JP3240972B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition,
In particular, the present invention relates to a silicone resin that imparts flame resistance to a non-silicone resin composition containing an aromatic ring.

[0002]

2. Description of the Related Art Flame-retardant resin compositions are widely used in products such as electric and electronic equipment parts, building materials, automobile parts, and daily necessities. In general, these resin compositions include an organic halogen compound,
Alternatively, flame resistance is imparted by adding this and antimony trioxide. However, these flame-retardant resin compositions have a drawback in that harmful halogen-based gases are generated during combustion.

[0003] On the other hand, it is known that by adding silicone to a base resin component, flame resistance can be imparted without generating harmful gases during combustion.

[0004] Silicone (organopolysiloxane)
Represents the following four units (M unit, D unit, T unit,
Q unit), wherein the silicone resin generally refers to a resin containing at least one of the T unit and the Q unit.

[0005]

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[0006] Japanese Patent Application Laid-Open Nos.
JP-A-150436 describes a flame retardant and a flame-retardant resin composition using a general silicone.
No. 60421, Japanese Patent Publication No. 3-48947,
A flame retardant using a silicone having a special structure such as a silicone resin containing a large number of specific units or a silicone resin containing only a specific unit is disclosed. Hereinafter, each related art will be described.

[0007] Japanese Patent Application Laid-Open No. 1-318069 discloses a silicone resin (R _x Si (OR ') _y O having an alkoxy group or a hydroxyl group, which is composed of all of the above four units.
_{(4-xy) / 2} ) and that a powdery polymer mixture comprising a thermoplastic polymer renders the thermoplastic material flame-retardant.

JP-A-2-150436 describes that a mixture of a commonly used general silicone powder such as dimethyl silicone, a metal hydroxide, and a zinc compound renders a thermoplastic resin flame-retardant. Have been.

Japanese Patent Publication No. Sho 62-60421 discloses a formula R
A polysiloxane resin containing at least 80% by weight of a T unit represented by SiO _1.5 renders a thermoplastic non-silicone polymer flame-retardant, and particularly has a polysiloxane resin having a molecular weight of 2,000.
It is described that it is preferable for the flame resistance of the polymer composition that 0 to 6,000, R in the formula is 80% or less in molar ratio, and the remainder is a phenyl group and the remainder is a methyl group.

Japanese Patent Publication No. 3-48947 discloses a silicone resin, particularly an MQ silicone resin comprising a unit (M unit) represented by an average formula R ₃ SiO _0.5 and a unit (Q unit) represented by an average formula SiO _2. , Silicones and Group IIA metal salts are said to render thermoplastics flame resistant.

[0011]

However, the general silicone resin alone disclosed in Japanese Patent Application Laid-Open Nos. 1-318069 and 2-150436 is insufficient in flame resistance, and in fact, it is not practically known. As described in Examples of No. 318069, halogen compounds and phosphorus compounds,
In JP-A-2-150436, it is necessary to add a known flame retardant such as an inorganic filler such as a metal hydroxide in combination.

Further, the silicone resin having a special structure described in Japanese Patent Publication No. 62-60421 and Japanese Patent Publication No. 3-48947 has a higher flame resistance effect than that of the above general silicone resin alone. The effect is still insufficient, so that it was necessary to increase the amount of addition. In Japanese Patent Publication No. 62-60421, flame resistance is achieved by adding 10 to 300 parts by weight of a silicone resin to 100 parts by weight of a non-silicone resin.
Particularly preferably, the silicone resin is used in an amount of not less than 20 parts by weight and not more than 100 parts by weight.
Not more than parts by weight. However, when the addition amount of the silicone resin is increased, there is a problem that various physical properties such as moldability and mechanical strength of the resin composition are significantly reduced.

Therefore, even if a flame retardant such as a halogen-based compound, a phosphorus-based compound, or a metal hydroxide is not contained, and even if a small amount of silicone resin is added, the flame-retardant effect is large, and the moldability and mechanical properties of the resin composition are improved. There is a need for a flame-retardant resin composition having excellent strength.

