JP3342323B2 - Flame retardant resin composition - Google Patents

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 and, more particularly, to a flame-retardant resin composition which does not generate harmful gas or flame-drops during combustion and has high safety.

[0002]

2. Description of the Related Art Thermoplastic resins are widely used for automobile parts, home electric parts, OA equipment parts, etc. because of their excellent moldability and impact resistance. Limited. Therefore, it has been practiced to improve the thermoplastic resin to make it flame-retardant.

Heretofore, as a method of flame retarding a thermoplastic resin, there has been known a method of adding an inorganic flame retardant such as a halogen-based, phosphorus-based, or metal hydroxide to a thermoplastic resin. Some flame retardancy has been achieved. However, when a halogen-based flame retardant is used, there is a problem that harmful gas is generated at the time of combustion, which may result in death of a person and corrosion of an electric system. Therefore, flame retardant resin is not sufficient, and flame retardant resin with high safety has been required.

[0004] Against this background, the development of non-halogen flame retardants has been studied, and in particular, silicone flame retardants have recently attracted attention. This is because silicone oil, silicone resin, and the like are not only flame retardants themselves, but also do not generate harmful gases during combustion, and are extremely safe compounds.

[0005] As an example using such a property of silicone, there is a silicone resin called MQ resin (see Japanese Patent Application Laid-Open No. 4-226159). Further, recently, as a novel flame retardant, a silicone polymer comprising a polydiorganosiloxane polymer and silica has been disclosed (see Japanese Patent Application Laid-Open No. 8-113712).

However, these silicone-based flame retardants have organic groups (particularly, methyl groups) substituted on Si and easily combustible, so that siloxane bonds are cracked by heat of combustion, and volatilization and scattering occur. As a result, there is a drawback that the effect of preventing dripping of flame burning cannot be sufficiently exhibited. As described above, even if a conventionally known silicone resin is used, a flame-retardant resin composition that is sufficiently satisfactory cannot be obtained from the viewpoint of preventing flame dripping.

[0007]

The present inventors have further studied a highly safe flame-retardant resin composition using a silicone-based flame retardant. The present inventors have found that extremely good results can be obtained when silica containing a small amount of weight loss by heating chemically modified with a specific polyorganosiloxane is contained, and the present invention has been achieved. Therefore, the object of the present invention is
An object of the present invention is to provide a flame-retardant resin composition which is excellent in safety and in which the generation of fire-flame drippings is significantly reduced.

[0008]

The objects of the present invention are as follows: 1) at least a thermoplastic resin: 100 parts by weight, 2) X
Silica chemically modified with polyorganosiloxane represented by _1.5 units of SiO (X is a radical polymerizable group-containing organic group): 1 to 20 parts by weight, and 3) metal hydroxide and / or fragrance Group-based phosphate: 1 to 100 parts by weight or at least 1) thermoplastic resin: 100 parts by weight, and 2) _1.5 units of XSiO (X is a radical polymerizable group-containing compound) Represented by an organic group), and a phosphate or phosphite unit.
That polyorganosiloxane chemically modified silica: 1
The present invention has been attained by a flame-retardant resin composition characterized in that the composition contains from 100 to 100 parts by weight. Hereinafter, the present invention will be described in detail.

The thermoplastic resin used in the present invention is, for example, one of conventionally known ones such as polyolefin, polyester, polystyrene, polyvinyl chloride, polycarbonate, polyphenylene ether and polyamide. Alternatively, two or more kinds can be appropriately selected and used. In the present invention, in particular, polyolefin-based,
It is preferable to use at least one selected from a polystyrene-based thermoplastic resin and a polyphenylene ether-based thermoplastic resin.

In the present invention, the average formula XSiO in the organopolysiloxane represented by XSiO _1.5 units is used.
X in _1.5 represents a radical polymerizable group-containing organic group. X
Specific examples include a vinyl group, an allyl group, a styryl group, an α-methylstyryl group, an acryloxyalkyl group, a methacryloxyalkyl group, an epoxyalkyl group, and a vinylbenzylaminoalkyl group.
Among them, from the viewpoint of easiness of production and economy,
Particularly, a vinyl group is preferable. The XSiO _1.5 unit refers to a hydrolyzable silane represented by XSiY ₃ (Y is a hydrolyzable group such as a halogen atom, a hydroxyl group, an alkoxy group or an alkenoxy group), or a hydrolytic condensation of a partial hydrolyzate thereof. Means things.

