JP3915926B2 - Flame retardant resin composition - Google Patents

Description

  The present invention relates to a flame retardant resin composition mainly composed of a synthetic resin containing an aromatic ring in a molecule such as an aromatic polycarbonate resin or an aromatic epoxy resin.

  Flame retardant resin compositions are often used in products such as electrical / electronic equipment parts, building materials, automobile parts, and daily necessities. These resin compositions are generally provided with flame retardancy by adding an organic halogen compound or this and antimony trioxide.

  However, these flame retardant resin compositions have a drawback that harmful halogen gases are generated during combustion.

  On the other hand, it is known that flame retardancy is imparted by adding a silicone resin that does not generate harmful gases.

  JP-A-54-36365 (Patent Document 1) describes a flame retardant resin composition to which a silicone resin containing 80% by weight or more of a trifunctional siloxane unit is added. However, for the organic resin, there is no description about the aromatic polycarbonate resin or the aromatic epoxy resin, and in consideration of the melt processability with the organic resin, substantially no crosslinkable functional group is contained. Since a relatively high molecular weight silicone resin exhibiting a softening temperature above room temperature is used, the flame retardancy effect is small, and it is necessary to add 10 to 300 parts by weight of the silicone resin to 100 parts by weight of the organic resin. There was a problem that the characteristics of the organic resin were impaired.

  JP-A-59-500909 (Patent Document 2), JP-A-4-226159 (Patent Document 3), and JP-A-7-33971 (Patent Document 4) disclose monofunctional siloxane units and tetrafunctionality. A flame retardant resin composition to which a silicone resin comprising a siloxane unit is added is disclosed in JP-A-6-128434 (Patent Document 5) in which a silicone resin containing a siloxane unit having a vinyl group is added. Things are listed. However, in any composition, in order to obtain a sufficient flame retardant effect, it is necessary to increase the amount of silicone resin added or to use an inorganic filler such as aluminum hydroxide, a halogen and a phosphorus compound in combination.

  Thus, when adding a silicone resin, a sufficient flame retardant effect cannot be obtained unless the addition amount is increased. However, increasing the addition amount greatly increases various physical properties such as moldability and mechanical strength of the resin composition. Development of an additive that can be improved in combination with a silicone resin additive having a greater flame retardant effect or a silicone resin has been studied.

  JP-A-8-176425 (Patent Document 6) discloses a flame retardant resin composition in which an organopolysiloxane containing an epoxy group and an alkali metal salt of an organic sulfonic acid are added. Reference 7) describes a flame retardant resin composition in which a polycarbonate resin modified with a phenolic hydroxyl group-containing organopolysiloxane and an organic alkali metal salt are added. Japanese Patent Application Laid-Open No. 9-169914 (Patent Document 8) describes a composition in which a petroleum-based heavy oil or pitch is used in combination with a silicone compound to improve the flame retardant effect. However, silicone resins with special organic functional groups are expensive, and the flame retardant effect sufficient to meet the cost increase due to the complicated manufacturing process cannot be obtained, and further improvement is desired. ing.

  In addition, it is known that it is effective to add a silicone resin having an alkoxy functional group that can be introduced at a relatively low cost for the purpose of improving the heat-resistant oxidation resistance of the polycarbonate resin. JP-A-54-102352 (Patent Document 9) describes a thermoplastic resin composition to which a silicone resin containing an alkoxy group shown below is added. A siloxane with a higher alkoxy group content forms a network and thus has better thermal oxidation resistance. However, the former does not contain a phenyl group, so the flame retardancy is insufficient, and the latter phenyl-containing low molecular weight organosiloxane is added. In this case, the active ingredient was drastically reduced due to vaporization by heat at the time of melt processing or combustion, and the flame retarding effect was insufficient.

