the above-mentioned hydrocarbon group, and the alkoxyl group. Hydroxyl groups and halogeno groups are not included here.

Further, in controlling the phase structure for effectively exhibiting the effects of the present invention, the ratio of phenyl group: methyl group is 1: 4 to
The ratio is preferably 7: 3, more preferably 1: 3 to 3: 2. When the ratio of phenyl group: methyl group is less than 1: 4, the molding processability of the obtained flame-retardant resin composition may be remarkably reduced, or the appearance of the composition may be poor. On the other hand, if the ratio exceeds 7: 3, the heat resistance of the obtained flame-retardant resin composition may decrease, or the mechanical strength may decrease.

From the viewpoint of the effects of the present invention (flame retardancy) and the balance of physical properties (moldability and mechanical properties), the structure of the organically modified silicone used in the present invention is such that the alkoxyl group directly bonded to the Si atom is entirely organic. It is preferably at most 10 mol%, more preferably at most 8 mol%, based on the group. The proportion is more preferably at most 3 mol%, particularly preferably at most 1 mol%.

The structure of the organically modified silicone used in the present invention is represented by the general formula (1), which is a structural unit, from the viewpoint of the balance of physical properties (moldability, mechanical properties, flame retardancy, etc.) or
The total of the units represented by (1) and (2) is preferably at least 20 mol%, more preferably at least 25 mol%. The unit represented by the general formula (3) is 6
It is preferably at most 0 mol%, more preferably at most 50 mol%. If the content exceeds 60 mol%, the heat resistance, workability, and the like of the obtained flame-retardant resin composition may decrease.

In the structure of the organically modified silicone used in the present invention, as a constituent unit other than the general formulas (1), (2) and (3), a terminal reactive group such as a silanol group is sealed. The M unit (R ₃ SiO _1/2 ) can be used as long as the effects of the present invention are not impaired, and there is no particular limitation on the ratio, the organic substituent, and the like.

The organically modified silicone used in the present invention comprises:
Various compounds can be copolymerized or modified with various functional groups within a range that does not impair the purpose of the present invention, in order to increase the affinity with the resin or impart various characteristics.
The method for copolymerizing various compounds is not particularly limited, and examples thereof include a graft copolymer, a block copolymer, a random copolymer, and a copolymer having only a terminal substituted. The method of denaturation with various functional groups is not particularly limited, and examples thereof include a method of copolymerizing a functional group-containing compound, a method of synthesizing a flame retardant and then denaturing the compound by various chemical reactions.
The compound to be copolymerized is not particularly limited as long as the purpose of the present invention is not impaired. As an example of the compound to be copolymerized,
Epoxy group containing compound, vinyl group containing compound, hydroxyl group containing compound, carbonyl group containing compound, carboxyl group containing compound, alkoxyl group containing compound, phenyl group containing compound, amino group containing compound, amide group containing compound, imide group containing compound, mercapto Group-containing compounds, nitrile group-containing compounds, ether group-containing compounds, ester group-containing compounds, various polymer compounds, and the like. In particular, by copolymerizing a compound or a polymer having a substituent having a high affinity with the added resin, it becomes possible to maintain various properties of the obtained flame-retardant resin composition.

The organic silicone used in the present invention comprises:
One type may be used, or two or more types may be used in combination. 2
When used in combination of more than one kind, the combination is not limited. For example, those having different polymerization components and molar ratios,
Those having different molecular weights can be arbitrarily combined.

The shape of the organically modified silicone used in the present invention is not particularly limited, and for example, any shape such as oil, gum, varnish, powder, pellet and the like can be used.

The flame-retardant resin composition of the present invention comprises a resin 100
It contains 0.1 to 50 parts by weight of the organically modified silicone with respect to parts by weight, but if less than 0.1 part by weight, the effect of improving the flame retardancy may not be obtained, and more than 50 parts by weight. In this case, the surface properties and the formability tend to deteriorate. Preferably it is 0.3 to 45 parts by weight, more preferably 0.5 to 40 parts by weight.

The resin used in the present invention is not particularly limited, and various polymer compounds to which a flame retardant can be mixed can be used. The resin may be a thermoplastic resin or a thermosetting resin, and may be a synthetic resin or a resin that exists in nature.

Among the resins, polycarbonate resins,
Polyester resin, polyphenylene ether resin,
Aromatic vinyl resin, polyphenylene sulfide resin, N-aromatic substituted maleimide resin, polyimide resin, polyamide resin, and at least one selected from the group consisting of polymer alloys composed of at least two of these It is preferable to use one kind. These resins may be used alone or as an alloy with other various resins.