The present invention has been made in view of the above circumstances, and has as its object to solve the above problems.
An object of the present invention is to provide a flame-retardant resin composition that does not generate harmful gas at the time of fire or incineration and that is safe and has a low environmental load.

[0015]

According to the present invention, there is provided a flame-retardant resin composition comprising a silicone resin having a specific structure and molecular weight, and a non-silicone resin having an aromatic ring. .

The flame-retardant resin composition of the present invention comprises a non-silicone resin (A) containing an aromatic ring and a silicone resin (B) having a unit represented by the formula R ₂ SiO _1.0 and a unit represented by the formula RSiO _1.5. (Where R is methyl and phenyl )
Has become more), the weight average molecular weight of the silicone resin (B) is not less than 10,000 270,000 or less, and a phenyl group of the R is not less than 40% at a molar ratio of 8
0%, the remaining R is a methyl group, and the silicone resin (B) is contained in a proportion of 0.1 to 30 parts by weight with respect to 100 parts by weight of the non-silicone resin (A). Features.

The aromatic ring of the non-silicone resin (A) containing an aromatic ring used in the present invention is a general term for aromatic rings such as a benzene ring, a condensed benzene ring, a non-benzene-based aromatic ring and a heteroaromatic ring. Point. A naphthalene ring is shown as an example of a condensed benzene ring, and a pyrrole ring is shown below as an example of a heteroaromatic ring.

[0018]

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Non-silicone resin containing aromatic ring (A)
Examples thereof include aromatic polycarbonate resins, alloys of aromatic polycarbonates, copolymers of acrylonitrile / butadiene / styrene (hereinafter referred to as ABS), thermoplastic resins containing aromatic rings such as polystyrene resins, and aromatic rings. Epoxy resins, thermosetting resins containing aromatic rings such as phenolic resins can be used alone or in combination of two or more. Among them, aromatic polycarbonate resins and alloys of aromatic polycarbonate resins are preferable for flame resistance. .

The silicone resin (B) used in the present invention
Is the unit represented by the formula R ₂ SiO _1.0 (D unit) and the formula R
It has a unit (T unit) represented by SiO _1.5 , each R is composed of a saturated hydrocarbon group and an aromatic hydrocarbon group, and the weight average molecular weight of the silicone resin (B) is from 10,000 or more to 270,000 or less. Things.

If the molecular weight (weight-average molecular weight) of the silicone resin (B) is less than 10,000, the viscosity is too low, and it is difficult to knead with the non-silicone resin (A) as a base resin, and the moldability is low. Is also bad. Furthermore, the flame retardant effect, especially the drip resistance of the resin composition during burning (dripping by melting of the resin)
Is reduced. On the other hand, if the molecular weight of the silicone resin (B) is too large, the melt viscosity becomes too high, and the kneadability and moldability of the base material with the non-silicone resin (A) decrease. Further, the transferability of the silicone resin to the surface of the non-silicone resin during molding or combustion is reduced, and the formation of a flame-resistant film on the resin surface is reduced, so that the flame retardant effect is also reduced. In particular, when it exceeds 270,000, the flame retardant effect is greatly reduced.

The R ₂ SiO _1.0 unit constituting the silicone resin (B) used in the present invention is expressed by RS
The _1.5 units of iO are preferably 0.5 times or more in molar ratio of 7 units.
Less than double is better. The unit represented by the formula RSiO _1.5 is a compound represented by the formula R ₂
If it is less than 0.5 times the unit represented by SiO _1.0 , the silicone resin tends to be oily,
Kneading with a non-silicone resin becomes difficult, and moldability also decreases. Furthermore, since the heat resistance of the silicone resin itself is reduced, the flame retardant effect on the non-silicone resin is reduced, and the drip easily occurs. Further, the unit represented by the formula RSiO _1.5 is 7 times the unit represented by the formula R ₂ SiO _1.0.
If the ratio is more than twice, dispersion in the non-silicone resin becomes worse due to steric hindrance, and condensation of phenyl groups in the silicone resin in the flame-resistant coating hardly occurs, and the flame resistance of the silicone resin itself is reduced. For this reason, the flame retardant effect on the non-silicone resin is reduced.