  Further, in JP-A-1-318069 (Patent Document 10), a powdery polymer mixture comprising a silicone resin having an alkoxy group or a hydroxyl group and a thermoplastic polymer is disclosed in JP-A-6-306265 (Patent Document 11). ) Describes a flame retardant polycarbonate resin composition containing an organic siloxane having an alkoxy group, a vinyl group and a phenyl group as essential components. However, the former also has insufficient flame retardancy with the silicone resin alone, so it is necessary to use a halogen and a phosphorus compound together. The latter substantially contains a lower alkoxy group such as a methoxy group as an alkoxy group. In addition, since the hydrolysis reactivity is too high, there is a problem that alcohol is generated and the transparency of the resin composition is impaired.

  In recent years, there has been an increasing demand for recycling of various plastic materials. However, the above-mentioned silicone compounds having reactive groups such as alkoxy groups, hydroxyl groups or epoxy groups can be used at the time of molding a resin composition or after molding. Over time, the molecular structure changes depending on the interaction between the silicone compounds or with other components in the resin composition and the usage environment, so that the moldability at the time of collection and use becomes poor and the recycling cannot be used.

On the other hand, in JP-A-10-139964 (Patent Document 12), a silicone resin comprising a bifunctional siloxane unit and a trifunctional siloxane unit and having a weight average molecular weight of 10,000 to 270,000 is added. A flame retardant resin composition is described. It is said that a monofunctional siloxane unit represented by R ′ ₃ SiO _0.5 is introduced as a terminal group, and the hydroxyl group and / or alkoxy group in this R ′ is preferably less than 10% by mole, The content of the hydroxyl group and alkoxy group in the inside is not specified, and since a high molecular weight silicone resin is used, further improvements in moldability and flame retardancy are required.

Therefore, it is possible to obtain a resin molded product excellent in flame retardancy by adding a small amount while maintaining the physical characteristics and optical transparency of a synthetic resin containing an aromatic ring in a molecule such as an aromatic polycarbonate or an epoxy resin. There is a need for flame retardant resin compositions that can be recycled and used.
JP 54-36365 A JP-T 59-500909 JP-A-4-226159 Japanese Unexamined Patent Publication No. 7-33971 JP-A-6-128434 JP-A-8-176425 JP-A-8-176427 JP-A-9-169914 JP-A-54-102352 JP-A-1-318069 JP-A-6-306265 Japanese Patent Laid-Open No. 10-139964

  Therefore, the first object of the present invention is to add an organopolysiloxane having substantially no reactive group and to be able to recycle it. It is safe and does not generate harmful gas during fire or incineration. An object of the present invention is to provide a flame retardant resin composition having a low content.

  The second object of the present invention is to select a material having a specific structure from among inexpensive organopolysiloxanes that do not have a special organic functional group, so that a sufficient flame retardant effect can be obtained even with a small amount of addition. Another object of the present invention is to provide a low-cost flame retardant resin composition.

  The third object of the present invention is to use an organopolysiloxane having a specific structure, so that there is hardly any deterioration in physical properties such as moldability of the resin composition, appearance of the molded product, optical transparency, and mechanical strength. It is in providing a flammable resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that synthetic resins containing aromatic rings in the molecule such as aromatic polycarbonate resins and aromatic epoxy resins, and phenyl groups in the molecules as silicon atoms. In addition to containing as an essential substituent to be bonded, a monofunctional siloxane unit is contained as an essential unit, and the content of alkoxy groups in the molecule and the content of hydroxyl groups as Si-OH groups are each less than 2% by weight. By adding a small amount of a specific molecular weight organopolysiloxane compound, it has been found that flame retardancy and anti-drip properties can be imparted, optical transparency can be ensured, and recycling can be used. It was. Since this product has high flame retardancy without containing halogen, phosphorus, antimony, etc., it is possible to prevent generation of harmful gases during combustion, and the organopolysiloxane is flame retardant with a small amount of addition. Since the effect is obtained, it was found that the original performance of a synthetic resin containing an aromatic ring in a molecule such as an aromatic polycarbonate resin or an aromatic epoxy resin is not deteriorated, and the present invention has been made. is there.