For the flame retardant resin composition of the present invention, a fluorine resin, a silicon-containing polymer other than the organically modified silicone used in the present invention, or the like can be used in order to further enhance the flame retardancy.

The fluororesin is a resin having a fluorine atom in the resin. Specifically, polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, and the like can be given. Also, if necessary, to the extent that the physical properties such as flame retardancy of the obtained molded article are not impaired, the monomer used for producing the fluororesin may be copolymerized with another copolymerizable monomer. The obtained copolymer may be used. These fluororesins are used alone or in combination of two or more.
The molecular weight of the fluororesin is preferably 1,000,000 to 20,000,000, more preferably 2,000,000 to 10,000,000.
Regarding the production method of these fluororesins, emulsion polymerization,
It can be obtained by a generally known method such as suspension polymerization, bulk polymerization, and solution polymerization.

The silicon-containing polymer other than the organically modified silicone used in the present invention includes diorganosiloxane compounds such as dimethylsiloxane and phenylmethylsiloxane, and copolymers obtained by polymerizing these compounds; polydimethylsiloxane, Examples include polyphenylmethylsiloxane, polysilane, polycarbosilane, polysilazane, silicon-boron copolymer, silicon-metal copolymer, and the like. A modified silicon polymer in which a part of the molecule is substituted by an epoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, an ether, or the like can also be used. Among them, a polymer having a number average molecular weight of 200 or more, more preferably a number average molecular weight in the range of 1,000 to 5,000,000 is preferable because flame retardancy can be further enhanced.
The shape is not particularly limited, and any shape such as oil, gum, varnish, powder, and pellet can be used. Among these, a silicon-boron copolymer is preferable because it has an effect of significantly increasing the flame retardant effect.

The amount of the fluorine-containing resin and the silicon-containing polymer is not limited as long as the properties (chemical resistance, heat resistance, etc.) of the present invention are not impaired.
The amount is preferably from 0.1 to 10 parts by weight, more preferably 0.0
3 to 8 parts by weight, particularly preferably 0.05 to 6 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving the flame retardancy will be small, and if it exceeds 10 parts by weight, the moldability may be reduced.

In order to make the flame-retardant resin composition of the present invention higher in performance, one or more heat stabilizers such as a phenol stabilizer, a thioether stabilizer and a phosphorus stabilizer are used. It is preferable to use them together. Further, if necessary, usually well-known lubricants, release agents, plasticizers, flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes,
Additives such as an antistatic agent, a conductivity-imparting agent, a dispersant, a compatibilizer, and an antibacterial agent can be used alone or in combination of two or more. However, the use of such additives that promote the decomposition and reaction of the organically modified silicone decreases the flame retardancy of the obtained composition, and thus it is not preferable to use such additives.

Further, the flame-retardant resin composition of the present invention may be used as a reinforcing material by combining a reinforcing filler within a range that does not impair the characteristics (flame retardancy and the like) of the present invention. That is, heat resistance, mechanical strength, etc. can be further improved by adding a reinforcing filler. Such a reinforcing filler is not particularly limited, and examples thereof include fibrous fillers such as glass fiber, carbon fiber, and potassium titanate fiber; glass beads, glass flakes; talc, mica, kaolin,
Silicate compounds such as wollastonite, smectite, and diatomaceous earth; and calcium carbonate, calcium sulfate, barium sulfate, and the like. Of these, silicate compounds and fibrous fillers are preferred.

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

The method for molding the flame-retardant resin composition of the present invention is not particularly limited.
For example, injection molding, blow molding, extrusion molding, vacuum molding,
Press molding, calender molding, foam molding and the like can be used.

The flame-retardant resin composition of the present invention can be suitably used for various uses. Preferred uses include injection molded products such as home appliances, OA equipment parts, automobile parts,
Blow molded articles, extruded molded articles, foam molded articles and the like can be mentioned.

[0040]

