JP2001311081A - Flame retardant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new flame retardant substantially free from atoms of a halogen, phosphorus, nitrogen or the like, capable of exhibiting extremely high flame-retardant effects, and capable of being obtained by using an inexpensive raw material, and further to provide a flame-retarded resin composition made flame-retardant by using the flame retardant. SOLUTION: This flame retardant comprises an organopolysiloxane compound having a structure consisting of RSiO3/2 unit (wherein, R is an organic group capable of bonding to Si) and SiO4/2 unit, regulated so that the molar ratio of R/Si in the RSiO3/2 unit and the SiO4/2 unit may be within the range of 0.2-0.95, and 1,000-200,000 number average molecular weight. The flame-retardant resin composition contains 0.1-50 pts.wt. flame retardant based on 100 pts. wt. resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a halogen, phosphorus,
A new flame retardant that does not contain atoms such as nitrogen and exhibits high flame retardancy, and by using this flame retardant, it is highly flame retarded without using compounds such as bromine, chlorine and phosphorus. And a flame-retardant resin composition.

[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 flame retardation is carried out using a phosphorus-based flame retardant such as a phosphoric ester compound or red phosphorus, an odor is generated at the time of extrusion / molding and adversely affects mechanical and thermal properties. For this reason, various types of flame retardants have been studied instead of halogen compounds and phosphorus compounds.

[0004] Silicone compounds are known as flame retardants containing no halogen or phosphorus. JP-A-54-3
In 6365, the non-silicone polymer is converted to RSiO _3/2
A resin composition flame-retarded with a unit-based silsesquioxane resin is disclosed. JP-A-10-139964 discloses that a non-silicone resin containing an aromatic ring is made of RSiO
A resin composition flame-retarded with a silicone resin having _3/2 units and R ₂ SiO _2/2 units is disclosed. However, in the silsesquioxane resin disclosed in JP-A-54-36365, it is necessary to add a large amount of an expensive silsesquioxane resin for flame retardation.
Not realistic. In addition, the silicone resin disclosed in JP-A-10-139964 is effective for polycarbonate, but has a small flame-retardant effect on other resins, so that it cannot be sufficiently flame-retarded. was there.

[0005]

DISCLOSURE OF THE INVENTION In view of the above situation, the present invention does not substantially contain atoms such as halogens, phosphorus, and nitrogen, and exhibits an extremely high flame-retardant effect on various resins. An object of the present invention is to provide a flame retardant and a flame-retardant resin composition flame-retarded using the same.

[0006]

Accordingly, the present inventors have conducted various studies on silicone compounds having various structures, and as a result, by strictly controlling the molecular structure of the silicone compound used as a flame retardant, The inventors succeeded in synthesizing a silicone compound having a high flame retardant effect with a small amount of addition, and completed the present invention.

That is, the present invention relates to RSiO _3/2 units (wherein R represents an organic group capable of bonding to Si) and S
having a structure consisting of iO _4/2 units,
R / S in _3/2 units and the SiO _4/2 units
A flame retardant comprising an organopolysiloxane compound having a molar ratio of i in the range of 0.2 to 0.95 and a number average molecular weight in the range of 1,000 to 200,000.

[0008] The present invention also relates to an RSiO _3/2 unit (wherein R represents an organic group capable of bonding to Si);
_4/2 units and R ' ₃ SiO _1/2 units (wherein R'
Has a structure selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and an aromatic group having 6 to 24 carbon atoms, which may be the same or different), and the RSiO _3/2
A flame retardant comprising an organopolysiloxane compound having a molar ratio of R / Si in the unit and the SiO _4/2 unit in the range of 0.2 to 0.95 and the number average molecular weight in the range of 1,000 to 200,000. is there. Further, in the present invention, the flame retardant is added in an amount of 0.1 to 100 parts by weight of the resin.
An object of the present invention is to provide a flame-retardant resin composition containing 1 to 50 parts by weight. Hereinafter, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The organopolysiloxane compound of the present invention comprises RSiO _3/2 units (where R is Si
Has a structure comprising a bondable an organic group) and _{SiO 4/2} units in a molar ratio of R / Si in the _{RSiO 3/2} units and the _{SiO 4/2} units 0.2
0.95 and the number average molecular weight is 1000
From 200,000 to 200,000. That is,
In order to improve the flame retardant effect of the organopolysiloxane, it is first important to improve the heat resistance of the organopolysiloxane compound itself, and the decomposition temperature is preferably close to the decomposition temperature of the resin. Methods for improving the heat resistance of the organopolysiloxane include a method of increasing the degree of siloxane crosslinking, increasing the molecular weight, and selecting an organic group bonded to a Si atom. To increase the degree of siloxane crosslinking, it is necessary to introduce a large amount of RSiO _3/2 units (where R represents an organic group capable of bonding to Si) and / or SiO _4/2 units into the main chain of the organopolysiloxane. Can be achieved by However, SiO
_{If 4/2} units are excessively large, the silica-like properties become strong and the flame retardancy tends to be poor.