Therefore, the present invention
(A) 100 parts by weight of a synthetic resin containing an aromatic ring in the molecule,
(B) A siloxane unit containing a phenyl group as an essential substituent for bonding to a silicon atom in the molecule and represented by R ¹ R ² R ³ SiO _1/2 (provided that R ¹ , R ² and R ³ are Each having the same or different carbon number 1 to 6 unsubstituted or substituted monovalent hydrocarbon group), and the hydroxyl group content as an alkoxy group and Si-OH group in the molecule is less than 2% by weight, respectively. And 0.1 to 10 parts by weight of an organopolysiloxane having a weight average molecular weight of 2,000 or less, and further sodium benzenesulfonate, disodium naphthalene-2,6-disulfonate, diphenylsulfone-3-sulfone Provided is a flame retardant resin composition characterized by containing one or more selected from sodium acid and sodium perfluorobutanesulfonate .

  According to the present invention, by containing an organopolysiloxane having a specific structure in a synthetic resin having an aromatic ring in the molecule, flame retardancy of the resin can be achieved without generating harmful gas during combustion, and the optical properties of the molded product can be achieved. The flame retardant resin composition can be obtained, which can maintain the transparency and can be recycled.

Hereinafter, the present invention will be described in more detail.
The synthetic resin containing an aromatic ring in the molecule of the component (A) used in the present invention is a resin produced from an aromatic compound such as phenol, styrene or phthalic acid as a raw material, such as polystyrene resin, polycarbonate resin, polyphenylene. Oxide resins, acrylonitrile-butadiene-styrene resins, acrylonitrile-styrene resins, aromatic epoxy resins, aromatic polyester resins, and the like are used. Of these, aromatic polycarbonate resins and aromatic epoxy resins are preferably used.

  As the aromatic polycarbonate resin, those produced by the reaction of dihydric phenol and phosgene or carbonic acid diester can be used. As the dihydric phenol, bisphenols are preferable, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable. Further, some or all of 2,2-bis (4-hydroxyphenyl) propane may be substituted with other dihydric phenol compounds. Examples of dihydric phenol compounds other than 2,2-bis (4-hydroxyphenyl) propane include hydroquinone, 4,4-dihydroxyphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and bis Compounds such as (4-hydroxyphenyl) ketone. It may be a homopolymer of these dihydric phenols or a copolymer of two or more kinds, or a blend thereof.

  The aromatic epoxy resin is a synthetic resin having two or more epoxy groups in one molecule and curable with various curing agents, and various conventionally known epoxy resins can be used. Examples thereof include novolac type epoxy resins, triphenolalkane type epoxy resins, dicyclopentadiene-phenol novolac resins, phenol aralkyl type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. In particular, an epoxy resin having a biphenyl skeleton having a low melt viscosity is preferable, and if necessary, another epoxy resin is preferably used in combination.

The organopolysiloxane of component (B) contains a monofunctional siloxane unit represented by R ¹ R ² R ³ SiO _1/2 which contains a phenyl group as an essential substituent for bonding to a silicon atom in the molecule. Use what is contained. The phenyl group affects dispersibility and compatibility in a synthetic resin containing an aromatic ring, and is necessary for improving the flame retardancy, moldability and transparency of the resin composition. R ¹ R ² R ³ SiO _The monofunctional siloxane unit represented by _1/2 is used for the purpose of blocking the end of the organopolysiloxane molecule and reducing the content of reactive hydroxyl groups and alkoxy groups.

Here, R ¹ , R ² and R ³ may be the same or different and are selected from an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, specifically, a methyl group, ethyl Group, propyl group, butyl group, hexyl group, cyclohexyl group and other alkyl groups, vinyl group, allyl group and other alkenyl groups, phenyl group and the like are exemplified, and methyl group and phenyl group are particularly preferable.

  This organopolysiloxane makes it possible to recycle the resin composition and to reduce the reactive groups in the molecule as much as possible in order not to lower the moldability, appearance and transparency of the molded product as described above. For this reason, it is necessary to make the content of the alkoxy group in the molecule and the content of the hydroxyl group as the Si-OH group each equal to or less than a certain amount.

