JP2003049060A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition having excellent impact resistance and flame-retardance while keeping the characteristic physical properties of polycarbonate resins such as transparency by compounding a specific silicon-containing compound having high flame-retarding effect. SOLUTION: This polycarbonate resin composition is composed of 100 pts.wt. of a polycarbonate resin and 0.1-20 pts.wt. of a silicon-containing polymer having a specific structure containing a phenolphthalein skeleton or a phenolphthalein derivative skeleton.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame retarded polycarbonate resin composition. For more details,
The present invention relates to a transparent polycarbonate resin composition containing no halogen or phosphorus element and having good flame resistance and impact resistance.

[0002]

2. Description of the Related Art Polycarbonate resin is widely used as an engineering plastic excellent in mechanical strength, electrical characteristics, transparency, etc. in various fields such as OA equipment, electric / electronic equipment fields, automobile fields, and construction fields. . Among these fields of application, there are fields that require a high degree of flame retardancy, mainly in the fields of office automation equipment and electric / electronic equipment, and flame retardant polycarbonate resin compositions to which various flame retardants have been added are It is used. Generally, an organic halogen compound, a halogenated polycarbonate copolymer, or these and antimony trioxide are added to these resin compositions. However, these flame-retardant resin compositions have a drawback that harmful halogen-based gas is generated during combustion. Therefore, phosphorus-based flame retardants have been used in place of halogen-based flame retardants. However, phosphorus compounds generate phosphoric acid due to hydrolysis, which may cause metal corrosion around the resin composition. Therefore, in recent years, a composition in which flame retardancy is imparted by a silicone compound that does not generate a harmful gas and does not generate an acid by hydrolysis has been disclosed.

Japanese Patent Publication No. 62-60421 discloses a flame-retardant resin composition containing a silicone resin containing 80% by weight or more of a trifunctional siloxane unit.
However, since the silicone resin substantially composed of only trifunctional siloxane units is used with an emphasis on melt processability with an organic resin, the flame retarding effect is small, and the silicone resin is 10% by weight or more. If it is not added, no effective flame retardant effect is obtained.

Japanese Patent Publication No. 63-31513 describes a heat-resistant and oxidation-resistant resin composition to which an alkoxy-terminated silicone resin is added. However, since a liquid low molecular weight silicone with a high content of alkoxy groups is preferably used, even if added in a small amount, it has a great adverse effect on the appearance and strength of the molded product, and it easily bleeds out from the resin molded product and further has a hydrolysis reactivity. However, since a flammable low boiling point compound such as alcohol is produced as a by-product, the flame retardant effect cannot be expected so much.

Japanese Patent Publication No. 3-48947, Japanese Patent Publication 7-78
171 and JP-A-7-33971 disclose a flame-retardant resin composition containing a silicone resin containing a monofunctional siloxane unit and a tetrafunctional siloxane unit.
128434 discloses a flame-retardant resin composition to which a silicone resin containing a siloxane unit having a vinyl group is added. However, in any of the compositions, in order to obtain a sufficient flame retardant effect, it is necessary to increase the amount of the silicone resin added, or to use an inorganic filler such as aluminum hydroxide, a halogen and a phosphorus compound together.

In order to enhance the flame retardancy of polycarbonate resin, for example, Japanese Patent Publication No. 47-40445 discloses a polycarbonate resin composition to which an alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid is added. Has been done. However, the technique disclosed herein has a drawback in that dripping occurs during combustion and the material immediately below is ignited.

Japanese Patent Publication No. 60-16473 discloses a technique for preventing dripping during combustion by mixing a polycarbonate resin with an organic alkali metal salt or an organic alkaline earth metal salt and further adding siloxane. ing. JP-A-8-176425 discloses a flame-retardant resin composition obtained by adding an organopolysiloxane having an epoxy group and an alkali metal salt of an organic sulfonic acid.
JP-A-176427 describes a flame-retardant resin composition containing a polycarbonate resin modified with a phenolic hydroxyl group-containing organopolysiloxane and an organic alkali metal salt. Further, JP-A-9-169914 describes a composition in which petroleum heavy oils or pitches are used in combination with a silicone compound to improve the flame retardant effect. However, these flame-retardant silicone resins have insufficient dispersibility and compatibility with the polycarbonate resin, and only low transparency or opaque ones when the blending amount is large.

In JP-A-7-258532, flame retardancy is imparted by adding an organic alkali (earth) metal salt to a mixture of a branched polycarbonate and a linear polycarbonate, but it is high in a thin molded product. In order to impart flame retardancy, it is necessary to increase the amount added, and transparency is lost.

Japanese Unexamined Patent Publication (Kokai) No. 11-222559 discloses a technique of imparting flame retardancy while maintaining transparency by adding an organosiloxane having a specific structure to a resin containing an aromatic ring. The transparency of the obtained resin composition is not high.

Japanese Unexamined Patent Publication No. 4-359960 discloses a technique for obtaining a transparent flame-retardant resin composition by adding poly (aryloxysiloxane) having a specific biphenyl structure to an aromatic polycarbonate resin. However, it is necessary to add 20 parts by weight or more of poly (aryloxysiloxane), the flame retardance is not sufficient, and it is not economically advantageous.

In addition to the above, a technique for a polycarbonate resin having flame retardancy by itself is also disclosed.
Phenolphthalein-containing polycarbonate resin is described in U.S. Pat. No. 3,360,036 and JP-B-60-4920.
No. 8, G.M. S. Lin et al. (Journal
of Polymer Science, Polym
er Chemistry Edition, Vo
l. 19, p. 2659 (1981)),
This resin has high heat resistance and flame retardancy.

Further, Japanese Patent Publication No. 62-56174 discloses an organosiloxane-containing phenolphthalein polycarbonate resin having improved high melting point and poor handling property during molding, which are disadvantages of the phenolphthalein-containing polycarbonate resin. . This resin is a copolymer of polysiloxane and polycarbonate. In addition, the synthetic method is an industrially disadvantageous method, since it requires a multi-step reaction of synthesizing a polyorganosiloxane having chlorine at the terminal and reacting phenolphthalein with phosgene. However, there is a disadvantage that it is not economically advantageous.

[0013]

As described above, when the silicone resin is added, a sufficient flame retardant effect cannot be obtained unless the addition amount is increased, but when the addition amount is increased, the moldability of the polycarbonate resin composition is improved. , Appearance and transparency of molded products,
There has been a problem that physical properties such as mechanical strength are significantly lowered. An object of the present invention is to provide a polycarbonate-based resin composition that does not contain halogen and phosphorus elements and that retains the original transparency of the polycarbonate-based resin and that has good flame resistance and impact resistance.