The silica used in the present invention may be either dry silica or wet silica, but has a specific gravity of 10 to 10.
It is preferably 300 g / l, especially 10 to 10 g / l.
150 g / l is preferred. In general, the smaller the specific gravity, the better the dispersibility when added to the resin. Chemical modification in silica chemically modified with a polyorganosiloxane represented by XSiO _1.5 unit is
In the present invention, the term is not broadly understood, but means a covalent bond, and does not include cases such as adsorption and ionic bond.

The silica chemically modified with a polyorganosiloxane represented by XSiO _1.5 unit refers to silica that has been treated once with a hydrolyzable silane having an organic group containing a radical polymerizable group or a partial hydrolyzate thereof. Thereafter, the remaining hydrolyzable group (Y) is further hydrolyzed and condensed, or the surface of the silica is treated with a hydrolyzable silane having the above-mentioned radically polymerizable group or a hydrolyzed condensate of a partial hydrolyzate thereof. This is silica obtained by performing

More specifically, the silica used in the present invention is prepared by coating the silica surface with a hydrolyzable silane having a radically polymerizable group or a partial hydrolyzate thereof in a solvent such as toluene, water or a Henschel mixer. After the treatment, the remaining hydrolyzable groups are hydrolyzed and condensed, or under the same conditions, the hydrolyzable silane having a radically polymerizable group or the hydrolyzed condensate of a partial hydrolyzate thereof is used for silica. It is silica obtained by treating the surface.

In this case, a catalyst such as dibutyltin dilaurate or tetrabutyl titanate is added to promote the surface treatment of silica, and a conventionally known acidic or basic catalyst is added to promote hydrolytic condensation. And may be further heated. When the treatment is performed in water, it is desirable to add a surfactant.
This is because the dispersibility of the raw material silica can be improved, and the particle size of the surface-treated silica can be reduced uniformly.

[0015] The thus-obtained chemically modified silica, average formula [XSiO _P Y ₃ - _{P / 2] a} [SiO _q
Y _{4 −q / 2} ] _b (X and Y are the same as those described above. P
Is a positive number from 0 to 3, and q is a positive number from 0 to 4. ), And has a fine particle size of 50 to 600 g / l and excellent dispersibility when added to a resin. In addition, since the core is silica and has a dendritic structure via a covalent bond, the crosslink density is considerably high.

The ratio of silica to XSiO _1.5 units (a / b
Ratio) is such that 1 mol of silica has an XSiO _1.5 unit of 0.1 mol.
01 to 50 mol (a / b = 0.01 to 5 in the average formula)
0), preferably 0.1 to 20 mol (a in the average formula
/B=0.1 to 20). When the amount is less than 0.01 mol, the flame retardant effect (particularly, the effect of preventing flame dripping) cannot be obtained,
If the amount is more than 0 mol, the particle diameter of the chemically modified silica obtained is coarse, so that the dispersibility at the time of addition of the resin is poor, which is not preferable.

Incidentally, chemically modified silica having the same average formula can also be obtained by utilizing the cohydrolytic condensation of SiY ₄ and XSiY ₃ (X and Y are the same as those described above). However, the chemically modified silica obtained in this case has a coarse particle size, is inferior in dispersibility when added to a resin, and is liable to gel during the production process, and has many disadvantages in operation.

The silica chemically modified with the polyorganosiloxane represented by XSiO _1.5 units thus obtained is used as a flame retardant auxiliary and is used in combination with the flame retardant. The amount used in this case is 1 to 100 parts by weight of the thermoplastic resin.
It is preferably 20 to 20 parts by weight, and particularly preferably 1 to 10 parts by weight. When the amount is less than 1 part by weight, the flame retardant effect (particularly
The effect of preventing flame drip is not obtained, and if the amount is more than 20 parts by weight, dispersibility at the time of adding the resin is deteriorated, which is not preferable.

In the present invention, a metal hydroxide and / or an aromatic phosphate ester is used as the flame retardant. The above compounds are flame retardants well known to those skilled in the art, and are characterized by not generating toxic gas during combustion.
As these flame retardants, for example, aluminum hydroxide,
Examples include magnesium hydroxide, triphenyl phosphate, tricresyl phosphate and the like. Further, the flame retardant is added in an amount of 1 to 100 parts by weight based on 100 parts by weight of the thermoplastic resin. It is apparent that the addition of the flame retardant as much as possible has an advantageous effect on the flame retardancy. However, 10
If the amount exceeds 0 parts by weight, it is not preferable from the viewpoints of compatibility with the resin, dispersibility, strength and the like.