  Therefore, the organopolysiloxane used in the present invention needs to have an alkoxy group content in the molecule of less than 2% by weight. The alkoxy group in the organopolysiloxane has an effect of suppressing drip during combustion. On the other hand, in terms of moisture resistance, the flame retardant resin composition is placed under high humidity conditions. There is a possibility that alcohol may be generated by hydrolysis reaction with moisture absorption, and the transparency of the molded product may be impaired. As a result, the Si—OH group produced adversely affects the moldability during recycling. By reducing the content of alkoxy groups in the molecule to less than 2% by weight and reducing the amount of alkoxy groups that contribute to the hydrolysis reaction, moisture resistance is greatly improved, and molded products with excellent transparency can be obtained. it can. From the point of hydrolysis reactivity and flame retardancy of the alkoxy group, the remaining alkoxy group is further selected from 2 to 3 carbon atoms selected from isopropoxy group, 2-butoxy group, tert-butoxy group, cyclohexyloxy group and the like. It is preferable to use a tertiary and / or tertiary alkoxy group.

  In addition, the content of hydroxyl groups as Si—OH groups in the molecule should be less than 2% by weight, preferably less than 1% by weight. This is because when the hydroxyl group content is 2% by weight or more, when melt-mixing with a synthetic resin containing an aromatic ring, a condensation reaction between Si-OH groups easily occurs, and the organopolysiloxane has a high molecular weight and is dispersed. The resin composition becomes poor in transparency and impact strength, and the surface transferability during combustion deteriorates and the flame retardancy decreases, resulting in poor moldability during rework and recycling. From this point, the hydroxyl group content is more preferably 1% by weight or less.

  It should be noted that the smaller the number of hydroxyl groups as the alkoxy group and Si—OH group, the better.

  Thus, an organopolysiloxane containing a phenyl group and having an alkoxy group content in the molecule and a hydroxyl group content of less than 2% by weight as a Si-OH group is essentially non-reactive, Since it has heat resistance, its structure hardly changes in a temperature range of 350 ° C. or lower, and thus it is possible to obtain a flame-retardant resin composition that can be recycled. Further, any of these organopolysiloxanes does not generate harmful gas during combustion.

  The weight average molecular weight of the (B) component organopolysiloxane is 2,000 or less, but if it is too small, the content of the low molecular weight substance becomes high, and when melt-mixed with a synthetic resin containing an aromatic ring, The component which volatilizes increases and there exists a possibility that a flame-retardant effect may not be exhibited. Therefore, from this point, it is preferable to set it to 410 or more and 2,000 or less, and further preferably set it to 500 or more and 2,000 or less.

  Although this organopolysiloxane has no reactive group other than the remaining hydroxyl group or alkoxy group, it can impart flame retardancy by adding a small amount of 10% by weight or less of the entire composition. When this composition is burned, an organopolysiloxane containing a phenyl group easily forms a non-flammable Si-C ceramic layer with a synthetic resin containing an aromatic ring by coupling each aromatic ring. It is thought that it forms a high flame retardant effect.

  Furthermore, the phenyl group content of the organopolysiloxane greatly affects the moldability of the resin composition, the transparency of the molded product, the mechanical strength, and the like. The higher the phenyl group content of the organopolysiloxane, the higher the dispersibility and compatibility with the synthetic resin containing the aromatic ring, and the better the moldability, transparency and mechanical strength.

Therefore, in order to make the above-mentioned flame retarding mechanism work effectively, and to make the moldability of the resin composition, the transparency of the molded product, the mechanical strength, etc. at a good level, it is bonded to the silicon atom of the organopolysiloxane molecule. The proportion of the phenyl group in all organic substituents is preferably 30 to 90% in terms of weight. In addition, said phenyl group content in this invention is defined as follows. That is, the organopolysiloxane of component (B) has the following average composition formula (1)
(C ₆ H ₅ ) _m R _n Si (OR ′) _p (OH) _q O _{(4-mnpq) / 2} (1)
(In the formula, R represents an organic substituent other than a phenyl group and an alkoxy group, is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ′ is a monovalent hydrocarbon having 1 to 6 carbon atoms. Group.)
Is represented by the following formula (where MW represents the molecular weight of each substituent).
Phenyl group content (% by weight) =
{MW (C ₆ H ₅ ) × m × 100}
/ {MW (C ₆ H ₅ ) × m + MW (R) × n + MW (R ′) × p}