As a result of earnest studies aimed at achieving such an object, the present inventors have found that a phenolphthalein or a phenolphthalein derivative skeleton is added to a polycarbonate resin, particularly a polycarbonate resin having a structural viscosity index of 1.36 or more. A resin composition containing a silicon-containing compound having a specific structure and, if necessary, an alkali or alkaline earth metal salt of an organic Bronsted acid having 1 or more carbon atoms is transparent, which is an inherent property of a polycarbonate resin. In addition to the properties, the inventors have found that excellent impact resistance and high flame retardancy are exhibited, and have reached the present invention.

[0015]

That is, according to the present invention, silicon comprising (A) 100 parts by weight of a polycarbonate resin (component A) and (B) a structural unit [1] represented by the following formula [1]: Containing polymer (component B) 0.1-2
A polycarbonate resin composition comprising 0 parts by weight is provided.

[0016]

[Chemical 7]

(In the structural unit [1], R ¹ is the structural unit [2] represented by the following formula [2], the structural unit [3-I] represented by the following formula [3-I] and the following formula [3] -II]
Of the structural unit [3-II], the structural unit [2] and the structural unit [3-I] + the structural unit [3-I
I]) is in a molar ratio range of 100: 0 to 20:80. R ² and R ³ are at least selected from the group consisting of a hydrogen atom, a saturated alkyl group having 1 to 12 carbon atoms, an unsaturated alkyl group having 2 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 5 to 16 carbon atoms. It is one group, and a part of hydrogen atoms thereof may be replaced by a fluorine atom. j and k are 0 or 1, and m is an integer of 1-10. )

[0018]

[Chemical 8]

(R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen atom, fluorine atom, nitro group, saturated alkyl group having 1 to 12 carbon atoms, unsaturated alkyl group having 2 to 12 carbon atoms. It is at least one group selected from the group consisting of a group and a substituted or unsubstituted aryl group having 5 to 16 carbon atoms, and a part of hydrogen atoms thereof may be substituted with a fluorine atom.
Q is an oxygen atom or —NR ¹⁰ — (wherein R ¹⁰ is a hydrogen atom, a saturated alkyl group having 1 to 12 carbon atoms, or 2 to 12 carbon atoms).
Of at least one group selected from the group consisting of an unsaturated alkyl group and a substituted or unsubstituted aryl group having 5 to 16 carbon atoms, some of which hydrogen atoms may be replaced by fluorine atoms. ), And Z is -C (=
O) - or -SO ₂ - it is. )

[0020]

[Chemical 9]

[0021]

[Chemical 10]

(In the formula, X is a single bond, -C (R ¹⁷ ) (R
^{18) -, - C (=} O) -, - SO 2 -, - S -, - O
-, At least one group selected from the group consisting of groups represented by the following formula [4-I] and the following formula [4-II]. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R
¹⁸ is a hydrogen atom, a fluorine atom, a nitro group, a carbon number of 1 to 12
Which is at least one group selected from the group consisting of a saturated alkyl group having 2 to 12 carbon atoms, an unsaturated alkyl group having 2 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 5 to 16 carbon atoms,
Some hydrogen atoms may be replaced by fluorine atoms. p is an integer of 0-2. )

[0023]

[Chemical 11]

[0024]

[Chemical 12]

(Wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ ,
R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are hydrogen atom, fluorine atom, nitro group, saturated alkyl group having 1 to 12 carbon atoms, unsaturated alkyl group having 2 to 12 carbon atoms and 5 to 16 carbon atoms. Is at least one group selected from the group consisting of the substituted or unsubstituted aryl groups of, and some of the hydrogen atoms may be substituted with fluorine atoms. ) Hereinafter, the present invention will be described in detail.

The polycarbonate resin used in the present invention is an aromatic polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor, or a divalent phenol and an aliphatic diacid and a carbonate precursor. Polyester carbonate resin, or a branched polycarbonate resin obtained by copolymerizing a dihydric phenol, a trifunctional or higher polyfunctional compound, a carbonate precursor and an aliphatic diacid as necessary, and the like, and as an example. It can be obtained by an interfacial polymerization method or a melting method.

Examples of the dihydric phenol used include hydroquinone, resorcinol, 4,4'-biphenol, bis (4-hydroxyphenyl) methane, 1,
1-bis (4-hydroxyphenyl) ethane, 2,2-
Bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4 -Hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-)
Methylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,
2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2-bis (4-
Hydroxy-3-methoxyphenyl) propane, 1,1
-Bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5
-Trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 4,4'-dihydroxy-3,3'- Dimethylphenyl ether, 4,4 '-(p-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediisopropylidene) diphenol, bis (4-
Hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfide, bis ( 4-hydroxyphenyl) ketone, 9,9-bis (4-hydroxyphenyl)
Fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and the like can be mentioned. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkane-based, with bisphenol A being especially preferred.

Examples of the aliphatic diacid include, for example, 8 to 2 carbon atoms.
It is 0, preferably an aliphatic diacid having 10 to 12 carbon atoms.
The aliphatic diacid may be linear, branched or cyclic, and α, ω-dicarboxylic acid is preferable.
Examples of preferable aliphatic diacids include linear saturated aliphatic dicarboxylic acids such as decanedioic acid (sebacic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and eicosanedioic acid, and sebacic acid and dodecane. Diacids are especially preferred.

Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate, and the like. Specifically, phosgene, diphenyl carbonate,
Examples thereof include dihaloformates of dihydric phenols.

In producing a polycarbonate resin, the above dihydric phenols may be used alone or in combination of two or more kinds, and the dihydric phenol and the aliphatic diacid may be used alone or You may use 2 or more types together. The content ratio of the dihydric phenol and the aliphatic diacid can be arbitrarily adjusted, but it is desirable that at least 40 mol% or more in the polycarbonate resin be derived from bisphenol A. In addition, the aliphatic diacid component is preferably 20 mol% or less in the polycarbonate resin from the viewpoint of improving heat resistance and flame retardancy.

Examples of the trifunctional or higher functional compound used as a branching agent include phloroglucin, phlorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 2,4. , 6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,2-bis (4,4-bis (4-hydroxyphenyl) cyclohexyl) propane, 2,6-bis (2- Hydroxy-5
-Methylbenzyl) -4-methylphenol, 4- {4
-[1,1-bis (4-hydroxyphenyl) ethyl]
Benzene} -α, α-dimethylbenzylphenol, bis (2-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl) methane, tetrakis (4-hydroxyphenyl) methane, tris (4- Hydroxyphenyl) phenylmethane, trisphenol, 2,2-bis (2,4-dihydroxyphenyl) propane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) Examples thereof include benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof. These branching agents may be used alone or in combination of two or more. Among them, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-)
4-hydroxyphenyl) ethane is preferred, especially 1,
1,1-tris (4-hydroxyphenyl) ethane is preferred. The branching agent is preferably used in an amount of 0.05 to 3 mol with respect to 100 mol of the dihydric phenol.