The flame retardancy of the flame-retardant resin composition of the present invention is obtained by a synergistic effect of the above-mentioned flame retardant and a silica chemically modified with a polyorganosiloxane represented by XSiO _1.5 unit which is a flame retardant aid. However, in order to prevent flame drip during combustion, the weight loss by heating of silica chemically modified with a polyorganosiloxane represented by XSiO _1.5 units is particularly important.

For example, in the case of silica chemically modified with polydiorganosiloxane as disclosed in JP-A-8-113712, siloxane substituted with a non-polymerizable dimethyl group or the like replaces silica. Since the siloxane bond is simply bonded, cracking of the siloxane bond easily occurs due to the heat of combustion, and the rate of weight loss by heating due to volatilization, scattering, and the like is much larger than the theoretical value. Similarly, silica chemically modified with methyl trialkoxysilane is accompanied by a large weight loss due to heating.

The heating weight reduction rate of silica chemically modified with vinyl trialkoxysilane and methyl trialkoxysilane is much lower than the theoretical value for the same reason as described above, despite having a radical polymerizable group. large. Further, in the case of a co-hydrolysis condensate of a vinyl trialkoxysilane and a tetraalkoxysilane represented by the same average formula but not the silica in the present invention chemically modified with a polyorganosiloxane represented by XSiO _1.5 unit In addition, despite having a radical polymerizable group as described above, the weight loss on heating is still extremely higher than the theoretical value.

As described above, in the case of the conventional device, the weight loss upon heating is large in any case.
Flame burning dripping prevention effect cannot be obtained. In contrast, XSiO
The silica of the present invention chemically modified with a polyorganosiloxane represented by _1.5 units has a feature that the weight loss upon heating is equal to or less than the theoretical value. This feature is derived from the fact that, as described above, the radically polymerizable silane is bonded to the silica surface and the silane is polymerized to form a dendritic structure having silica as a core. That is, since this structure suppresses cracking of the siloxane bond due to the heat of combustion, volatilization and scattering are prevented.

In addition, the radical polymerizable group not only suppresses combustion by burning active OH radicals (propellant for combustion) generated during polymer combustion, but also promotes cross-linking during combustion. A non-burning shielding layer is formed, which advantageously acts to block oxygen. Thereby, a flame-retardant effect, in particular, a flame-burning dripping preventing effect can be obtained.

XS in the invention described in claim 2
Silica chemically modified with polyorganosiloxane represented by not only _1.5 units of iO but also a phosphoric acid ester or a phosphite ester unit is originally added to a resin as a flame retardant and a flame retardant auxiliary separately and independently. It is a highly safe flame retardant that improves the dispersibility and compatibility with the resin, which is a problem when performing, and does not generate toxic gas during combustion.

The silica chemically modified with a polyorganosiloxane represented by _1.5 units of XSiO and a phosphate or phosphite unit can be prepared as follows. Hydrolyzable silane having a radical polymerizable group on the surface of silica (XSiY ₃ , Y is a hydrolyzable group such as a halogen atom, a hydroxyl group or an alkoxy group, an alkenoxy group) or a partial hydrolyzate thereof, and a phosphate ester (POZ ₃ and Z are a hydroxyl group or a methoxy group,
It is an alkoxy group such as an ethoxy group and a phenoxy group. Preferred among these are methoxy groups. ) Or a phosphite (PZ ₃ and Z are the same as in the case of the phosphate), and then the remaining hydrolyzable groups (Y and Z) are further co-hydrolyzed and condensed.
The surface of the silica is treated with the hydrolyzable silane or a partial hydrolyzate thereof and a co-hydrolyzate of a phosphate or a phosphite.

Specifically, in a solvent such as toluene, water, or a Henschel mixer, a hydrolyzable silane having a radically polymerizable group or a partial hydrolyzate thereof and a phosphoric ester or phosphorous acid as described above. After treating the silica surface with the ester, the remaining hydrolyzable groups are co-hydrolyzed and condensed. Alternatively, under the same conditions, the surface of the silica is treated with a hydrolyzable silane having a radical polymerizable group or a partial hydrolyzate thereof and a co-hydrolyzate of a phosphate or a phosphite. At this time, in order to promote the surface treatment of the silica, a catalyst such as dibutyltin dilaurate or tetrabutyltitanate may be added, or heating may be further performed. In this case, when performing the treatment in water, it is desirable to add a surfactant.