Further, in order to exhibit good flame retardancy and resin properties, it is necessary to improve the dispersibility of the organopolysiloxane in the resin. To this end, compatibility and dispersibility can be improved by appropriately selecting an organic group on Si of the organopolysiloxane according to the target resin.
The organic group R capable of bonding to Si in the RSiO _3/2 unit is not particularly limited and includes, for example, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms; an epoxy group, a hydroxyl group, a vinyl group,
An alkyl group having 1 to 16 carbon atoms modified with a functional group selected from an acryl group and a methacryl group;
And the like. Examples of the aromatic group include a phenyl group, a cresyl group, a xylenyl group, a naphthyl group, and an anthracenyl group. Further, it may be an aromatic group substituted with a halogen atom. As the organic group R, only one kind may be contained, or two or more kinds may be contained.

Among them, when heat resistance and flame retardancy are considered, an aliphatic hydrocarbon group having 1 to 6 carbon atoms and a C 6
~ 12 aromatic groups are preferred. As the aliphatic hydrocarbon group, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. In order to improve the flame retardancy and the dispersibility in the resin, R is particularly preferably an aromatic group having 6 to 12 carbon atoms, and particularly preferably a phenyl group.

In order to achieve a good balance between the amount of organic groups in the RSiO _3/2 unit and the properties of the organopolysiloxane compound, and a good flame-retardant effect, the R group in the RSiO _3/2 unit and the SiO _4/2 unit is preferably used. The molar ratio of / Si is in the range of 0.2 to 0.95. Preferably 0.2 to
0.8, more preferably 0.25-0.8, even more preferably 0.3-0.7, most preferably 0.35-0.0.
It is in the range of 65. When the molar ratio of R / Si is smaller than 0.2 or larger than 0.95, both have insufficient flame retardancy.

Such an organopolysiloxane can be easily synthesized by an existing silicone synthesis method. That, RSiX 3 _(wherein, R, .X represents the same groups as above are the same or different, halogen, hydroxyl, or a dehydration condensate of hydroxyl group) at least one silicon compound represented by the And at least one silicon compound selected from the group consisting of silicon tetrachloride, tetraalkoxysilane, water glass, and metal silicate. The charging ratio of both compounds is determined according to the desired unit ratio in the organopolysiloxane. Known reaction conditions can be applied depending on the compound used. It is also a feature of the present invention that the above-mentioned inexpensive silicone raw materials can be used as SiO _4/2 units.

When the organopolysiloxane compound contains a reactive silicon group in which an alkoxy group, a hydroxy group, or the like is bonded to a silicon atom, the flame retardancy tends to decrease. Therefore, the organopolysiloxane compound is
Those containing no such reactive silicon group are preferred.