The polycarbonate resin of the present invention may be a mixture of two or more of the above polycarbonate resins.

The basic means for producing a polycarbonate resin will be briefly described below. It should be noted that even a polycarbonate-based resin obtained by a production method other than the following means does not hinder the achievement of the object of the present invention.

The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, which is carried out in the presence of an acid binder and an organic solvent.

As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amine compounds such as pyridine are used.

Examples of the organic solvent include methylene chloride,
A halogenated hydrocarbon such as chlorobenzene is used.

In order to accelerate the reaction, for example, triethylamine, tetra-n-butylammonium bromide,
A tertiary amine such as tetra-n-butylphosphonium bromide, a quaternary ammonium compound, a catalyst such as a quaternary phosphonium compound can be used, and examples of the terminal terminator include phenol, p-tert-butylphenol, p- Monofunctional phenols such as cumylphenol and isooctylphenol can be used.

The reaction temperature is usually 0 to 40 ° C., and the reaction time is 1
The pH during the reaction is preferably maintained at 9 or higher for about 0 minutes to 5 hours. In addition, it is not necessary that all of the molecular chain terminals have a structure derived from the terminal stopper.

The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonate ester,
It is carried out by a method in which a dihydric phenol and a carbonate ester are heated and mixed in the presence of an inert gas to distill off the alcohol or phenol produced.

The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually 120 to 350 ° C.
Is the range. At the initial stage of the reaction, a terminal stopper can be added simultaneously with the dihydric phenol or the like or at an intermediate stage of the reaction. In the latter half of the reaction, the system is 1000 to 10 Pa.
The pressure is reduced to a certain degree to facilitate the distillation of the produced alcohol or phenol. The reaction time is about 1 to 10 hours. Further, in order to accelerate the polymerization rate, a polymerization catalyst usually used in esterification reaction and transesterification reaction can be used.

The carbonate ester used in this transesterification reaction has a substituted or unsubstituted carbon number of 6
-10 aryl group, aralkyl group or 1 to 10 carbon atoms
And an ester such as an alkyl group of 4. Examples thereof include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable. When the aliphatic diacid is contained, it is preferable that the aliphatic diacid is converted into an ester such as diphenyl ester in advance.

The viscosity average molecular weight of the polycarbonate resin (component A) used in the present invention is 10,000 to 4
A range of 10,000 is preferred. Viscosity average molecular weight (Mv)
Is a specific viscosity (η obtained from a solution of 0.7 g of a polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C.
_SP ) is inserted in the following equation. η _SP /C=[η]+0.45[η] ² C [η] = 1.23 × 10 ⁻⁴ Mv ^0.83 (where [η] is the intrinsic viscosity and C is the polymer concentration is 0.7) In the present invention In the polycarbonate resin used,
The structural viscosity index is preferably 1.36 or more,
A range of 1.36 to 3.5 is more preferable, and a range of 1.5
Those in the range of to 3.5 are particularly preferable. The structural viscosity index (N) is obtained from the following equation representing the melting characteristics of the polycarbonate resin.

Q = K.P ^N (where Q is the flow rate of the molten resin (mL / sec), K is a constant, P is the pressure (MPa), and N is the structural viscosity index). It shows fluidity, and shows that non-Newtonian fluidity increases as N increases.

The polycarbonate resin having such a structural viscosity index has a viscosity average molecular weight of 70,000 to 2
50,000 high molecular weight polycarbonate resins and branched polycarbonate resins are included. In addition, these high-molecular-weight polycarbonate-based resins and branched polycarbonate-based resins and viscosity-average molecular weights of 10,000 to 40,0
A mixture of No. 00 with a linear polycarbonate resin can also be suitably used as long as it satisfies the above range of structural viscosity index.

In the present invention, one of the preferred embodiments of the polycarbonate resin (component A) is (A-1)
A polycarbonate resin (A-1 component) having a viscosity average molecular weight of 10,000 to 40,000 and a high molecular weight polycarbonate resin (A-2 component) having a viscosity average molecular weight of 70,000 to 250,000. Mention may be made of mixtures.

The mixing ratio of the A-1 component and the A-2 component is
Assuming that the total of the components A-1 and A-2 is 100% by weight,
The A-1 component is preferably 65 to 95% by weight, the A-2 component is 5 to 35% by weight, and more preferably the A-1 component is 75 to 95% by weight.
95% by weight, and A-2 component is 5 to 25% by weight.

The viscosity average molecular weight of the blended polycarbonate resin is preferably 11,000 to 40,000, more preferably 18,000 to 40,000, and even more preferably 20,000 to 40,000.

The high molecular weight polycarbonate resin is
70,000 to 250, which cannot be used alone for melt molding,
000, preferably 100,000-160,000 viscosity average molecular weight. Viscosity average molecular weight 70,000
When the above is used, the compounding amount for improving the melting property becomes an appropriate amount, which is preferable because molding is easy, and
When a viscosity average molecular weight of 250,000 or less is used, a molded product having a good dispersion during mixing and an excellent appearance can be obtained.

In the present invention, as another preferable embodiment of the polycarbonate resin (component A), A-3
Assuming that the total of the component and the A-4 component is 100% by weight, (A-
3) Linear polycarbonate resin (A-3 component) 0
It is a polycarbonate resin composed of 95% by weight and 5 to 100% by weight of (A-4) branched polycarbonate resin (A-4 component).

The viscosity average molecular weight of the branched polycarbonate resin (component A-4) is 10,000 to 40,000.
Is preferred, 15,000 to 35,000 is more preferred, and 20,000 to 30,000 is even more preferred. By using a branched polycarbonate resin having such a molecular weight range, sufficient flame retardancy can be obtained, a good molded product can be easily obtained by melt molding, and transparency is sufficient, which is preferable.

Further, the linear polycarbonate resin (A
-3 component) has a viscosity average molecular weight of 10,000 to 40,
000 is preferable, 15,000 to 35,000 is more preferable, and 20,000 to 30,000 is further preferable.

The viscosity average molecular weight of the mixture of the A-3 component and the A-4 component is preferably in the range of 10,000 to 40,000.

In the present invention, the silicon-containing polymer used as the component B is a silicon-containing polymer composed of the structural unit [1] represented by the above formula [1], and R ¹ is represented by the above formula [2]. The structural unit [2], the structural unit [3-I] represented by the formula [3-I], and the formula [3-II]
Of the structural unit [3-II], the structural unit [2] and the structural unit [3-I] + the structural unit [3-I
I]) is in a molar ratio of 100: 0 to 20:80, preferably 100: 0 to 30:70, and more preferably 100: 0 to 50:50. Also,
The ratio between the structural unit [3-I] and the structural unit [3-II] is arbitrary, but the structural unit [3-I] and the structural unit [3-I]
I] is preferably in the range of 100: 0 to 50:50, and more preferably in the range of 100: 0 to 70:30, in terms of molar ratio.