The thus obtained chemically modified silica surface has an average formula [XSiO _P Y _{3-P / 2] a} [S
iO _q Y _{4-q / 2] b [POZ 3-r / 2] c} or the average formula [XSiO _P Y _{3-P / 2] a [SiO} q Y
_{4-q / 2} ] _b [PZ _{3-r / 2} ] _c (X and Y are the same as above. P is a positive number of 0 to 3, p is a positive number of 0 to 4, and r is 0 to Is a positive number of 3.), and the specific gravity is 5
It has a fine particle size of 0 to 600 g / l and is excellent in dispersibility and compatibility when added to a resin.

In the present invention, the ratio of the XSiO _1.5 unit to the phosphate or phosphite unit (a /
c ratio) is such that the phosphoric acid ester or phosphite ester unit is 0.01 to 20 per 1 mol of XSiO _1.5 unit.
Mole, and particularly preferably 0.05 to 10 mole. When the amount is less than 0.01 mol, gelation is apt to occur in the production process, so that there are many disadvantages in working.

Silica and XSiO_1.5Units and phosphate
Stele or phosphiteunitRatio ((a +
c) / b) is the ratio of XSiO_1.5single
Position and phosphate or phosphiteunit
Is from 0.01 to 50 mol ((a + c) /
b is preferably from 0.01 to 50), and particularly preferably from 0.
1 to 20 mol ((a + c) / b in the average formula is 0.1
To 20). Not more than 0.01 mol
If not, the flame retardant effect cannot be obtained,
Dispersion during resin addition due to the coarse particle size of the modified silica
Is reduced.

The thus obtained XSiO _1.5 unit and a phosphate or phosphite unit are represented by
Chemically modified silica polyorganosiloxane is a flame retardant also has a flame sintered drip preventing effect with the effect as a flame retardant aid. Therefore, only 1 to 100 parts by weight, preferably 5 to 50 parts by weight, is added to 100 parts by weight of the thermoplastic resin, and it is not necessary to add another flame retardant. If the amount is less than 1 part by weight, the flame retardant effect cannot be obtained,
When the amount is more than the weight part, the strength of the resin is reduced, which is not preferable. In addition, an antioxidant, a lubricant, and the like can be appropriately added to the flame-retardant resin composition of the present invention, in addition to the above main components.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition of the present invention comprises silica or XSiO chemically modified with a polyorganosiloxane represented by _1.5 units of XSiO.
_1.5 units and a silica chemically modified with a polyorganosiloxane represented by a phosphoric acid ester or a phosphite ester unit are prepared, and the silica 1 to 20 parts by weight based on 100 parts by weight of a known thermoplastic resin. Part by weight and 1-100 parts by weight of a metal hydroxide and / or an aromatic phosphate ester, and in the case of the latter silica, 100 parts by weight of a known thermoplastic resin is chemically modified. Can be obtained by mixing 1 to 100 parts by weight of silica.

[0033]

The flame-retardant resin composition of the present invention does not generate toxic gas during combustion, and the radical polymerizable group suppresses the cracking of siloxane bonds. .

[0034]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
Production Examples 1 to 6 are production examples of chemically modified silica used in the present invention, and Production Examples 7 to 10 are production examples of conventionally used chemically modified silica.

Production Example 1 Preparation of Silica Chemically Modified with Polyorganosiloxane Represented by XSiO _1.5 Unit (X is a Vinyl Group) In a 1-liter flask equipped with a condenser, a thermometer and a dropping funnel, put silica (Nipsil LP: Nippon Silica Kogyo Co., Ltd.) stock)
(Trade name) 12 g (0.2 mol), 59.2 g (0.4 mol) of vinyltrimethoxysilane, 0.3 g of dibutyltin dilaurate, 3 g of a cationic surfactant, and 50 g of water
After charging 0 g, 80 g of a 0.05 N aqueous hydrochloric acid solution was added using a dropping funnel.