  In the present invention, the phenyl group content is preferably in the range of 30 to 90% by weight. If the phenyl group content is too low, the compatibility with the synthetic resin containing an aromatic ring in the molecule is lowered, so that the dispersibility is insufficient and the moldability of the resin composition and the transparency and impact strength of the molded product are poor. In addition, since the number of phenyl groups decreases, the flame retardant effect also decreases. On the other hand, if the phenyl group content is too high, the compatibility with the synthetic resin containing an aromatic ring becomes too high, and the surface migration at the time of combustion deteriorates, so that the flame retardant effect also decreases in this case. More preferably, the phenyl group content is 50 to 90% by weight.

  In the above formula (1), R is preferably an alkyl group, particularly a methyl group, and R 'is also preferably an alkyl group, but a secondary or tertiary alkyl group having 3 to 6 carbon atoms is particularly preferable. m, n, p, q are 0.5 ≦ m ≦ 2.0, 0.1 ≦ n ≦ 2.3, 0 ≦ p ≦ 0.13, 0 ≦ q ≦ 0.17, 0.92 ≦ m + n + p + q. It is preferably selected from positive numbers satisfying ≦ 2.85.

In addition, the organopolysiloxane of component (B) contains ¹⁰ to 75 mol% of monofunctional siloxane units represented by R ¹ R ² R ³ SiO _1/2 in the molecule,
R ⁴ R ⁵ difunctional siloxane units represented by SiO _2/2 0 to 80 mol%,
0 to 80 mol% of trifunctional siloxane units represented by R ⁶ SiO _3/2,
0 to 15 mol% of tetrafunctional siloxane unit represented by SiO _4/2
What is contained can be used. Preferably,
20 to 70 mol% of monofunctional siloxane units represented by R ¹ R ² R ³ SiO _1/2
R ⁴ R ⁵ difunctional siloxane units represented by SiO _2/2 0 to 80 mol%,
0 to 80 mol% of trifunctional siloxane units represented by R ⁶ SiO _3/2,
0 to 10 mol% of tetrafunctional siloxane unit represented by SiO _4/2
Use what is contained. Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each selected from an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different. And alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and cyclohexyl group, alkenyl groups such as vinyl group and allyl group, phenyl group and the like, but methyl group and phenyl group are particularly preferable. .

  In general, the structure of organopolysiloxane is composed of monofunctional siloxane units (M units), bifunctional siloxane units (D units), trifunctional siloxane units (T units), and tetrafunctional siloxane units (Q units). It is configured by any combination. In the present invention, preferred combinations of these units are M / D system, M / T system, M / D / T system, M / D / Q system, M / T / Q system, M / D / T / The Q system, more preferably the M / D / T system, provides good flame retardancy and dispersibility. On the other hand, the molecular weight is too low for the M alone system and the flame retardant effect is not exerted. In the M / Q system, the inorganic properties of the organopolysiloxane are too strong and the dispersibility in the synthetic resin containing the aromatic ring is poor. There is. For the same reason, in the M / D / Q system and the M / D / T / Q system, the content of the Q unit is preferably 15 mol% or less, more preferably 10 mol% or less.

  The organopolysiloxane of component (B) contains only methyl groups as organic substituents other than phenyl groups and residual alkoxy groups in the molecule, that is, R = methyl group in the average composition formula (1). This is preferable from the viewpoint of ease of production and cost.