In the structural unit [1], R ¹ is structural unit [2], structural unit [3-I] and structural unit [3-I
When it is composed of two or more kinds of constitutional units in I], the silicon-containing polymer of the present invention includes copolymers such as block copolymers and random copolymers, and random copolymers are particularly preferable. .

R ² and R ³ of the structural unit [1] are hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group and the like having 1 to 12 carbon atoms.
Unsaturated alkyl group having 2 to 12 carbon atoms such as saturated alkyl group, vinyl group and propenyl group, and 5 carbon atoms such as cyclopentadienyl group, phenyl group, pyridyl group, tolyl group, xylyl group and naphthyl group It is at least one group selected from the group consisting of 16 substituted or unsubstituted aryl groups, and a part of hydrogen atoms thereof such as trifluoropropyl may be substituted with a fluorine atom. Especially hydrogen atom, methyl group, ethyl group, propyl group, vinyl group,
Butyl and phenyl groups are preferred. Particularly, the methyl group is economically desirable because the raw material is inexpensive. In the structural unit [1], when the number of siloxane units is two or more, examples of the silicon-containing polymer include copolymers such as block copolymers and random copolymers, and random copolymers are particularly preferable. .

In the structural unit [1], j and k are 0 or 1, and preferably both j and k are 0. m is a positive number of 1 to 10, preferably a positive number of 1 to 2, and particularly preferably 1.

R ⁴ , R ⁵ , R ⁶ , R ⁷ in the structural unit [2],
R ⁸ and R ⁹ are hydrogen atom, fluorine atom, nitro group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, saturated alkyl group having 1 to 12 carbon atoms such as cyclohexyl group, vinyl group, 2 to 1 carbon atoms such as propenyl group
2 unsaturated alkyl groups, and cyclopentadienyl groups, phenyl groups, pyridyl groups, tolyl groups, xylyl groups,
It is at least one group selected from the group consisting of a substituted or unsubstituted aryl group having 5 to 16 carbon atoms such as a naphthyl group, and even if a part of hydrogen atoms thereof such as a trifluoropropyl group is substituted with a fluorine atom. good. Of these, a hydrogen atom, a fluorine atom, a methyl group, a nitro group, a vinyl group, a butyl group and a phenyl group are preferable, and a hydrogen atom is particularly preferable.

Q in the structural unit [2] is an oxygen atom or-
NR ^10- (wherein R ¹⁰ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Saturated alkyl group having 1 to 12 carbon atoms such as cyclohexyl group, unsaturated alkyl group having 2 to 12 carbon atoms such as vinyl group and propenyl group, and cyclopentadienyl group, phenyl group, pyridyl group, tolyl group, xylyl group , A naphthyl group or the like having at least one group selected from the group consisting of a substituted or unsubstituted aryl group having 5 to 16 carbon atoms, in which a part of hydrogen atoms such as a trifluoropropyl group is replaced by a fluorine atom. Is also good. ) At least one group selected from the group consisting of), and an oxygen atom is particularly preferable.

Z in the structural unit [2] is at least 1 selected from the group consisting of --C (═O)-or --SO _2-.
It is one group, and -C (= O)-is particularly preferable.

X in the structural unit [3-I] is a single bond, -C
(R¹⁷) (R¹⁸)-(R¹⁷And R ¹⁸Is a hydrogen atom,
Fluorine atom, methyl group, ethyl group, propyl group, butyl
Group, pentyl group, hexyl group, cyclohexyl group, etc.
Saturated alkyl group having a prime number of 1 to 12, vinyl group, propenyl
An unsaturated alkyl group having 2 to 12 carbon atoms such as a group, and cycl
Lopentadienyl group, phenyl group, pyridyl group, tolyl
Group, xylyl group, naphthyl group, etc., having 5 to 16 carbon atoms
Alternatively, a small number selected from the group consisting of unsubstituted aryl groups
At least one group, such as trifluoropropyl group
Some hydrogen atoms of are replaced by fluorine atoms
Good), -C (= O)-, -SO₂-, -S-, -O
-In the formula [4-I] and the formula [4-II]
At least one group selected from the group consisting of
is there. Among them, single bond, isopropylidene, -SO₂
-, -O- are preferable, and a single bond and isopropylide are particularly preferable.
And -O- are preferred. p represents an integer of 0 to 2, particularly
1 is desirable.

Structural unit [3-I] and structural unit [3-
II] in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R
¹⁶ is a hydrogen atom, a fluorine atom, a nitro group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a saturated alkyl group having 1 to 12 carbon atoms such as a cyclohexyl group, a vinyl group, a propenyl group, etc. An unsaturated alkyl group having 2 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 5 to 16 carbon atoms such as cyclopentadienyl group, phenyl group, pyridyl group, tolyl group, xylyl group, and naphthyl group. At least one group selected from
A part of the hydrogen atoms such as a trifluoropropyl group may be replaced by a fluorine atom.

R in the formula [4-I] and the formula [4-II]
¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷
And R ²⁸ represents a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group or another saturated alkyl group having 1 to 12 carbon atoms, a vinyl group, a propenyl group or the like. From an unsaturated alkyl group having 2 to 12 carbon atoms and a substituted or unsubstituted aryl group having 5 to 16 carbon atoms such as cyclopentadienyl group, phenyl group, pyridyl group, tolyl group, xylyl group and naphthyl group. At least one group selected,
A part of the hydrogen atoms such as a trifluoropropyl group may be replaced by a fluorine atom.

Among the silicon-containing polymers of the present invention, in R ¹ in the structural unit [1], R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ of the structural unit [2] which is an essential structural unit. , R ⁹
Is a hydrogen atom, Q is an oxygen atom, and Z is —C (═O) —, which is economically advantageous because phenolphthalein is used as a raw material.

Further, R in the structural unit [1]¹At
From the structural unit of structural unit [2] and structural unit [3-I]
And R of the structural unit [2]^Four, R^Five, R⁶, R⁷, R⁸, R⁹
Is a hydrogen atom, Q is an oxygen atom, and Z is -C (= O)-.
R of the structural unit [3-I] ¹¹, R¹², R¹³, R¹⁴But water
Elementary atom, X is -C (CH₃)₂-, Those in which p is 1
The raw materials are phenolphthalein and bisphenol A.
Therefore, it is economically advantageous and preferable.