Next, the bath temperature was maintained at 100 ° C., and the mixture was stirred for 3 hours, cooled, and filtered to obtain a white powder. When the obtained powder was dried in a dryer at 105 ° C. for 8 hours, the yield was 40.5 g, and the yield was 93%. ²⁹ Si-DD / MAS-NMR, ²⁹ Si-C
From the results of P / MAS-NMR and IR measurements, it was confirmed that this powder was the above compound. ²⁹ Si-MAS-NMR (δ, ppm): -70.1, -79.9 (CH ₂ = CH Si O _P Y _{3-P / 2} ), -110.1 ( Si O _q Y _{4-q / 2} ) IR (KBr, cm ^-1 ): 1640 (CH ₂ = CH), 1093 (Si-O-Si)

Production Example 2 Production of silica chemically modified with polyorganosiloxane represented by _1.5 units of XSiO (X is a vinyl group) 148.0 g (1.0 mol) of vinyltrimethoxysilane
Except for that, the same procedure as in Production Example 1 was carried out.
1 g of a white powder was obtained. The yield was 98%. The same analysis as in Production Example 1 confirmed that the powder was the above compound.

Production Example 3 Preparation of Silica Chemically Modified with Polyorganosiloxane Represented by XSiO _1.5 Units (X is Methacryloxypropyl Group) Instead of 59.2 g of vinyltrimethoxysilane, 248.4 g of methacryloxypropyltomexisilane (1.
0 mol), except that Production Example 1 was used.
185.3 g of a white powder were obtained. The yield was 97%. The same analysis as in Production Example 1 confirmed that the powder was the above compound.

Production Example 4 XSiO _1.5 unit (X is 3-glycidoxypropyl group)
Production of silica chemically modified with polyorganosiloxane represented by the formula: In a 1-liter flask equipped with a cooling tube, a thermometer and a dropping funnel, put silica (Nipsil LP: Nippon Silica Industry Co., Ltd.)
12g (0.2 mol), 236.4 g (1.0 mol) of 3-glycidoxypropyltrimethoxysilane, 0.2 g of tetrabutyl titanate and toluene 4
After charging 50 g, the mixture was stirred at a constant temperature for 2 hours while maintaining the bath temperature at 100 ° C.

After cooling, isopropyl alcohol 19.8
g and 32.4 g of a 0.05 N aqueous hydrochloric acid solution were added using a dropping funnel, and the mixture was heated and stirred at 70 ° C. for 2 hours.
Next, when a solvent such as toluene was distilled off under reduced pressure of 100 mmHg, a white powder was obtained. The obtained powder is 1
After drying in a dryer at 05 ° C for 5 hours, the yield was 17
The yield was 95% at 0.1 g. The same analysis as in Production Example 1 confirmed that the powder was the above compound.

Production Example 5 Preparation of Silica Chemically Modified with Organopolysiloxane Consisting of _1.5 Units of XSiO (X is a Vinyl Group) and Trimethyl Phosphite In a 1 liter flask equipped with a cooling tube, a thermometer and a dropping funnel, put silica (Erosil 200: Japan) 12 g (0.2 mol), 59.2 g (0.4 mol) of vinyltrimethoxysilane, 0.3 g of dibutyltin dilaurate, 3 g of a cationic surfactant and 500 g of water After that, trimethyl phosphite 49.6
g (0.4 mol) was added using a dropping funnel, and the mixture was stirred for 5 hours while maintaining the bath temperature at 100 ° C. After cooling and filtration, 63.6 g (97% yield) of white powder was obtained.
Obtained. The same analysis as in Production Example 1 confirmed that the powder was the above compound.

Production Example 6 Preparation of Silica Chemically Modified with Organopolysiloxane Consisting of XSiO _1.5 Units (X is a Vinyl Group) and Trimethyl Phosphate In a 1-liter flask equipped with a condenser, a thermometer and a dropping funnel, put silica (Nipsil LP: Nippon Silica) Industrial Co., Ltd.
12g (0.2 mol), 59.2 g (0.4 mol) of vinyltrimethoxysilane, 56.0 g (0.4 mol) of trimethyl phosphate, 0.2 g of tetrabutyl titanate and 450 g of toluene. After charging, the mixture was constantly stirred for 2 hours under reflux of toluene.

After cooling, isopropyl alcohol 19.8
g and 26.0 g of a 0.05 N aqueous hydrochloric acid solution were added using a dropping funnel, and the mixture was stirred constantly for 2 hours under reflux of the solvent. Next, the solvent such as toluene was distilled off under reduced pressure of 100 mmHg, and the obtained powder was dried in a dryer at 105 ° C for 5 hours. As a result, the yield was 69.1 g and the yield was 96%. The same analysis as in Production Example 1 confirmed that the powder was the above compound.