In order to eliminate reactive silicon groups from an organopolysiloxane compound containing reactive silicon groups, R ' ₃ S
What is necessary is just to block a reactive silicon group by iO _1/2 unit. That is, the organopolysiloxane compound preferably further has R ′ ₃ SiO _1/2 units. Therefore, preferred organopolysiloxane compounds in the present invention include RSiO _3/2 units (where R represents an organic group capable of bonding to Si), SiO _4/2 units, and R ′ ₃ S
iO _1/2 unit (wherein, R 'is selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and an aromatic group having 6 to 24 carbon atoms, and may be the same or different) The RSiO _3/2 unit and the SiO
The molar ratio of R / Si in _4/2 units is 0.2 to 0.9.
5 and a number average molecular weight of 1,000 to 2
It is in the range of 00000. The organic group R ′ on the terminal Si atom (in R ′ ₃ SiO _1/2 unit) is an alkyl group having 1 to 4 carbon atoms or an aromatic group having 6 to 24 carbon atoms. The aromatic group is the same as described above. As the organic group R ', only one kind may be contained, or two or more kinds may be contained. R 'is preferably a methyl group, an ethyl group, or an aromatic group having 6 to 12 carbon atoms in order to sufficiently exhibit the flame retardant effect. Of these, a methyl group is particularly preferred.

Such an organopolysiloxane compound is selected from the group consisting of at least one silicon compound represented by RSix ₃ as described above, silicon tetrachloride, tetraalkoxysilane, water glass and metal silicate. After a condensation reaction with at least one silicon compound to obtain an organopolysiloxane containing a reactive silicon group, an excess amount of R ′ ₃ SiX (where R ′ is
Represents the same group as described above. X is the same or different and is a halogen, a hydroxyl group or a dehydration condensate of a hydroxyl group), and can be synthesized by subjecting at least one silicon compound to a condensation reaction.

The organic group in the organopolysiloxane compound preferably comprises substantially both a methyl group and an aromatic group. In addition, “substantially” means 8 out of all organic groups.
It means that the above group accounts for 0 mol% or more, preferably 90 mol% or more. In this case, the molar ratio of methyl group / aromatic group is preferably in the range of 0.01 to 9, and 0.0
5-9 are more preferable, and the range of 0.1-8 is still more preferable. When the molar ratio of methyl group / aromatic group is less than 0.01, flame retardancy and compatibility in resin may be inferior,
When the molar ratio of methyl group / aromatic group is more than 9, flame retardancy may not be sufficient. The RSiO _3/2 unit may have both a methyl group and an aromatic group, may have only a methyl group, or may have only an aromatic group. Further, the R ′ ₃ SiO _1/2 unit may have both a methyl group and an aromatic group, may have only a methyl group, or may have only an aromatic group. Is also good. From the viewpoint of ease of synthesis and flame retardancy, R ' ₃ Si
It is preferred that O _1/2 units have a methyl group and RSiO _3/2 units have a phenyl group.

Further, the number average molecular weight of the organopolysiloxane compound is in the range of 1,000 to 200,000. It is preferably 1500 to 150000000, and 20
The range of 00 to 100000 is more preferable. When the number average molecular weight is less than 1000, the heat resistance of the organopolysiloxane is low and the flame retardancy is insufficient. When the number average molecular weight is more than 200000, there is a problem that the dispersibility in a resin and the processability are inferior. In addition,
The molecular weight of the organopolysiloxane compound can be easily determined by controlling the conditions of the synthesis reaction.

The organopolysiloxane of the present invention can be used to increase the affinity with a resin or to impart various properties, by copolymerizing various compounds within the range not impairing the purpose of the present invention, or by using various functional groups. Can be metamorphosed. 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. Examples of the compound to be copolymerized include an epoxy group-containing compound, a vinyl group-containing compound, a hydroxyl group-containing compound, a carbonyl group-containing compound, a carboxyl group-containing compound, an alkoxyl group-containing compound, a phenyl group-containing compound, an amino group-containing compound, and an amide group-containing compound. Examples include compounds, imide group-containing compounds, 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 resin to be added, it is possible to maintain various properties of the obtained flame-retardant resin composition.

The shape when the flame retardant of the present invention is used is not particularly limited, and may be any shape such as oil, gum, varnish, powder, and pellet. When the flame retardant of the present invention is used, only one type of organopolysiloxane compound may be used alone, or two or more types may be used in combination. The combination of two or more types is not particularly limited, and those having different polymerization components and molar ratios, those having different molecular weights, and the like can be used in any combination. Further, it does not exclude that other additives are added to the flame retardant of the present invention within a range not to impair the purpose of the present invention.