R ₂ SiO _1.0 of silicone resin (B)
R in the unit and RSiO _1.5 unit is a methyl group and a phenyl group, and more preferably, the ratio of the phenyl group is 40% or more and less than 80% by mole ratio, and the remainder is a methyl group. When the ratio of the phenyl group is less than 40% by mole ratio,
Since the compatibility with the non-silicone resin containing an aromatic ring is reduced, the kneading property is reduced. Further, the flame resistance of the non-silicone resin is reduced because the flame resistance of the silicone itself is reduced. On the other hand, the ratio of phenyl groups is 80
% Or more, the compatibility with the non-silicone resin containing an aromatic ring becomes too high, so that the transferability of the silicone resin to the non-silicone resin surface during molding or burning of the non-silicone resin decreases. As a result, it becomes difficult to form a flame-resistant film on the resin surface, so that the flame retardant effect is reduced. Furthermore, steric hindrance between phenyl groups in the silicone resin makes it difficult for efficient condensation between phenyl groups in the flame-resistant film to occur, and the flame resistance of the film decreases.

[0024]

The silicone resin (B) used in the present invention
Is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the non-silicone resin (A) component. If the content of these components is less than the above range, the flame resistance is reduced as compared with the above range, and if the content exceeds this range, the mechanical strength of the molded body is reduced as compared with the above range.

The silicone resin (B) used in the present invention
May be independently kneaded with the non-silicone resin (A), or a plurality of types of silicone resins (B) may be mixed and kneaded with the non-silicone resin before use. Similarly, the non-silicone resin (A) can be used alone or as a mixture of a plurality of non-silicone resins.

Further, if necessary, a reinforcing agent can be added to the flame retardant resin composition of the present invention. As reinforcing agents, antioxidants, neutralizers, ultraviolet absorbers, antistatic agents,
Pigments, dispersants, lubricants, thickeners, fillers, carbonization promoting catalysts,
If necessary, a resin composition such as an anti-drip agent can be added.

Particularly, as the filler, the silicone resin (B) used in the present invention is used in combination with an inorganic filler such as silica powder, calcium carbonate powder, talc powder, etc., particularly silica powder, to thereby contain an aromatic ring. Kneadability with the non-silicone resin (A) can be improved. In this case, the flame retardancy can be maintained well. The amount of the inorganic filler to be added is preferably 0.1 times or more by weight relative to the silicone resin (B).

[0029]

Next, one embodiment of a method for producing a flame-retardant resin comprising the flame-retardant resin composition of the present invention will be described.

Examples of the non-silicone resin component (A) containing an aromatic ring include aromatic polycarbonate resins, alloys of aromatic polycarbonates, and copolymers of acrylonitrile / butadiene / styrene (hereinafter referred to as AB).
S), a thermoplastic resin containing an aromatic ring such as a polystyrene resin, a thermosetting resin containing an aromatic ring such as an epoxy resin containing an aromatic ring, or a phenol resin is used alone or in combination of two or more.

The silicone resin component (B) is produced according to a general method for producing a silicone resin. That is, in accordance with the ratio of the unit represented by the formula RSiO _1.5 units (D units) of the formula R ₂ SiO _1.0 which constitute the molecular weight and the silicone resin of the silicone resin component (B) (B) (T units), A suitable amount of diorganodichlorosilane and monoorganotrichlorosilane is hydrolyzed to form a partially condensed silicone resin, which is further reacted with triorganochlorosilane to form a cross-linked terminal group of the silicone resin (B) with R ′ ₃ The polymerization is terminated with _0.5 unit of SiO.