In R ¹ in the structural unit [1],
A silicon-containing polymer having a structure in which R ² and R ³ are methyl groups, j and k are 0, and m is 1 is preferable because it is economically advantageous because dimethyldichlorosilane is used as a raw material.

Further, when the silicon-containing polymer of the present invention is produced by using phenolphthalein, dimethyldichlorosilane and optionally bisphenol A as raw materials,
It is economically advantageous and preferable.

The silicon-containing polymer composed of the repeating unit represented by the structural unit [1] in the present invention has a number average molecular weight of preferably 2,000 to 200,000, more preferably 5,000 to 100,000. Is more preferable. If the number average molecular weight is 2,000 or more, extrude
It is preferable because it hardly volatilizes during molding and there is no problem such as mold contamination. Further, those of 200,000 or less are preferable because they are easy to produce and excellent in productivity.

The silicon-containing polymer used as the component B of the present invention can be produced by a known method. Generally, an aromatic compound having two hydroxyl groups (phenolphthalein, bisphenols, etc.) and a disubstituted silane having two reactive groups (halogen, amino group, etc.) (dimethyldichlorosilane, methylphenyldichlorosilane, etc.) are used. ,
In the presence of a catalyst such as triethylamine, triisopropylamine and pyridine, a solvent such as toluene, xylene and dichlorobenzene is used at the reflux temperature of the solvent (or 30
To 200 ° C.) for 1 to 20 hours for condensation polymerization.

Journal of Polymer
Science, Vol. 18, p. 3119 (19
80) shows a method of obtaining a silicon-containing polymer having bisphenol A and a dimethylsiloxy skeleton by condensation polymerization of bisphenol A and dimethyldichlorosilane in a toluene solvent. In addition, JP-A-5
A melt polymerization method for synthesizing a silicon-containing polymer without using a solvent as disclosed in Japanese Patent Publication No. 247215 is also possible.

According to the above-mentioned literature, the silicon-containing polymer used in the present invention is synthesized by subjecting an aromatic compound having two hydroxyl groups and a disubstituted silane having two reactive groups to condensation polymerization in the presence of a catalyst. It was possible to The aromatic compound and the disubstituted silane can be used alone or in combination of two or more kinds.

Further, for the purpose of controlling the molecular weight of the silicon-containing polymer to be formed and sealing the terminal phenolic hydroxyl group, a compound having one hydroxyl group such as phenol or xylenol is used, whereby a phenoxy group or A polymer having a 2,6-dimethylphenoxy group introduced can be obtained. Since the stability of the produced polymer is improved by sealing the end of the produced polymer, it is preferable to introduce a phenoxy group or a 2,6-dimethylphenoxy group at the end.

In the present invention, the amount of the silicon-containing polymer used as the component B is 0.1 to 20 parts by weight, preferably 0.2, based on 100 parts by weight of the component A polycarbonate resin. 10 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight. The amount of B component is 0.
If it is less than 1 part by weight, the flame retardancy of the resin composition will not be exhibited, and if it exceeds 20 parts by weight, the transparency will be poor and the heat resistance and impact resistance will be unfavorable.

Examples of the alkali or alkaline earth metal salt (C component) of an organic Bronsted acid having 1 or more carbon atoms which can be preferably added to the polycarbonate resin composition of the present invention include organic sulfonic acid and organic Examples thereof include alkali or alkaline earth metal salts of Bronsted acids such as carboxylic acids, organic phosphoric acids, organic phosphonic acids, and organic phosphinic acids. The Brönsted acid in the present invention is by Fizer and Fizer, Organic Chemistry,
Interscience publisher (Interscience)
publishers, N.M. Y. ), 1965
Year, p. 595. The organic Bronsted acid constituting the component C may be partially esterified, such as diphenylphosphoric acid. Among these organic Bronsted acids, organic sulfonic acid is preferable. On the other hand, the alkali metal is sodium, potassium, lithium, cesium, etc., and the alkaline earth metal is magnesium, calcium, strontium, barium, etc.

Therefore, examples of the alkali metal salt or alkaline earth metal salt of the organic Bronsted acid include an alkali metal salt of an organic sulfonic acid, an organic carboxylic acid, an organic phosphoric acid, or an alkaline earth metal salt. Particularly, sodium, potassium and cesium salts are preferably used. Further, a part of the salt of the organic acid or the organic acid ester may be substituted with fluorine.

[0075] Among the alkali metal or alkaline earth metal salts of the various organic Bronsted acids, for example, in the case of organic sulfonic acid, the following formula _{[5] (C q F 2q} + 1 SO 3) p M [ 5] (In the formula, q represents an integer of 1 to 10, M represents an alkali metal such as lithium, sodium, potassium, and cesium, or an alkaline earth metal such as magnesium, calcium, strontium, and barium, and p represents M. The alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid represented by the formula (1) is preferably used.

In the above formula [5], examples of the perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid. , Perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, etc., and potassium salts thereof are particularly preferably used.

Further, other alkali metal salts or alkaline earth metal salts of organic sulfonic acids include diphenylsulfone-3-sulfonic acid and diphenylsulfone-3,3 '.
-Alkaline metal salts such as sulfonic acid and naphthalenetrisulfonic acid, alkaline earth metal salts, and the like. Of these, potassium perfluorobutane sulfonate and potassium diphenyl sulfone sulfonate are particularly preferably used.

Examples of the organic carboxylic acid include perfluoroformic acid, perfluoromethanecarboxylic acid, perfluoroethanecarboxylic acid, perfluoropropanecarboxylic acid, perfluorobutanecarboxylic acid, perfluoromethylbutanecarboxylic acid, perfluorohexanecarboxylic acid. Acid, perfluoroheptanecarboxylic acid, perfluorooctanecarboxylic acid, etc., and alkali metal salts or alkaline earth metal salts of these organic carboxylic acids are used.

The organic phosphoric acid has the following formula [6-I] or [6-II]

[0080]

[Chemical 13]

[0081]

[Chemical 14]

(In the formula, R ²⁹ , R ³⁰ and R ³¹ may be the same or different and each represents an alkyl group or an aryl group, and R ³⁰ and R ³¹ may be bonded directly or by an alkylene group. And may form one fused ring.), And a compound in which a hydrogen atom in the above formula is replaced with an alkali metal or an alkaline earth metal is used. Examples of the alkali (earth) metal salt of organic phosphoric acid include phosphoric acid ester alkali (earth) metal salt of di (p-tert-butylphenol) and di (p-cumylphenol) phosphoric acid. Ester alkali (earth) metal salts and the like are preferably used.