The desired purpose can be achieved by adding 0.1 to 50 parts by weight of the flame retardant of the present invention to 100 parts by weight of the resin. If the amount is less than 0.1 part by weight, the effect of improving the flame retardancy may not be obtained, and if the amount exceeds 50 parts by weight, the surface properties, moldability and the like tend to deteriorate. Preferably it is 0.3 to 30 parts by weight, more preferably 0.1 to 30 parts by weight.
5 to 20 parts by weight. Therefore, even when used in an extremely small amount of 10 parts by weight or less, the effect of flame retardancy can be exhibited. In addition, by using the flame retardant of the present invention in combination with various other known flame retardants, a higher degree of flame retardancy can be obtained. It is possible to obtain a flame-retardant composition with the addition amount of. When the flame retardant of the present invention has another additive component, the compounding amount of the organopolysiloxane compound may be in the above-mentioned range.

The resin used in the flame-retardant resin composition of 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. By combining the flame retardant of the present invention with other known various flame retardants, high flame retardancy can be exhibited.

Among resins, it is preferable to use an aromatic resin as the resin because it is easy to make the resin flame-retardant using the present invention. The aromatic resin indicates a resin having at least one aromatic ring in a molecule.

Among the aromatic resins, aromatic polycarbonate resins, aromatic polyester resins, polyphenylene ether resins, aromatic vinyl resins, polyphenylene sulfide resins, N-aromatic substituted maleimide resins, and polyimide resins And at least one selected from the group consisting of polymer alloys composed of at least two of these. 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 organopolysiloxane compound used in the present invention, or the like can be used in order to further enhance the flame retardancy. .

The fluorinated resin 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. The method for producing these fluororesins can be obtained by a generally known method such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization.

The silicon-containing polymer other than the organopolysiloxane compound used in the present invention includes a diorganosiloxane compound such as dimethylsiloxane and phenylmethylsiloxane, and a triorganosiloxane compound such as trimethylsilhemioxane and triphenylsilhemioxane. Organosyl hemioxane compounds, and copolymers obtained by polymerizing them, polydimethylsiloxane, polyphenylmethylsiloxane, polysilane, polycarbosilane, polysilazane, silicon-boron copolymer, silicon-metal copolymer, And the like.
Part of the molecule is epoxy group, hydroxyl group, carboxyl group,
A modified silicon polymer substituted by 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 of the silicone is not particularly limited, and any shape such as an oil, a gum, a varnish, a powder, and a pellet can be used. Among these, a silicon-boron copolymer is preferable because it has the 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.
It is preferably from 0.1 to 10 parts by weight, more preferably from 0.0 to 10 parts by weight.
3 to 8 parts by weight, particularly preferably 0.05 to 6 parts by weight. If the addition amount is less than 0.01, the effect of improving the flame retardancy becomes small, and if it exceeds 10 parts by weight, the moldability and the like may be reduced.

In order to make the flame-retardant resin composition of the present invention higher in performance, one or two kinds of heat stabilizers such as a phenol stabilizer, a thioether stabilizer and a phosphorus stabilizer are used.
It is preferable to use more than one kind in combination. Further, if necessary, usually well-known, lubricant, release agent, plasticizer, flame retardant, flame retardant auxiliary, ultraviolet absorber, light stabilizer, pigment, dye, antistatic agent, conductivity imparting agent, Additives such as dispersants, compatibilizers, and antibacterial agents can be used alone or in combination of two or more. However, the use of such additives that promote the decomposition or reaction of the organopolysiloxane compound reduces the flame retardancy of the resulting 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 molding method of 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.

[0034]

The present invention will be described in more detail with reference to the following examples.
As will be described, the present invention is limited to only these examples.
is not. In the following, unless otherwise specified, "parts"
Means parts by weight, and "%" means% by weight.Example 1 Production of flame retardant for resin addition (S-1)  Trimethoxyphenylsilane (159g, 0.8mo
l) and tetraethoxysilane (167 g, 0.8 mol)
l) water containing 0.2N HCl (1.1 g) in the mixture of 1)
(86 g, 4.8 mol) and stirred at 60 ° C. for 3 hours.
Was. After allowing the reaction mixture to come to room temperature,
Add run (87g, 0.8mol) and 2 hours at 60 degrees
Reacted. Then, toluene was added and washed several times with water.
After that, the solvent, alcohol and water
An organopolysiloxane was obtained. The molecular weight of the product is GP
As a result of C analysis, Mn = 2583, Mw = 3355 (poly
(Styrene conversion, RI detection). Analysis by NMR
As a result, Ph-Si-O_3/2Join
Is 36 mol%, Si-O_4/234 mol% bonding, Me
₃-Si-O_1/2The bond is 29 mol% and Me / P
h ratio = 2.4.