The silicone resin component (B) used in the present invention has a molecular weight (weight average molecular weight) of the formula R ₂ SiO
It is characterized by a ratio of a unit (D unit) represented by _1.0 to a unit (T unit) represented by the formula RSiO _1.5 , a ratio of a phenyl group and a methyl group of R, and the like. The molecular weight is measured by gel permeation chromatography (GP
C). The structural formula (general formula) of the silicone resin used in the present invention is shown.

[0033]

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The molecular weight of the silicone resin component (B) used in the present invention is from 10,000 to 270,000, and the molecular weight is controlled by controlling the reaction time during the production of the silicone resin.

Formula R ₂ SiO _1.0 in the silicone resin component
The ratio of the unit represented by the formula (D unit) to the unit represented by the formula RSiO _1.5 (T unit) can be adjusted by the amount of diorganodichlorosilane and monoorganotrichlorosilane used during the production of the silicone resin. Note that chlorine in the silicone resin production raw material becomes hydrochloric acid during the hydrolysis reaction and is removed by liquid-liquid extraction, so that it is not contained in the silicone resin component. In the present invention, R ₂ SiO _1.0
It has both units (D units) and RSiO _1.5 units (T units). Preferably, the RSiO _1.5 units are 0.5 times or more in molar ratio to the R ₂ SiO _1.0 units constituting the silicone resin (B). Less than 7 times is good.

The ratio of the methyl group to the phenyl group of R in the silicone resin component is determined by using a methylsilane-based raw material such as dimethyldichlorosilane or monomethyltrichlorosilane, and diphenyldichlorosilane or monophenyltrichlorosilane during the production of the silicone resin. Adjust by volume.

Each component of the non-silicone resin component (A) having an aromatic ring and the silicone resin component (B) are respectively weighed and mixed, and are formed by the same apparatus and method as in the case of conventional plastic formation. That is, after thoroughly mixing and dispersing the raw materials of each of the components A and B using a mixing stirrer such as a ribbon blender or a Henschel mixer, the non-silicone resin component (A) and the silicone are mixed with a melt kneader such as a Banbury roll or an extruder. The desired product is obtained by kneading with the resin component (B). However, in the case of the silicone resin (B) which is not solid at room temperature, it can be directly kneaded with the non-silicone resin (A) by a melt kneader.

After kneading, the mixture is molded into a desired shape by a molding method such as an injection molding method, an extrusion molding method, a compression molding method, or a vacuum molding method to obtain a flame-retardant resin molded article.

After molding, the flame retardancy was evaluated in accordance with JIS K7201 (a method for testing combustion of a polymer material by an oxygen index method). The combustion test method of a polymer material by the oxygen index method means that a test piece of a predetermined size burns continuously for 3 minutes or more, or the burning length after burning is 50 mm.
This is a method for determining the minimum oxygen flow rate necessary to keep burning and the nitrogen flow rate at that time, and the numerical value of the minimum oxygen concentration (volume percent) obtained by the above method is called an oxygen index. The higher the oxygen index value, the better the flame resistance.

[0040] As in the present invention, the non-silicone resin containing an aromatic ring (A), both units (T units) represented as a unit (D unit) represented by the formula R ₂ SiO _1.0 by the formula RSiO _1.5 Weight average molecular weight of 10,000 or more 2
When the silicone resin (B) having a hydrocarbon group of 70,000 or less and R is a hydrocarbon group is contained, flammable gas is not generated at the time of combustion, and the flame resistance of the resin is achieved with a smaller amount of the silicone resin than before. can do.

Next, examples of the present invention and the results of combustion tests thereof will be described.

[0042]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, according to the above-mentioned silicone resin production method, the molecular weight (weight-average molecular weight) of the silicone resin, the formula R
₂ units (D units) represented by SiO _1.0 and formula RSiO
The ratio of the unit represented by _1.5 (T unit) and the ratio of the phenyl group and the methyl group of R in the silicone resin are different from each other.
Various kinds of silicone resins 1 to 37 were synthesized.