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

[0041](Reference Example 1) Organized silicone (A-1)  80 g of diphenyldichlorosilane and tetrahydrofuran
1250 g was placed in a flask and cooled to 0 ° C. This mix
While stirring the mixed solvent vigorously, the SiO₂Of 29.2%
No.3 water glass 260g (made by Nippon Chemical Co., Ltd.)
Diphenyldichlorosilane diluted 5 times with water
200 g, in a mixed solvent in two separate dropping funnels
At the same time over 2 hours. Acetone 80 after dropping
After adding 0 g, the mixture was heated to 40 ° C. and stirred for 2 hours.
Add 200 g of trimethylchlorosilane to the mixture for about 10 minutes.
And dropped. Thereafter, the mixture is stirred at 60 ° C. for 2 hours and at room temperature.
Stirred for 24 hours. After that, 2500 g of pure water and methyl iso
After adding 1250 g of butyl ketone and stirring, the mixture was allowed to stand still and water was added.
The phases were separated from the organic phase and the aqueous phase was removed. This operation is
Was repeated until neutral. With anhydrous sodium sulfate
The organic phase is dehydrated and dried, and after filtration, using an evaporator
The solvent was removed at 180 ° C under reduced pressure to obtain a colorless viscous solid silica.
400 g of corn was obtained. XL-30 made by Varian
As a result of measuring the NMR spectrum using the
Position: D unit: M unit = 40: 36: 24, phenyl group:
Methyl group = 50:50, remaining in all organic substituents
The ratio of the alkoxyl group was 0% in molar ratio. Also,
100% by weight based on methyl isobutyl ketone at 23 ° C
Is soluble and gel permeation chromatography (GPC,
Waters 510, UV detector)
The number average molecular weight in terms of styrene was 1,700.

[0042](Reference Example 2) Organized silicone (A-2)  45 g of phenyltrichlorosilane and tetrahydrofuran
400 g were placed in a flask and cooled to 0 ° C. This mix
While stirring the mixed solvent vigorously, the SiO₂Of 29.2%
No. 3 water glass 142g (Nippon Chemical Co., Ltd.)
Diluted 3 times with water, phenyltrichlorosilane
100 g in a mixed solvent in separate dropping funnels
At the same time over 1 hour. After dropping acetone 50
After adding 0 g, the mixture was heated to 40 ° C. and stirred for 3 hours.
After cooling the mixture to 0 ° C., trimethylchlorosilane 1
00g was added dropwise over about 10 minutes.
While stirring. Thereafter, 1500 g of pure water, methyl isobutyl
Add 800 g of ketone, stir, and allow to stand still
The phases were separated and the aqueous phase was removed. This operation is performed when the aqueous phase is neutral.
Repeated until: Organic phase with anhydrous sodium sulfate
After dehydration and drying, filtration and use of an evaporator under reduced pressure
The solvent was removed at 80 ° C., and the colorless solid silicone 150 was removed.
g was obtained. Using a Varian XL-300 device
As a result of measuring the NMR spectrum, Q unit: T unit: M
Unit = 43: 43: 14, phenyl group: methyl group = 3
0:70, alkoxyl remaining in all organic substituents
The ratio of the groups was 0% by molar ratio. Also, at 23 ° C
100% by weight soluble in isobutyl ketone
Gel permeation chromatography (GPC, Warte
styrene conversion measured by rs510, UV detector)
The calculated number average molecular weight was 2,100.

[0043](Reference Example 3) Organized silicone (B-1)  Dimethoxydiphenylsilane (244 g) and tetraeth
0.2 N HCl in a mixture of xysilane (208 g)
(1.1 g), water (86 g), methyl isobutyl ketone
Ton (500 g) was added and the mixture was stirred at 60 ° C. for 6 hours. reaction
After returning the mixture to room temperature, chlorotrimethylsilane (2
16 g) was added and reacted at 60 ° C. for 2 hours. Then water
(1000 g), washed with anhydrous sodium sulfate
The organic phase was dehydrated and dried with and filtered. Evaporator
The solvent was removed at 180 ° C using a colorless solid silicone
200 g was obtained. XL-300 equipment made by Varian
The NMR spectrum was measured using a unit, and the Q unit: D
Unit: M unit = 39: 39: 22, phenyl group: methyl
Group = 54: 46, Alcohol remaining in all organic substituents
The proportion of xyl groups was 18% in molar ratio. Also, 23
100% by weight based on methyl isobutyl ketone at ℃
And gel permeation chromatography (GPC, Wa
rts510, UV detector)
The number average molecular weight in terms of len was 2,500.

[0044](Example 1)  Bisphenol A type polymer with a viscosity average molecular weight of about 22,000
100 parts by weight of a carbonate resin (PC) in Reference Example 1
10 parts by weight of the organically produced silicone (A-1),
In addition, as phosphorus-based and phenol-based stabilizers
Castab HP-10 and AO-60 (both manufactured by Asahi Denka)
0.1% by weight of each was dry-blended in advance
After that, a vented cylinder with the cylinder temperature set to 270 ° C
E of a screw extruder [TEX44 (trade name): manufactured by Nippon Steel Works]
The resin composition is supplied to the
Obtained.