[0035]Preparation of resin composition  Bisphenol A type polymer with a viscosity average molecular weight of about 22,000
100 parts by weight of carbonate resin (A-1), manufactured on
3 parts by weight of the flame retardant for resin addition (S-1), and phosphorus
Adekastab as a phenolic and phenolic stabilizer
HP-10 and AO-60 (both manufactured by Asahi Denka)
Name) 0.1 part by weight of each, tetrafluoroethylene
Reflon FA-500 (trade name, manufactured by Daikin Industries) 0.2
Parts by weight, after dry blending, cylinder temperature
Twin-screw extruder [TEX4
4 (trade name: manufactured by Japan Steel Works, Ltd.)
By extruding, a resin composition was obtained.

[0036]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
0.9mm thickness, 1.6mm, 3.2 at mold temperature of 50 ° C
mm bar (width 12mm, length 127mm)
The following evaluation was performed. Table 1 shows the results.

[0037]Evaluation method  -Flame retardancy: 0.9 mm thick according to UL-94 standard
The flame retardancy of 1.6 mm bars was evaluated in the V test. In addition,
The case where the fire did not occur was indicated as "measurable". -Impact resistance: 3.2 in thickness according to ASTM D-256
Evaluated by 23 ° C notched Izod impact test for mm bar
did.・ Molded product appearance: The transparency, surface properties, etc. of the obtained test specimens
It was evaluated visually.

[0038]Examples 2 to 4 and Comparative Examples 1 to 3  Except that the amount of flame retardant added was changed to the number shown in Table 1,
A resin composition was obtained in the same manner as in Example 1. Thus obtained
Each test piece was prepared from the pellets in the same manner as above.
The above evaluation method was performed on these test pieces. Evaluation results
It is shown in Table 1. However, S used in Examples 4, 5 and 6
-2, S-3 and S-4, and used in Comparative Examples 2, 3 and 4
The obtained Si-1, Si-2 and Si-3 are as follows.
Was used.

[0039]Production of flame retardant for resin addition (S-2)  Trimethoxyphenylsilane (159g, 0.8mo
l) and tetraethoxysilane (250 g, 1.2 mol)
l) water containing 0.2N HCl (1.1 g) in the mixture of 1)
(110 g, 6.1 mol) and stirred at 60 ° C. for 3 hours.
did. After returning the reaction mixture to room temperature, chlorotrimethyl
Add silane (109g, 1mol), 60 degrees for 2 hours
Reacted. Then, toluene was added and washed several times with water.
After that, the solvent, alcohol and water
An organopolysiloxane was obtained. The molecular weight of the product is GP
As a result of C analysis, Mn = 4230, Mw = 5820 (poly
(Styrene conversion, RI detection). Analysis by NMR
As a result, Ph-Si-O_3/2Join
Is 31 mol%, Si-O_4/248 mol% bonding, Me
₃-Si-O_1/2The bond is 21 mol% and Me / P
h ratio = 2.0.

[0040]Production of flame retardant for resin addition (S-3)  Trimethoxyphenylsilane (238 g, 1.2 mo
l) and tetraethoxysilane (125 g, 0.6 mol
l) water containing 0.2N HCl (1.1 g) in the mixture of 1)
(92 g, 5.1 mol) and stirred at 60 ° C. for 3 hours.
Was. After allowing the reaction mixture to come to room temperature,
Add run (109 g, 1 mol) and react at 60 ° C for 2 hours.
I responded. Then, toluene was added and washed several times with water.
After that, the solvent, alcohol and water
An organopolysiloxane was obtained. The molecular weight of the product is GP
As a result of C analysis, Mn = 3028, Mw = 4407 (poly
(Styrene conversion, RI detection). Analysis by NMR
As a result, Ph-Si-O_3/2Join
Is 46 mol%, Si-O_4/223 mol% bonding, Me
₃-Si-O_1/2The bond is 31 mol% and Me / P
h ratio = 2.1.