The alkali metal salt or alkaline earth metal salt of the organic Bronsted acid having 1 or more carbon atoms, which is optionally used as the C component, may be used alone or in combination of two or more kinds. You may use it. Further, the blending amount of the component C is preferably 0.01 to 1 part by weight, particularly preferably 0.02 to 0.5 part by weight, relative to 100 parts by weight of the polycarbonate resin of the component A. When the blending amount of the C component is within such a range, it is possible to impart a higher flame retardancy and it is economically advantageous.

The transparency, which is one of the characteristics of the polycarbonate resin composition of the present invention, is closer to the original transparency of the polycarbonate resin. Specifically 1/1
In a 6 inch (1.59 mm) thick molded flat plate, J
Haze (cloudiness value) measured according to IS-K-7105
The value means 10 or less, preferably 9 or less, and more preferably 4 or less. The total light transmittance is 8
0.0% or more, more preferably 84.0% or more,
87.0% or more is more preferable.

An anti-drip agent can be added to the polycarbonate resin composition of the present invention within a range that does not impair the object of the present invention. As the drip preventing agent, polytetrafluoroethylene having a fibril forming ability is preferably used. As such polytetrafluoroethylene, those coated with an acrylonitrile-styrene copolymer, polymethylmethacrylate resin or the like can be preferably used in order to maintain the transparency of the resin. The compounding amount of the anti-drip agent is the above-mentioned polycarbonate resin (component A).
0.01 to 1 part by weight is preferable with respect to 100 parts by weight.

A heat stabilizer can be added to the polycarbonate resin composition of the present invention in order to prevent a decrease in molecular weight and deterioration of hue during molding so long as the object of the present invention is not impaired.

Examples of such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and specifically, triphenyl phosphite,
Tris (nonylphenyl) phosphite, Tris (2,
4-di-tert-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite Fight, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert) -Butylphenyl)
Octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t
ert-Butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl mono-orthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4, Tetrakis (2,4-di-tert-butylphenyl) 4'-biphenylene diphosphosphinate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like can be mentioned. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite and dimethyl benzenephosphonate are preferably used. You may use these heat stabilizers individually or in mixture of 2 or more types. The amount of the heat stabilizer blended is 0.0001 with respect to 100 parts by weight of the polycarbonate resin (component A).
To 1 part by weight is preferred, 0.0005 to 0.5 part by weight is more preferred, and 0.001 to 0.1 part by weight is even more preferred.

The polycarbonate resin composition of the present invention may be mixed with a generally known antioxidant within a range that does not impair the object of the present invention. Examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis [3 -(3-tert-butyl-5
-Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,
4,6-Tris (3,5-di-tert-butyl-4-
(Hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl Ester, tris (3,5-di-tert-butyl-
4-hydroxybenzyl) isocyanurate, 4,4 ′
-Biphenylenediphosphophosphinic acid tetrakis (2,4
-Di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2, 4,8,10-tetraoxaspiro [5,5] undecane and the like can be mentioned. The blending amount of these antioxidants is the above-mentioned polycarbonate resin (A
Ingredient) 0.0001 to 0.05 parts by weight is preferable to 100 parts by weight.

A release agent may be added to the polycarbonate resin composition of the present invention within a range not impairing the object of the present invention in order to further improve the releasability from the mold during melt molding. . Examples of such a release agent include higher fatty acid esters of monohydric or polyhydric alcohols, paraffin wax, beeswax and the like. The higher fatty acid ester is preferably a partial ester or whole ester of a monohydric or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of the partial ester or total ester of monohydric or polyhydric alcohol and saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol. Tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2- Examples thereof include ethylhexyl stearate. Among them, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol. Tetrastearate are preferably used. The compounding amount of such a release agent is preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A).

A light stabilizer can be added to the polycarbonate resin composition of the present invention within a range that does not impair the object of the present invention. Examples of such a light stabilizer include 2-
(2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-methyl-2) -Hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazole) Phenyl), 2,2'-p-phenylene bis (1,3-benzoxazin-4-one), polyalkylene naphthalate and the like. The amount of such a light stabilizer blended is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A).

An antistatic agent may be added to the polycarbonate resin composition of the present invention within a range that does not impair the object of the present invention. Examples of the antistatic agent include polyether ester amide, glycerin monostearate, ammonium dodecylbenzene sulfonate, phosphonium dodecylbenzene sulfonate, maleic anhydride monoglyceride, maleic anhydride diglyceride and the like. The amount of the antistatic agent blended is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A).

The polycarbonate resin composition of the present invention may be blended with other resins and elastomers within a range that does not impair the purpose of the present invention, that is, within a range capable of maintaining high flame retardancy, transparency and impact resistance. You can also Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polysulfone resins, polyethylene, and polyolefin resins such as polypropylene. , Polystyrene resin, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polymethacrylate resin, phenol resin, epoxy resin and the like.

As the elastomer, for example, isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate-sterene methacrylate) which is a core-shell type elastomer. -Butadiene) rubber, MA
Examples thereof include S (methyl methacrylate-acrylonitrile-styrene) rubber and the like.

The polycarbonate resin composition of the present invention generally comprises a polycarbonate resin as component A, a silicon-containing compound as component B, and optionally an alkali metal salt or alkaline earth metal salt of an organic Bronsted acid as component C, and If necessary, other additives or the like are supplied from separate feeders, or a mixture obtained by premixing a part of the components with a mixer and each component other than the mixture are supplied from the respective feeders or from the same charging port or 2 It can be obtained by supplying the mixture to the kneading machine through more than one charging port and melting and mixing.

Further, as a method for obtaining the polycarbonate resin composition of the present invention, a method of preparing a master by mixing a part or all of the component B with a part of the component A in advance, and introducing the master,
Any method of charging the master in the middle of the extruder can be used. Examples of the mixer include a tumbler, a V-type blender, a super mixer, a super floater, and a Henschel mixer.
As the kneader, various melt mixers can be used, and for example, a kneader, a single-screw or twin-screw extruder can be used.
Among them, a method in which the resin composition is melted and extruded using a twin-screw extruder or the like and pelletized by a pelletizer is preferably used. It is preferable to use an extruder equipped with one or more degassing holes at a temperature of about 250 to 320 ° C., and to carry out melt kneading under reduced pressure.

The pellets of the polycarbonate resin composition thus obtained can be formed into a molded product by a commonly known method such as an injection molding method, an extrusion molding method and a compression molding method. Of course, it is also possible to form a molded product by injection molding, extrusion molding or the like as it is from the mixture obtained by the above mixer.

[0097]

The present invention will be described in detail below with reference to examples.
The scope of the invention is not limited to these examples. The various properties in the examples were measured by the following methods.

(1) Structural Viscosity Index Polycarbonate resin pellets were placed in a cylinder of a flow tester (Shimadzu Corporation) and the temperature was set to 280.
The applied pressure P (9.8 to 17.6MP, with the temperature kept constant at ℃)
a) and the outflow rate Q (mL / sec) of each molten resin
Was measured, and each value was plotted on a log-log graph to obtain the slope of the regression line obtained.