  In the present invention, the flame retardant effect is insufficient when the blending amount of the organopolysiloxane of the component (B) is less than 0.1 parts by weight with respect to 100 parts by weight of the synthetic resin containing an aromatic ring in the molecule of the component (A). However, if the amount exceeds 10 parts by weight, not only the flame retardancy effect is improved, but also the mechanical properties such as impact strength are greatly reduced. The amount is preferably 0.2 to 5 parts by weight.

  The organopolysiloxane used in the present invention can be produced by a conventionally known method. For example, according to the molecular structure and molecular weight of the desired organopolysiloxane, after reacting appropriate water with organochlorosilanes having a phenyl group, an organic solvent added as necessary, by-product hydrochloric acid and low boiling point are added. By removing, an organopolysiloxane containing a phenyl group and a monofunctional siloxane unit can be obtained. In this case, as a method for introducing a monofunctional siloxane unit, triorganochlorosilane can be reacted with a partial condensate from the initial hydrolysis or after hydrolysis. It is also possible to react hexaorganodisiloxane with the partially condensed product after hydrolysis. In this case, use an acid catalyst such as hydrochloric acid or sulfuric acid or a basic catalyst such as potassium hydroxide or sodium hydroxide. It is preferable to do. Furthermore, it is also suitable to use a variety of silylating agents such as hexaorganodisilazane to block the remaining alkoxy groups and hydroxyl groups as Si—OH groups. It is not limited.

  In addition, when alkoxysilanes having a phenyl group are used as starting materials, a predetermined amount of water is added according to the molecular structure and molecular weight of the target organopolysiloxane, and the hydrolysis reaction proceeds. In this case, it is preferable to use an acid catalyst such as hydrochloric acid or acetic acid, or a basic catalyst such as ammonia or sodium hydroxide. Polysiloxane can be obtained. The above-described means may be applied to the method of introducing the monofunctional siloxane unit. In any case, the phenyl group content, the content of each siloxane unit, and the molecular weight can be adjusted by changing the type and amount of each raw material.

  When flame retardancy is improved by adding an organic alkali metal salt and / or an organic alkaline earth metal salt such as sodium diphenylsulfone-3-sulfonate or sodium perfluoroalkanesulfonate to the flame-retardant resin composition of the present invention There is. These compounds act as carbonization promoters that promote the formation of non-combustible Si-C ceramic layers by coupling aromatic rings, and all conventionally known compounds can be applied to the composition of the present invention. When adding, 0.001-5 weight part is suitable with respect to 100 weight part of synthetic resins containing the aromatic ring of (A) component. If it is less than 0.001 part by weight, the added effect cannot be expected, and if it exceeds 5 parts by weight, the appearance and strength of the molded product may be adversely affected. Specific examples include sodium benzenesulfonate, disodium naphthalene-2,6-disulfonate, sodium diphenylsulfone-3-sulfonate, sodium perfluorobutanesulfonate, and the like.

  Moreover, the flame retardant resin composition of this invention can mix | blend an inorganic filler as a reinforcing agent. Examples thereof include silicas such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, and the like. The average particle size and shape of these inorganic fillers are not particularly limited, but spherical fused silica having an average particle size of 5 to 40 μm is particularly preferable from the viewpoints of moldability and fluidity. When blended, 400 to 1200 parts by weight is appropriate for 100 parts by weight of the synthetic resin containing the aromatic ring of component (A). If it is less than 400 parts by weight, the reinforcing effect cannot be expected so much, and if it exceeds 1200 parts by weight, the moldability may be adversely affected. In addition, in order to strengthen the bond strength between the synthetic resin and the inorganic filler, it is preferable to blend a material that has been surface-treated with a coupling agent such as a silane coupling agent or a titanate coupling agent. Examples of such coupling agents include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, aminosilane such as N-phenyl-γ-aminopropyltrimethoxysilane, and mercapto such as γ-mercaptopropyltrimethoxysilane Examples include silane. Here, the blending amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

  If necessary, the flame retardant resin composition of the present invention further includes drip such as an antioxidant, a neutralizer, an ultraviolet absorber, an antistatic agent, a pigment, a dispersant, a lubricant, a thickener, and a fluororesin. What is normally mix | blended, such as an inhibitor, a low stress agent, waxes, and a coloring agent, can be mix | blended.