[0041]Production of flame retardant for resin addition (S-4)  Trimethoxyphenylsilane (159g, 0.8mo
l), methyltrimethoxysilane (54 g, 0.4 mol
l) and tetraethoxysilane (125 g, 0.6 mol
l) water containing 0.2N HCl (1.1 g) in the mixture of 1)
(92 g, 5.1 mol) and stirred at 60 ° C. for 3 hours.
Was. After allowing the reaction mixture to come to room temperature,
Add run (109 g, 1 mol) and react at 60 ° C for 2 hours.
I responded. Then, toluene was added and washed several times with water.
After that, the solvent, alcohol and water
An organopolysiloxane was obtained. The molecular weight of the product is GP
As a result of C analysis, Mn = 2622, Mw = 3645 (poly
(Styrene conversion, RI detection). Analysis by NMR
As a result, among all the silicon atoms, Si—O_3/247 binding
Mol%, Si-O_4/225 mol% bonding, Me₃-S
i-O_1/2The bond is 28 mol% and the Me / Ph ratio =
2.9.

[0042]Production of silicone compound (Si-1)  Phenyltriethyl in methyl isobutyl ketone solution (1 L)
Dissolve chlorosilane (342.7 g, 1.62 mol)
Then, 250 ml of pure water was added dropwise under ice cooling, and then refluxed for 5 hours.
The following reaction was performed. Then, trimethylchlorosilane (1
76 g, 1.62 mol) and reflux for another 3 hours.
To complete the reaction. After finishing, clean until the washing water becomes neutral.
Washing with water was repeated. To remove the solvent under vacuum
Thus, a silsesquioxane compound was obtained. Molecular weight is GPC
As a result of analysis, Mn = 9650, Mw = 11700 (poly
(Styrene equivalent, UV detector). Minutes by NMR
As a result of the analysis, Me₃-Si-O_1/2
8 mol% bonding, Ph-Si-O_3/292 mol bond
%Met.

[0043]Production of silicone compound (Si-2)  Phenyltriethyl in methyl isobutyl ketone solution (1 L)
Chlorosilane (85g, 0.4mol) and dichlorodiph
Phenylsilane (203 g, 0.8 mol)
After cooling, 250 ml of pure water was added dropwise, and the reaction was carried out under reflux for 5 hours.
Was done. Thereafter, trimethylchlorosilane (130
g, 1.2 mol) and refluxed for another 3 hours for reaction.
Finished. After completion, use pure water until the wash water becomes neutral
The washing was repeated. The solvent is distilled off under vacuum to
A sesquioxane compound was obtained. The molecular weight is determined by GPC analysis.
As a result, Mn = 3520, Mw = 5139 (polystyrene
Conversion, UV detector). Analysis results by NMR
As a result, Ph-Si-O_3/22 bindings
7 mol%, Ph₂-Si-O_2/254 mol% of bonds,
Me₃-Si-O_1/2The binding was 19 mol%.

[0044]Production of silicone compound (Si-3)  Trimethoxyphenylsilane (40g, 0.2mo
l), dimethoxydiphenylsilane (171 g, 0.7
mol) and tetraethoxysilane (21 g, 0.1 mol)
l) water containing 0.2N HCl (1.1 g) in the mixture of 1)
(43 g, 2.4 mol) and stirred at 60 ° C. for 3 hours.
Was. After allowing the reaction mixture to come to room temperature,
Add run (109 g, 1 mol) and react at 60 ° C for 2 hours.
I responded. Then, toluene was added and washed several times with water.
After that, the solvent, alcohol and water
An organosiloxane was obtained. The molecular weight of the product is
As a result of the analysis, Mn = 2844, Mw = 4956 (Polystyrene)
Len conversion, RI detection). Analysis results by NMR
As a result, Ph-Si-O_3/21 bond
5 mol%, Ph₂-Si-O_2/254 mol% of bonds,
Si-O_4/28 mol% bonding, Me₃-Si-O
_1/2The binding was 23 mol%.