(2) Viscosity Average Molecular Weight of Polycarbonate Resin The viscosity average molecular weight (Mv) is calculated by using the following formula as the specific viscosity (η _SP ) obtained from a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. Inserted and asked. η _SP /C=[η]+0.45[η] ² C [η] = 1.23 × 10 ⁻⁴ Mv ^0.83 (where [η] is the intrinsic viscosity and C is the polymer concentration is 0.7)

(3) Measurement of Molecular Weight / Molecular Weight Distribution of Silicon-Containing Compound Using a HPLC measuring apparatus LC-10A (manufactured by Shimadzu Corporation) equipped with a GPC column KF-805L manufactured by Showa Denko KK, the number was measured by size exclusion chromatography. The average molecular weight and molecular weight distribution were obtained. For the measurement, chloroform was used as an eluent, and standard polystyrene was used for calibration.

(4) Infrared absorption spectrum measurement of silicon-containing compound It was measured by the KBr disk method using an apparatus manufactured by Perkin Elmer.

(5) ¹ H NMR measurement of silicon-containing compound Using a 300 MHz NMR measurement apparatus manufactured by Varian,
It was measured at room temperature using deuterated chloroform as a solvent.

(6) Flame retardance (I) Oxygen index It was measured according to JIS-K-7201.

(Ii) UL-94 Test Using a test piece having a thickness of 1/16 inch (1.59 mm), evaluation was performed according to a vertical combustion test specified in UL-94 of the US UL standard.

(7) Transparency (Haze Value) The haze value of a test piece having a thickness of 1/16 inch (1.59 mm) was measured according to JIS-K-7105.

(8) Impact resistance (Izod impact strength with notch) Notched Izod impact strength was measured for a 1/8 inch (3.18 mm) test piece in accordance with ASTM D256.

Reference Example 1 Synthesis of high molecular weight polycarbonate resin (PC-2) 100 parts by weight of bisphenol A was prepared in a reactor equipped with a thermometer, a stirrer and a reflux condenser by ion exchanged water under a nitrogen stream 10. While dissolving 550 parts by weight of an aqueous sodium hydroxide solution (320 parts by weight), 320 parts by weight of methylene chloride was added, and 50 parts by weight of phosgene was blown thereinto at 25 ° C. for 100 minutes while stirring. During this period, a 15% aqueous sodium hydroxide solution was added to adjust the pH value of the aqueous layer to 12-14. The concentration of the reaction product in the methylene chloride layer after the reaction is 25%
Met. Then, with vigorous stirring, methylene chloride 550
Parts by weight were added to make a uniform emulsion. At this time, the concentration of the reaction product in the methylene chloride layer was 11%.
Then, a 15% aqueous sodium hydroxide solution was added to add p to the aqueous layer.
While adjusting H to 13, p-tert as a terminal stopper
0.23 parts by weight of butylphenol, 0.2 parts by weight of triethylamine as a catalyst and 550 parts by weight of methylene chloride were added. At this time, the concentration of the reaction product in the methylene chloride layer was 7%. 10 minutes later methylene chloride 550
By adding 10 parts by weight, the concentration of the reaction product in the methylene chloride layer was adjusted to 5%, and after 10 minutes, 550 parts by weight of methylene chloride was added and polycondensation reaction was carried out at 30 ° C. for 3 hours. At the end of the reaction, the concentration of the reaction product in the methylene chloride layer was 4%. After the reaction is completed, the aqueous layer is separated, and the organic layer is thoroughly washed with water,
After concentrating, the solution was dropped into methanol to obtain a linear high molecular weight polycarbonate resin as a precipitate, which was dried. The linear high molecular weight polycarbonate resin obtained had a viscosity average molecular weight of 121,000.

Reference Example 2 Synthesis of Branched Polycarbonate Resin (PC-4) In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 114 parts by weight of bisphenol A was dissolved in an aqueous 12.3% sodium hydroxide solution 394 parts by weight. And 300 parts by weight of methylene chloride were added thereto, and 70 parts by weight of phosgene was blown thereinto under stirring at 25 ° C. for 40 minutes. To this was added 2.8 parts by weight of p-tert-butylphenol and 9 parts by weight of a 10% aqueous sodium hydroxide solution in which 0.9 parts by weight of 1,1,1-tris (4-hydroxyphenyl) ethane were added, and the mixture was stirred for 5 minutes. After that, 0.23 parts by weight of triethylamine was added and stirred for 10 minutes. Then, 23 parts by weight of bisphenol A was dissolved 4
Add 237 parts by weight of an aqueous solution of sodium hydroxide at a concentration of about 4
The reaction was completed by stirring for 0 minutes. The aqueous layer was separated, the organic layer was thoroughly washed with water, and concentrated to obtain a branched polycarbonate resin. The branched polycarbonate resin obtained had a viscosity average molecular weight of 25,100.

[Reference Example 3] Silicon-containing polymer (B-1)
While stirring a mixture of 300.0 parts by weight of phenolphthalein, 156.6 parts by weight of pyridine, and 740 parts by weight of toluene under a synthetic nitrogen atmosphere, dimethyldichlorosilane 12
1.6 parts by weight was added dropwise at room temperature over 5 minutes. Then
The mixture was heated and refluxed for 3 hours to cause a reaction. To this, 13.2 parts by weight of 2,6-dimethylphenol was added, and the mixture was further refluxed for 1 hour to cause a reaction, then 350 parts by weight of toluene was added, and the pyridine hydrochloride precipitated by filtering was filtered off while hot. When the obtained filtrate was allowed to cool to room temperature, a solid was precipitated in the solution, so 890 parts by weight of chloroform was added to dissolve the precipitate, and this solution was washed with dilute hydrochloric acid, an aqueous solution of sodium hydrogen carbonate and water, and then dried. When added to a large amount of hexane, a white precipitate was formed. The precipitate was recovered and dried in vacuum at 80 ° C. for 12 hours.
0 part by weight of white powder was obtained.