The molecular weight of each of the silicone resins 1 to 37 and D
Table 1 shows the ratio of the unit to the T unit, and the ratio (molar ratio) of the phenyl group to the methyl group in the hydrocarbon group R of the silicone resin. The ends of the silicone resins listed in Table 1 were blocked with an excess of trimethylchlorosilane.

[0044]

[Table 1]

The silicone resin component (B) used in the flame-retardant resin composition of the present invention has a weight average molecular weight of 10,
2,000 to 270,000 and the formula R ₂ SiO
_It has both _1.0 units (D units) and _1.5 units of the formula RSiO (T units), and R is a methyl group and a phenyl group;
The phenyl group is 40% or more and less than 80% by mole ratio,
Consists of a methyl group . Therefore, the silicone resin component which can be used in the present invention is the silicone resin 1 shown in Table 1.
1 to 13, 19 , 22 to 24 , 27 and 33 , 36 , and silicone resins 1 to 5 , 14 to 18 and 28 to 31.
Are comparative examples, and silicone resins 6 to 10, 20, 21, and
25, 26, 32, 34, 35, and 37 are silicone resins used as reference examples .

Since the silicone resin 14 has a large molecular weight and a too high melt viscosity, it cannot be kneaded with a non-silicone resin (polycarbonate resin).

As the non-silicone resin (A), bisphenol A type polycarbonate resin (Calibur 301-10 manufactured by Sumitomo Dow) or an alloy of bisphenol A type polycarbonate and ABS (H-270 manufactured by Sumitomo Dow)
The following silicone resin (B) and non-silicone resin (A) were melt-kneaded with a stone mill type extruder using PC / ABS) or polystyrene resin (H-65 manufactured by Nippon Steel Chemical Co., Ltd.). The kneading temperature at that time is 280 ° C. (preferably 270 ° C. to 290 ° C.) for the polycarbonate resin and 260 ° C. (250 ° C. to 270 ° C.) for PC / ABS.
Is preferred. ), 220 ° C (210
C. to 230 C. are preferred. ).

The silicone resin (6, 9, 11)
Is the above-mentioned bisphenol A-type polycarbonate resin and silica powder A (FB-48 manufactured by Denki Kagaku Kogyo: average particle size of 16).
μm) or silica powder B (AER made by Nippon Aerosil)
OSIL130 (average particle diameter: 16 nm) was also melt-kneaded with a millstone extruder. The kneading temperature at that time is 280 ° C.

The melt-kneaded resin composition was heated at 120 ° C. for 3 hours.
After drying for a time, a flat plate having a thickness of 3.0 mm was formed by a compression molding method. The molding temperature is 270 for polycarbonate.
℃, 240 ℃ for PC / ABS system, 20 for polystyrene system
0 ° C. and the molding time is 1 minute.

The formed flat plate is 150 mm long and 6 mm wide.
Processed into a test specimen of 5 ± 0.5 mm and JIS K720
The flame retardancy was evaluated according to 1 (combustion test method of polymer material by oxygen index method), and the oxygen index was determined.

Tables 2 to 10 and FIGS. 1 and 2 show the amounts of the silicone resin (B) and the oxygen index of each resin composition in 100 parts by weight of the non-silicone resin (A) of each resin composition. Is shown.

Tables 11 to 12 show the amounts of the silicone resin (B) and the silica powder relative to 100 parts by weight of the non-silicone resin (A) of each resin composition, and the results of the kneading properties of each resin composition.

Table 2 shows the results according to the embodiment of the present invention.
Table 3 shows the results of Comparative Examples in which no silicone resin was added and in which a silicone resin having a weight average molecular weight of less than 10,000 or having no D unit or T unit was used.

[0054]

[Table 2]

[0055]

[Table 3]

Reference Examples 1 to 3 in Table 2 and Comparative Examples 1 to 3 in Table 3
As described in Reference Example 7, both the unit (D unit) represented by the formula R ₂ SiO _1.0 and the unit (T unit) represented by the formula RSiO _1.5 of the reference example have a weight average molecular weight of 1
The polycarbonate resin composition containing a silicone resin (6 to 8) having a methyl group and a phenyl group of from 000 to 270,000 and R is a silicone resin (1 To 5) (Comparative Examples 2 to 7) and those not containing a silicone resin (Comparative Example 1), thereby obtaining a higher oxygen index value.
It can be seen that the flame retardancy has improved.