[0045]

[Table 1]

As shown in Table 1, in each of the examples, even though the test piece had a small thickness, it exhibited very good flame retardancy, good impact resistance, and the appearance of the molded product was translucent. ,
Comparative Example 1 was inferior in flame retardancy because no flame retardant was used. In Comparative Examples 2 to 4, since a silicone polymer different from that of the present invention was used as a flame retardant, the flame retardancy of a thin test piece was particularly poor. In Comparative Example 5, since the amount of the flame retardant added was out of the range of the present invention, molding was difficult.

[0047]Examples 7 to 13 and Comparative Examples 6 to 12  The following materials were used as the resin at the ratios shown in Tables 2-3.
Same as Example 1 except that the resin and the flame retardant were blended.
A resin composition was obtained.・ PET: polyethylene terephthalate with logarithmic viscosity 0.70
PBT: Polybutylene terephthalate with logarithmic viscosity of 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 ・ PMI: Styrene ・ N-phenylmaleimide ・ Anhydride
It is a maleic acid copolymer resin (produced by Denki Kagaku Kogyo Co., Ltd.
Product name) IP Polymer MS-NA

[0048]

[Table 2]

[0049]

[Table 3]

As shown in Tables 2 and 3, it can be seen that the flame retardancy is improved by adding the flame retardant of the present invention.

[0051]

The flame retardant of the present invention comprises chlorine, bromine, phosphorus,
Even if a generally used flame retardant such as nitrogen is not used, it shows very excellent flame retardancy with a small amount of addition, and hardly impairs the inherent characteristics of the resin. Further, it has a flame retardant effect on various resins, and can be synthesized relatively easily using inexpensive raw materials. Such flame retardants are very useful industrially.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Tatsufumi Yoshida 5-1-1 Torigai Nishi, Settsu-shi, Osaka Kanebuchi Chemical Industry Co., Ltd. F-term (reference) 4H028 AA42 AA44 AA49 BA06 4J002 BH021 CF161 CG011 CH071 CM041 CN011 CP012 CP032 FD132 4J035 BA11 BA15 EA01 LB20

Claims (6)

[Claims] 1. A RSiO _3/2 units (wherein, R represents a possible bonded organic groups in Si) and has a structure consisting of _{SiO 4/2} units, wherein _{RSiO 3/2} units and the S
R / Si molar ratio in iO _4/2 unit is 0.2 to 0.2
0.95 and the number average molecular weight is 1000
A flame retardant comprising an organopolysiloxane compound in the range from 1 to 200,000. 2. RSiO _3/2 units (wherein R represents an organic group capable of bonding to Si), SiO _4/2 units and R ′ ₃ SiO _1/2 unit (where R ′ is carbon Numbers 1-4
Selected from the group consisting of an alkyl group and an aromatic group having 6 to 24 carbon atoms, which may be the same or different), wherein the RSiO _3/2 unit and the S
R / Si molar ratio in iO _4/2 unit is 0.2 to 0.2
0.95 and the number average molecular weight is 1000
A flame retardant comprising an organopolysiloxane compound in the range from 1 to 200,000. 3. The organopolysiloxane compound according to claim 1, wherein the organic group substantially comprises a methyl group and an aromatic group, and the molar ratio of methyl group / aromatic group is in the range of 0.01 to 9. 3. The flame retardant according to 2. 4. A flame-retardant resin composition comprising 0.1 to 50 parts by weight of the flame retardant according to claim 1 based on 100 parts by weight of the resin. 5. The flame-retardant resin composition according to claim 5, wherein the resin is an aromatic resin. 6. The resin includes an aromatic polycarbonate resin, an aromatic polyester resin, a polyphenylene ether resin, an aromatic vinyl resin, a polyphenylene sulfide resin, an N-aromatic substituted maleimide resin, a polyimide resin, and 7. The flame-retardant resin composition according to claim 5, which is at least one selected from the group consisting of a polymer alloy consisting of at least two of these.