[0045]Preparation of test specimen  After drying the obtained pellets at 120 ° C. for 5 hours,
Using a 35t injection molding machine, cylinder temperature 270 ° C, gold
1.6mm, 2.2mm thickness bar at mold temperature 50 ℃
(Width 12mm, length 127mm)
Was done. Table 1 shows the results.Evaluation method  Flame retardancy: 1.6 mm thick according to UL-94 standard;
The flame resistance of the 2 mm bar was evaluated by the V test. Fire extinguishing
The case where there was no data was expressed as "non-standard".

[0046]Example 2 and Comparative Examples 1-4  Change the amount of organically modified silicone to the number of parts shown in Table 1.
Except for the above, a resin composition was obtained in the same manner as in Example 1. This
From the pellets obtained in this manner, test specimens
It was created. The above evaluation method was performed on these test pieces.
Was. Table 1 shows the evaluation results. (A-2) Organized silicone obtained in Reference Example 2 (B-1) Organized silicone obtained in Reference Example 3 (B-2) Phenylmethylsilicone (KF-53:
Ogaku Chemical Industry Co., Ltd.)

[0047]

[Table 1]

As shown in Table 1, while the Examples show excellent flame retardancy, Comparative Example 1 is inferior in flame retardancy because no flame retardant is used. In Comparative Examples 2 and 3, since a silicone polymer different from the present invention was used as a flame retardant,
Poor flame retardancy. Further, in Comparative Example 4, since the amount of the flame retardant added was outside the range of the present invention, molding was difficult.

[0049]Examples 3 to 7 and Comparative Examples 5 to 9  The following materials were used as the resin, and the ratio of the resin was as shown in Table 2.
And the same as Example 1 except that the organic silicone was blended.
To obtain a resin composition.・ PET: polyethylene terephthalate with logarithmic viscosity 0.70
PBT: Polybutylene terephthalate with logarithmic viscosity 1.20
Rate resin • PPE: poly (2,6-dimethyl) having a logarithmic viscosity of 0.50
H-1,4-butadiene / styrene copolymer resin
(Trade name of Nippon Steel Chemical Co., Ltd.) Estyrene HI H-
53 ・ ABS: Acrylonitrile, butadiene and styrene
Polymerized resin (Kanebuchi Chemical Industry Co., Ltd.)
MUH E-1300

[0050]

[Table 2]

As shown in Table 2, it can be seen that all of the flame-retardant resin compositions of the present invention have excellent flame retardancy.

[0052]

Since the flame-retardant resin composition of the present invention has the above-mentioned constitution, it is relatively inexpensive, has excellent flame retardancy, and is industrially very useful.

Continued on the front page F term (reference) 4H028 AA42 AA44 AA49 BA03 BA06 4J002 BC001 BH021 CF001 CG001 CH071 CL001 CM041 CN011 CP032 CP052 CP062 CP122 CP162 FA010 FA040 FD010 FD060 GM00 GQ00 4J035 AA03 CA01N CA11NCA CA13

Claims (6)

[Claims] 1. A flame-retardant resin composition containing 100 parts by weight of a resin and 0.1 to 50 parts by weight of an organically modified silicone, wherein the organically modified silicone is synthesized from a silicate and an organosilane compound, A flame-retardant resin composition comprising a unit represented by the following structural formula (1) and a unit represented by the following structural formulas (2) and / or (3). (SiO _4/2 ) (1) (RSiO _3/2 ) (2) (R ₂ SiO _2/2 ) (3) (In each formula, R represents 1 carbon atom modified with a reactive group selected from the group consisting of an epoxy group, a hydroxyl group, a vinyl group, an acryl group and a methacryl group. Represents up to 16 modified alkyl groups or monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R may be the same or different.) 2. The organically modified silicone is soluble in methyl isobutyl ketone in an amount of 80% by weight or more at 23 ° C.,
The flame-retardant resin composition according to claim 1, which has a number average molecular weight of 1,000 or more. 3. Among all organic groups of the organically modified silicone, 8
2. The method according to claim 1, wherein 0 mol% or more is a methyl group or a phenyl group.
Or the flame-retardant resin composition according to 2. 4. A phenyl group: methyl group molar ratio of 1: 4.
The flame-retardant resin composition according to claim 3, wherein the ratio is 7 to 3: 7. 5. The organically modified silicone according to claim 1, wherein the alkoxyl group directly bonded to the Si atom has a molar ratio of not more than 10 mol% based on all organic groups.
The flame-retardant resin composition according to the above. 6. The resin is a polycarbonate resin, a polyester resin, a polyphenylene ether resin, an aromatic vinyl resin, a polyphenylene sulfide resin, N
The flame-retardant resin composition according to claim 1, which is at least one selected from the group consisting of an aromatic substituted maleimide resin, a polyamide resin and a polyimide resin.