Next, Table 4 shows the effect on the flame resistance by the ratio of the D unit and the T unit constituting the silicone resin and the ratio of the methyl group and the phenyl group.

[0058]

[Table 4]

As shown in Reference Examples 4 and 5, Reference Examples 1 to 3
In addition to the characteristics of the silicone resin (6-8),
The polycarbonate resin compositions containing the silicone resin (9, 10), wherein the molar ratio of the T unit to the unit is 0.5 times or more and less than 7 times, are referred to in Reference Examples 1 to 3 and Comparative Example 1. It can be seen that they exhibit even higher flame resistance than those containing the silicone resins (1 to 5).

Further, as shown in Examples 1 to 4 , in addition to the features of the silicone resins (6 to 10) shown in Reference Examples 1 to 5, R is more than 40% and less than 80% by mole of phenyl group. In the polycarbonate resin composition containing the silicone resin (11 to 13), wherein the remainder is a methyl group, than those containing the silicone resin of Comparative Examples 1 to 7 and Reference Examples 1 to 5, It can be seen that the composition exhibits even higher flame retardancy.

Further, the effects on the flame resistance by the molecular weight of the silicone resin, the ratio of the D unit to the T unit (D / T ratio), and the ratio of the phenyl amount were examined in detail.

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

Comparative Examples 8 to 15 and Examples 5 to 5 in Tables 5 to 7
9, Reference Examples 6 to 9 and FIG. 1 show the results of the oxygen index when 4 phr of a silicone resin having a different molecular weight and a different phenyl content was added to a polycarbonate resin.

Examples 6 to 8 and Examples 10 to 10 in Tables 5 to 7
11 , Reference Examples 6 to 13 and FIG. 2 show the results of the oxygen index when 4 phr of a silicone resin having a changed D / T ratio and phenyl content was added to a polycarbonate resin.

Comparative Examples 8, 10, 13, 1 in Tables 5 to 7
5 and Examples 5, 7 , and 9 show the results of the oxygen index when 4 phr of a silicone resin having a changed molecular weight was added to a polycarbonate resin.

FIG. 1 is a graph showing the results of oxygen index when adding 4 pbr to a polycarbonate resin for a silicone resin having a changed molecular weight and phenyl content, and FIG. 2 is a graph showing the D / T ratio and the phenyl content. 4p for the silicone resin with the
It is a graph which shows the result of the oxygen index at the time of hr addition,
The numbers in the graph correspond to the example numbers.

As shown in Tables 5 to 7, FIGS. 1 and 2,
When the weight average molecular weight is 10,000 or more and 270,000 or less, the T unit is 0.5 times or more and less than 7 times the molar ratio of the D unit, and the R is 40% or more and less than 80% by molar ratio. It can be seen that a silicone resin characterized by a phenyl group and the remainder being a methyl group significantly increases the flame resistance of a polycarbonate resin containing an aromatic ring.

Next, the influence of the terminal group in the silicone resin will be described below.

In synthesizing the silicone resin, the amounts of trimethylmethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, and triphenylmethoxysilane were adjusted, and all the added silane was reacted with the silicone resin to form a terminal. 11 kinds of silicone resins having different functional groups (M units) were synthesized. Table 8 shows the results of evaluating the oxygen index and drip property of each of the added silanes with respect to the polycarbonate resin to which 4 phr of the silicone resin was added. The evaluation of the drip property was performed by the following method. Using a polycarbonate resin pellet to which a silicone resin was added, a test piece having a thickness of 3.0 mm was molded by a compression method (a molding temperature of 270 ° C.), and then a length of 1 mm was formed.
A test piece having a size of 25 ± 5 mm and a width of 13.0 ± 0.5 mm was cut out and determined by Underlatters Laboratories 2
The drip property after 10 seconds of indirect flame was evaluated according to the 0 mm vertical combustion test (UL94V). The silicone resins shown in Table 8 all had a molecular weight of 40,000, D / T = 1/4, and R
Ph / Me = 60/40.