Production Example 7 Production of Silica Chemically Modified with α, ω-Hydroxydimethylsiloxane In a 500 ml flask equipped with a cooling tube, a thermometer and a dropping funnel, 12 g of silica (Aerosil 200, trade name of Nippon Aerosil Co., Ltd.) was added. 0.2 mol),
α, ω-hydroxydimethylsiloxane 22.2 g
(0.3 mol), 0.1 g of dibutyltin dilaurate, 2 g of cationic surfactant and 200 g of water, and then 1
10 g of a 0% aqueous ammonia solution was added using a dropping funnel, and the mixture was stirred for 5 hours while maintaining the bath temperature at 100 ° C., cooled, and filtered to obtain a white powder. When the obtained white powder was dried in a dryer at 105 ° C. for 8 hours, the yield was 32.1 g, and the yield was 93%. The same analysis as in Production Example 1 confirmed that the powder was the above compound.

Production Example 8 Production of silica chemically modified with polyorganosiloxane represented by MeSiO _1.5 unit (Me is a methyl group) In a 1-liter flask equipped with a condenser, a thermometer and a dropping funnel, silica (Nipsil LP: Nippon Silica Kogyo Co., Ltd.) stock)
12g (0.2 mol), 54.4 g (0.4 mol) of methyltrimethoxysilane, 0.3 g of dibutyltin dilaurate, 3 g of a cationic surfactant and 50 of water
After charging 0 g, 37.9 g of a white powder was obtained in exactly the same manner as in Production Example 1, except that 80 g of a 0.05 N hydrochloric acid aqueous solution was added using a dropping funnel. The yield was 98%. The same analysis as in Production Example 1 confirmed that the powder was the above compound.

Production Example 9 XSiO _1.5 unit (X is a vinyl group) and MeSiO _1.5
Production of silica chemically modified with polyorganosiloxane represented by a unit (Me is a methyl group) Silica (Erosil 200, Nippon Aerosil Co., Ltd.) was placed in a 500 ml flask equipped with a cooling tube, a thermometer and a dropping funnel. 12g (0.2 mol), 3.0 g (0.02 mol) of vinyltrimethoxysilane, 51.7 g (0.38 mol) of methyltrimethoxysilane,
Except that 0.2 g of dibutyltin dilaurate, 2 g of a cationic surfactant and 270 g of water were charged, and 80 g of a 0.05 N aqueous hydrochloric acid solution was added using a dropping funnel, the same procedure as in Preparation Example 1 was followed. 0.8 g of a white powder was obtained. The yield was 97%. The same analysis as in Production Example 1 confirmed that the powder was the above compound.

Production Example 10 Production of co-hydrolyzate of vinyl trialkoxysilane and tetraalkoxysilane In a 500 ml flask equipped with a condenser, a thermometer and a dropping funnel, 22.8 g of tetramethoxysilane was added.
(0.15 mol), vinyltrimethoxysilane 44.5
g (0.3 mol), 9.3 g of isopropyl alcohol and 163 g of toluene, 13.8 g of a 0.05 N hydrochloric acid aqueous solution was added using a dropping funnel.
The mixture was heated and stirred at 0 ° C. for 5 hours. Then, when a solvent such as toluene was distilled off under reduced pressure of 100 mmHg, a white powder was obtained. When the obtained white powder was dried in a dryer at 105 ° C for 5 hours, the yield was 32.5 g. The yield was 99%. The same analysis as in Production Example 1 confirmed that the powder was the above compound.

Embodiment 1 Polyethylene (Heisex 2
100J: 100 parts by weight of Mitsui Petrochemical Co., Ltd.), 5 parts by weight of the chemically modified silica obtained in Production Example 1 and 30 parts by weight of triphenyl phosphate were added,
After melt-kneading at 190 ° C, injection molding was performed at a nozzle temperature of 200 ° C. This molded product is 127 × 12.7 × 3 mm
And its flame retardance was determined by the following V rating of UL-94 (flammability test for classification of substances according to the Bulletin Underwriters Laboratory).