  Each of these components is metered and mixed, and conventional equipment and methods for rubber and plastic can be used. That is, each component can be sufficiently mixed and dispersed using a mixing stirrer such as a ribbon blender or a Henschel mixer, and then kneaded using a melt kneader such as a Banbury roll or an extruder to obtain the target product.

  Examples of the molding method include an injection molding method, an extrusion molding method, a compression molding method, and a vacuum molding method.

EXAMPLES Hereinafter, although a preparation example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, phenyl group content (weight%) in all the organic substituents in each organopolysiloxane obtained in the following preparation examples is calculated by the following formula from the NMR measurement data, and the alkoxy group content in all molecules. Methane gas produced by reacting a predetermined amount of organopolysiloxane with a methyl Grignard reagent according to the Grignard method according to NMR measurement data and the hydroxyl group content (wt%) as Si-OH groups in all molecules. The weight average molecular weight was converted from GPC measurement data using a calibration curve prepared with a polystyrene standard sample.
Phenyl group content (% by weight) =
{MW (C ₆ H ₅ ) × m × 100}
/ {MW (C ₆ H ₅ ) × m + MW (R) × n + MW (R ′) × p}

[Preparation Example 1]
A 2 L flask equipped with a stirrer, a cooling device, and a thermometer was charged with 423 g (2 mol) of phenyltrichlorosilane, 434 g (4 mol) of trimethylchlorosilane, and 194 g of toluene. A mixture of 108 g (6 mol) of water and 30 g (0.5 mol) of isopropanol was charged into the dropping funnel and added dropwise to the flask with stirring for 1 hour. The hydrogen chloride gas generated during the hydrolysis-condensation reaction was removed from the system. The reaction proceeded while removing. After completion of the dropwise addition, the mixture was further heated in an oil bath and aged at an internal temperature of 60 ° C. for 1 hour. Subsequently, excess water, unreacted isopropanol, hydrogen chloride and toluene were removed by distillation under reduced pressure to obtain 490 g of liquid phenyl group-containing organopolysiloxane-1.

[Preparation Example 2]
In Preparation Example 1, 212 g (1 mol) of phenyltrichlorosilane, 253 g (1 mol) of diphenyldichlorosilane, 326 g (3 mol) of trimethylchlorosilane, and 190 g of toluene were placed in a 2 L flask, and 90 g (5 mol) of water and isopropanol were added to the dropping funnel. 480 g of liquid phenyl group-containing organopolysiloxane-2 was obtained in the same manner except that 30 g (0.5 mol) of the mixed solution was charged and subjected to hydrolysis condensation reaction.

[Preparation Example 3]
In Preparation Example 1, 212 g (1 mol) of phenyltrichlorosilane and 759 g (3 mol) of diphenyldichlorosilane were charged into a 2 L flask, and a mixture of 63 g (3.5 mol) of water and 180 g (3 mol) of isopropanol was added to the dropping funnel. Then, hydrolytic condensation reaction and alkoxylation reaction were carried out, 324 g (4 mol) of hexamethyldisiloxane and 120 g of 20% aqueous hydrochloric acid were added, and stirring was continued for 1 hour at an internal temperature of 40 ° C. 810 g of liquid phenyl group-containing organopolysiloxane-3 was obtained in the same manner except that the reaction was carried out.

[Preparation Examples 4 to 10]
In the same preparation method as in Preparation Example 1, various types of organopolysiloxanes 4 to 10 were obtained by changing the types of organochlorosilane and alcohol to be used and the charged amounts (molar ratio) of organochlorosilane, water and alcohol.

  Table 1 shows various physical property values of organopolysiloxanes 1 to 10 obtained in Preparation Examples 1 to 10.