[0072]

[Table 8]

As shown in Examples 12 to 22 , the units of formula R ₂ SiO _1.0 (D units) and the units of formula RSi
O _1.5 units (T units) and _0.5 unit (M units) of the formula R ' ₃ SiO, and their weight average molecular weight is 10,000.
0 to 270,000, R is a methyl group and a phenyl group, and among R ′, a hydroxyl group and / or a methoxy group is less than 10% in a molar ratio, and the remainder is a methyl group and / or a phenyl group. The polycarbonate resin composition containing a silicone resin (Examples 12 to 14 and 22 ) characterized in that it is a base is a polycarbonate resin composition containing a silicone resin not having these characteristics (Examples 15 to 14 ). 21 ) More flame-retardant effect
In particular, it can be seen that there is a remarkable effect on the improvement of the drip property.

Next, Table 9 shows the evaluation results of flame resistance when PC / ABS was used as the non-silicone resin (A) containing an aromatic ring.

[0075]

[Table 9]

As shown in Example 23, Reference Examples 14 and 15 and Comparative Examples 16 to 18, the formula R ₂ S
It has both iO _1.0 unit (D unit) and formula RSiO _1.5 unit (T unit), and has a weight average molecular weight of 10,000.
PC containing silicone resin (6, 9, 12) having a molecular weight of 270,000 or less and R is a hydrocarbon group.
The ABS composition containing the silicone resin (2, 4) not having these characteristics of the comparative example (Comparative Examples 15 to 1)
6) and Comparative Example 16 containing no silicone resin, a higher oxygen index value was obtained, indicating that the flame resistance was improved.

Next, Table 10 shows the evaluation results of flame resistance when a polystyrene resin was used as the non-silicone resin (A) containing an aromatic ring.

[0078]

[Table 10]

Example 24, Reference Examples 16 and 17 and Comparative Example 1
As shown in Nos. 9 to 21, both the formula R ₂ SiO _1.0 unit (D unit) and the formula RSiO _1.5 unit (T unit) in the examples have a weight average molecular weight of 10,000 or more and 27
The polystyrene resin compositions (Examples 24 and Reference Examples 16 and 17 ) containing a silicone resin (6, 9, 12) having a molecular weight of 000 or less and R is a hydrocarbon group have these characteristics of Comparative Examples. And a higher oxygen index value than those containing the silicone resin (2, 4) having no silicone resin (Comparative Examples 20 to 21) and those not containing the silicone resin (Comparative Example 19), and have improved flame resistance. ing.

Next, since the molecular weight is low and the proportion of D units is high, the silicone resin (6,
Tables 11 to 12 show the results obtained by improving the kneading properties by using silica powder in combination with 9 and 11).

[0081]

[Table 11]

[0082]

[Table 12]

As shown in Examples 25 to 27, Reference Examples 18 to 20 and Comparative Examples 22 to 26, silicone resins (6, 9, 11) having some problems in kneading properties in these Examples were
The kneadability is improved by using an inorganic filler such as silica powder in combination with the above components. The added silica powder is preferably 0.1 times or more, and the average particle size is 10 nm or more and 30 μm or less. If it is larger than 30 μm, the flame retardancy is low, and 1
Those smaller than 0 nm have a high danger at the time of work.

As described above, as shown in this example, the non-silicone resin (A) containing an aromatic ring and the formula R ₂ SiO _1.0
In made of a silicone resin (B) having a unit represented by the unit of formula RSiO _1.5 indicated a weight average molecular weight of B is 10,000 or more 270,000 or less, R is main
A phenyl group and a phenyl group, and the phenyl group has a molar ratio of
And the remaining R is a methyl group, and has a significant effect of improving flame resistance.