VO: The maximum combustion time after removing the ignition flame is within 10 seconds, the average flaming combustion and / or non-flaming combustion must not exceed 5 seconds and all tests Pieces must not be dripped with particles that ignite absorbent cotton. V-1: The maximum burning time after removing the flame for ignition was within 30 seconds, the average flaming combustion and / or non-flaming combustion did not exceed 25 seconds, and all test pieces were made of cotton wool. Do not drop particles that will ignite. V-2: The maximum combustion time after removing the ignition flame was within 30 seconds, the average flaming combustion and / or the non-flaming combustion did not exceed 25 seconds, and at least one test piece was Particles that ignite absorbent cotton may be dropped. N94V: Not applicable to any of the above. The results of the determination are as shown in Table 1.

[0050]

[Table 1]

Embodiment 2 FIG. Except that the chemically modified silica obtained in Production Example 2 was used, a test piece was prepared in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 1. Embodiment 3 FIG. Except that the chemically modified silica obtained in Production Example 3 was used, a test piece was prepared in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 1. Embodiment 4. FIG. Except that the chemically modified silica obtained in Production Example 4 was used, a test piece was prepared in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 1.

Embodiment 5 FIG. Polyethylene (Heisex 2
100 J, 100 parts by weight of Mitsui Petrochemical Co., Ltd.) and 20 parts by weight of the chemically modified silica obtained in Production Example 5 were melt-kneaded at 190 ° C., and then the nozzle temperature was 200 ° C. Was injection molded. Test pieces were prepared in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 1. Embodiment 6 FIG. Except for using the chemically modified silica obtained in Production Example 6, a test piece was prepared in exactly the same manner as in Example 5, and the flame retardancy was determined. The results are as shown in Table 1.

Comparative Example 1 Except for using the chemically modified silica obtained in Production Example 7, a test piece was prepared in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 1. Comparative Example 2. Except that the chemically modified silica obtained in Production Example 8 was used, a test piece was prepared in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 1. Comparative Example 3 Except that the chemically modified silica obtained in Production Example 9 was used, a test piece was prepared in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 1. Comparative Example 4. Except for using the chemically modified silica obtained in Production Example 10, a test piece was prepared in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 1.

Embodiment 7 FIG. The correlation between the reduction of the heated weight and the flame retardancy of the chemically modified silica used in each Example and Comparative Example was tested. The heating weight was reduced to 800 ° C. The results are as shown in Table 2.

[0055]

[Table 2]

Embodiment 8 FIG. Polyethylene (Heisex 2
100J: 5 parts by weight of the chemically modified silica obtained in Production Example 2 and 100 parts by weight of magnesium hydroxide were added to 100 parts by weight of Mitsui Petrochemical Co., Ltd.
After melt-kneading at 0 ° C., injection molding was performed at a nozzle temperature of 215 ° C. A test piece was prepared in exactly the same manner as in Example 1,
Flame retardancy was determined. The results are as shown in Table 3.

[0057]

[Table 3]

Embodiment 9 FIG. Polyethylene (Toporex 855-51: trade name, manufactured by Mitsui Toatsu Chemicals, Inc.) 100
In parts by weight, the chemically modified silica 5 obtained in Production Example 2 was added.
Parts by weight and 30 parts by weight of triphenyl phosphate, and melt-kneaded at 170 ° C .;
Injection molding was performed at ℃. Test pieces were prepared in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 3.

Embodiment 10 FIG. Polyethylene (Toporex 855-51: trade name, manufactured by Mitsui Toatsu Chemicals, Inc.) 10
0 parts by weight and polyphenylene ether (Noryl 731:
5 parts by weight of the chemically modified silica obtained in Production Example 2 and 20 parts by weight of triphenyl phosphate were added to 50 parts by weight of a trade name of GE Plastics Japan Co., Ltd.
After melt-kneading at 90 ° C, injection molding was performed at a nozzle temperature of 200 ° C. Test pieces were prepared in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 3.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (2)

(57) [Claims] 1. At least 1) thermoplastic resin: 100
Parts by weight, 2) silica chemically modified with a polyorganosiloxane represented by _1.5 units of XSiO (X is an organic group containing a radical polymerizable group): 1 to 20 parts by weight, and 3) metal water A flame-retardant resin composition comprising: oxide and / or aromatic phosphate: 1 to 100 parts by weight. 2. At least 1) thermoplastic resin: 100
Parts by weight, and 2) chemically modified with _1.5 units of XSiO (X is a radical polymerizable group-containing organic group) and a polyorganosiloxane represented by a phosphate or phosphite unit Silica: a flame-retardant resin composition comprising 1 to 100 parts by weight.