[ Reference Examples 1-6, Comparative Examples 1-6]
In the composition shown in Table 2, 3 parts by weight of organopolysiloxane is added to 100 parts by weight of aromatic polycarbonate resin, and 10 parts by weight of organopolysiloxane is added to 100 parts by weight of aromatic epoxy resin, and premixed in an automatic mortar. After that, melt kneading (kneading temperature: 280 ° C.) was performed with a single screw extruder.

  The polycarbonate resin is Caliber 200-20 (viscosity average molecular weight of about 20,000) manufactured by Sumitomo Dow Co., Ltd., and the epoxy resin is YX4000HK (epoxy equivalent 190) manufactured by Yuka Shell Co., Ltd. as a phenol resin curing agent. What added the same weight part XL-225-3L (phenol equivalent 168) by Corporation | KK was used.

  Evaluation of flame retardancy conforms to the standard set by Underwriters Laboratories INC (UL94: Standard for Flammability Test of Plastic Materials for Equipment Parts), and uses 1/16 inch thick plate did.

  For optical transparency, a visible absorptiometer was used. The test piece is a 10 mm-thick molded plate, the visible light transmittance per 10 mm of the optical path length in the thickness direction is measured, and evaluated by the ratio of the transmittance of each test piece to the test piece to which no organopolysiloxane is added. did. In this case, a transmittance ratio of 70% or more was evaluated as ◯, and a transmittance ratio of less than 70% was evaluated as ×.

Recyclability was evaluated by adding 1 part by weight of organopolysiloxane to 100 parts by weight of the aromatic polycarbonate resin composition once molded by the above method, performing melt-kneading and molding. Evaluation was made by observing the external appearance, and the case where molding was possible without any problem as in the first time was evaluated as ◯, and the case where the external appearance was uneven or the shape was incomplete was evaluated as X.
The results are shown in Table 2.

Claims (7)

(A) 100 parts by weight of a synthetic resin containing an aromatic ring in the molecule,
(B) A siloxane unit containing a phenyl group as an essential substituent for bonding to a silicon atom in the molecule and represented by R ¹ R ² R ³ SiO _1/2 (provided that R ¹ , R ² and R ³ are Each having the same or different carbon number 1 to 6 unsubstituted or substituted monovalent hydrocarbon group), and the hydroxyl group content as an alkoxy group and Si-OH group in the molecule is less than 2% by weight, respectively. And 0.1 to 10 parts by weight of an organopolysiloxane having a weight average molecular weight of 2,000 or less, and further sodium benzenesulfonate, disodium naphthalene-2,6-disulfonate, diphenylsulfone-3-sulfone A flame retardant resin composition comprising one or two or more selected from sodium sulfate and sodium perfluorobutanesulfonate .   The flame-retardant resin composition according to claim 1, wherein the organopolysiloxane (B) has a weight average molecular weight of 410 to 2,000.   The flame retardant according to claim 1 or 2, wherein the organopolysiloxane of component (B) has a proportion of phenyl groups in the total organic substituents bonded to silicon atoms in the molecule of 30 to 90% in terms of weight. Resin composition. The organopolysiloxane of component (B) contains ¹⁰ to 75 mol% of siloxane units represented by R ¹ R ² R ³ SiO _1/2 in the molecule,
Siloxane units represented by R ⁴ R ⁵ SiO _2/2 0~80 mol%,
Siloxane units represented by R ⁶ SiO _3/2 0 to 80 mol%,
0-15 mol% of siloxane units represented by SiO _4/2
(However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are the same or different unsubstituted or substituted monovalent hydrocarbon groups having 1 to 6 carbon atoms.)
The flame retardant resin composition according to any one of claims 1 to 3, wherein the flame retardant resin composition is contained.   The organopolysiloxane as component (B) contains only a methyl group as an organic substituent bonded to a silicon atom other than a phenyl group and a residual alkoxy group in the molecule. Flame retardant resin composition.   The flame retardant resin composition according to any one of claims 1 to 5, wherein the synthetic resin containing an aromatic ring in the molecule of component (A) is an aromatic polycarbonate resin or an aromatic epoxy resin. The flame-retardant resin composition according to any one of claims 1 to 6 , comprising an inorganic filler.