Further, the flame-retardant resin composition of the present invention has a flame resistance equivalent to or higher than that of the conventional flame-retardant resin composition in the safety standard (UL94) for flammability test defined by Underwriters Laboratories. effective.

Further, since the flame resistance is improved as compared with the conventional one, the amount of the silicone resin component added can be reduced, and the physical properties such as the moldability and the mechanical strength of the resin composition are also improved.

Further, according to the flame-retardant resin composition of the present invention, since the flame resistance is improved, it is not necessary to use another flame retardant (for example, a halide, a combination of a halide and antimony oxide, or a phosphorus compound). As described above, it is possible to form a molded product that has considerable flame resistance, generates no harmful gas during combustion, and is safe and has a low environmental load.

The silicone resin of the present invention can utilize the synergistic effect in combination with the flame retardant.
Since the flame resistance of the flame-retardant resin composition of the present invention has been improved as compared with the related art, the amount of the silicone resin and other flame retardants used can be significantly reduced.

[0089]

As described above, the flame-retardant resin composition of the present invention has excellent flame resistance with a small amount of silicone resin added, and can provide a molded article which does not generate harmful gas during combustion. Therefore, it is suitably used as a material for various molded articles, for example, OA equipment parts and electric / electronic parts.

Further, since the flame resistance is improved as compared with the conventional one, the amount of the silicone resin component added can be reduced, and the resin composition is excellent in physical properties such as moldability and mechanical strength.

[Brief description of the drawings]

FIG. 1 is a graph showing the results of oxygen index when 4 phr is added to a polycarbonate resin for a silicone resin having a changed molecular weight and phenyl content.

FIG. 2 is a graph showing the results of the oxygen index when adding 4 phr to a polycarbonate resin for a silicone resin in which the D / T ratio and the amount of phenyl were changed.

[Explanation of symbols]

Example 11 Reference Example 6 Example 12 Reference Example 7 Example 13 Example 6 Example 14 Example 7 Example 15 Example 8 Example 16 Reference Example 8 Example 17 Reference Example 9 Example 19 Reference Example 10 Example 20 Example 10 Example 21 Reference Example 11 real 22 reference example 12 real 23 example 11 real 24 reference example 13 ratio of 9 Comparative example 9 ratio 10 Comparative example 10 ratio 11 Comparative example 11 ratio 12 Comparative example 12 ratio 13 Comparative example 13 ratio 14 Comparative example 14

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (5)

(57) [Claims] 1. A non-silicone resin containing an aromatic ring (A)
And a unit represented by the formula R ₂ SiO _1.0 and the formula RSiO _1.5
(B) (where R
Comprises a methyl group and a phenyl group) , and the silicone resin (B) has a weight average molecular weight of 10,000 or more and 2
70,000 or less, and the phenyl group of R is
40% or more and less than 80% by mole ratio, the remaining R is a methyl group
Rannahli, the non-silicone resin (A) the silicone resin (B) is a flame retardant resin composition characterized in that it contains a proportion of 0.1 part by weight to 30 parts by weight per 100 parts by weight. 2. The non-silicone resin (A) containing an aromatic ring is an aromatic polycarbonate resin, an aromatic polycarbonate alloy, or acrylonitrile.
The flame-retardant resin composition according to claim 1, wherein the flame-retardant resin composition is at least one of a butadiene-styrene copolymer (ABS), a polystyrene resin, an epoxy resin containing an aromatic ring, and a phenol resin. . 3. The RSi in the silicone resin (B)
3. The flame-retardant resin composition according to claim 1, wherein the molar ratio of O _1.5 units to the R ₂ SiO _1.0 units is 0.5 times or more and less than 7 times. 4. A flame-retardant resin composition according to claim 1-3, wherein the non-silicone resin containing the aromatic ring (A) is an alloy of an aromatic polycarbonate resin, or an aromatic polycarbonate object. As wherein a reinforcing agent, silica powder, calcium carbonate powder, claim 1-4 flame-retardant resin composition, wherein it contains an inorganic filler such as talc powder.