The molecular weight of the obtained white powder was measured by size exclusion chromatography to find that the number average molecular weight was 9,
900, weight average molecular weight 17,800, molecular weight distribution 1.
It was found to be 80 polymers. When the infrared absorption spectrum of this polymer was measured, Si--O--C ₆
An absorption derived from H ₄ was observed at 921 cm ^-1 . ¹ HN
When the MR spectrum was measured, the peak derived from the phenolphthalein structure was 6.8 ppm to 8.0 ppm,
The peak of the methyl group of the dimethylsiloxy structure is 0 ppm
Observed at 0.4 ppm. From the relative intensities of these peaks, it was found that the relative ratio of the phenolphthalein structure and the dimethylsiloxy structure was about 1/1 (mol / mol). Further, the peak at 2.2 ppm was assigned to the methyl group of 2,6-dimethylphenol, and the relative strength thereof did not decrease even after repeated reprecipitation and washing of the obtained polymer. Was attributed to From the above results, in the obtained polymer, R ¹ of the structural unit [1] is the same as the structural unit [2] (R ⁴ , R ⁵ in the formula,
R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen atoms, Q is an oxygen atom, and Z is-.
C (= O)-), R ² and R ³ are methyl groups, j and k are 0, and m is 1 and the number average molecular weight thereof is 9,900, and 2 at the end. It was found that a 6-dimethylphenoxy group was introduced.

[Reference Example 4] Silicon-containing polymer (B-2)
In a synthetic nitrogen atmosphere of 150.0 parts by weight of phenolphthalein, 107.6 parts by weight of bisphenol A, and pyridine 15
While stirring a mixture of 6.5 parts by weight and 740 parts by weight of toluene, 121.6 parts by weight of dimethyldichlorosilane was added dropwise at room temperature over 5 minutes. Next, after heating and refluxing for 3 hours to cause reaction, 350 parts by weight of toluene was added, and pyridine hydrochloride precipitated by filtering while hot was filtered off. After 890 parts by weight of chloroform was added to the obtained filtrate, this solution was washed with dilute hydrochloric acid, an aqueous solution of sodium hydrogen carbonate and water and dried, and when added to a large amount of hexane, a white precipitate was formed. After collecting this precipitate, 8
When vacuum-dried at 0 ° C. for 12 hours, 257 parts by weight of white powder was obtained.

The molecular weight of the obtained white powder was measured by size exclusion chromatography to find that the number average molecular weight was 1
It was found that the polymer was 0,800, the weight average molecular weight was 19,500, and the molecular weight distribution was 1.81. When the infrared absorption spectrum of this polymer was measured, Si--O--
An absorption derived from C ₆ H ₄ was observed at 924 cm ^-1 . ¹
When the 1 H NMR spectrum was measured, the peak derived from the phenolphthalein structure was 7.6 ppm to 8.0 p.
pm, the peak derived from phenolphthalein and bisphenol A structure is 6.7 ppm to 7.2 ppm, and the peak of the methyl group derived from the dimethylsiloxy structure is 0 ppm to
Observed at 0.4 ppm. From the relative intensities of these peaks, it was found that the ratio of the phenolphthalein structure to the bisphenol A structure was about 1/1 (mol / mol). It was also found that the relative ratio of the phenolphthalein structure and the dimethylsiloxy structure was about 0.5 / 1 (mol / mol). From the above results, in the obtained polymer, R ¹ of the structural unit [1] is the structural unit [2] (in the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, Q is an oxygen atom, Z is —C (═O) — in an amount of 50 mol%, and structural unit [3-I] (in the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms, and X is −). C (CH ₃ ) ₂ −, p is 1) 50 mol%, R ² and R ³ are methyl groups, j and k are 0, and m is 1
It was found that the polymer had a repeating structure represented by and its number average molecular weight was 10,800.

[Reference Example 5] Silicon-containing polymer (B-3)
In a synthetic nitrogen atmosphere of 150.0 parts by weight of phenolphthalein, 107.6 parts by weight of bisphenol A, and pyridine 15
While stirring the mixture of 6.5 parts by weight and 740 parts by weight of toluene, a mixture of 60.8 parts by weight of dimethyldichlorosilane and 66.5 parts by weight of methylvinyldichlorosilane was added dropwise at room temperature over 5 minutes. Then, it was heated and refluxed for 3 hours to cause a reaction. 2,6-dimethylphenol 1
After 2.1 parts by weight was added and the mixture was refluxed for another 1 hour for reaction, 350 parts by weight of toluene was added and the pyridine hydrochloride precipitated by filtering while hot was filtered off. After 890 parts by weight of chloroform was added to the obtained filtrate, this solution was washed with dilute hydrochloric acid, an aqueous solution of sodium hydrogen carbonate and water and dried, and when added to a large amount of hexane, a white precipitate was formed. The precipitate was collected and vacuum dried at 80 ° C. for 12 hours to obtain 276 parts by weight of white powder.

The molecular weight of the obtained white powder was measured by size exclusion chromatography to find that the number average molecular weight was 1
It was found that the polymer was 0,900, the weight average molecular weight was 20,100, and the molecular weight distribution was 1.84. When the infrared absorption spectrum of this polymer was measured, Si--O--
An absorption derived from C ₆ H ₄ was observed at 923 cm ^-1 . ¹
When the 1 H NMR spectrum was measured, the peak derived from the phenolphthalein structure was 7.6 ppm to 8.0 p.
The peaks derived from the pm, phenolphthalein, and bisphenol A structures are 6.7 ppm to 7.2 ppm, and the vinyl group peak of the methylvinylsiloxy group is 6.0 to 6.0 ppm.
6.2 ppm, the peak of the methyl group of the dimethylsiloxy structure and the methylvinylsiloxy group is 0 ppm to 0.4 p
Observed at pm. From the relative intensities of these peaks, the ratio of the phenolphthalein structure to the bisphenol A structure is about 1/1 (mol / mol), and the ratio of the dimethylsiloxy structure to the methylvinylsiloxy structure is also about 1/1 (mol / mol). It turned out that It was also found that the relative ratio of the phenolphthalein structure and the methylvinylsiloxy structure was about 1/1 (mol / mol). Further, the two peaks at 2.2 ppm were assigned to the methyl group of 2,6-dimethylphenol, and the relative strength thereof did not decrease even after repeated reprecipitation and washing of the obtained polymer. Introduced and attributed. From the above results, in the obtained polymer, R ¹ of the structural unit [1] is the structural unit [2] (R ⁴ , R ⁵ , R ⁶ in the formula,
R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, Q is an oxygen atom, and Z is -C.
(= O)-) 50 mol%, structural unit [3-I]
(In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms, and X is —C.
(CH ₃ ) ₂ −, p is 1) 50 mol% and R
² is a methyl group, 50% of R ³ is a methyl group, 50% is a vinyl group, and is a polymer having a repeating structure in which j, k are 0 and m is 1, and the number average molecular weight thereof is 10,900 It was found that a 2,6-dimethylphenoxy group was introduced into.

The raw materials used in the examples are as follows. (A component) (A-1 component) or (A-3 component) PC-1: Panlite L-1250 (linear polycarbonate resin, Teijin Chemicals Ltd., Mv = 25,000) (A-2 Component) PC-2: Linear high molecular weight polycarbonate resin (A-4 component) obtained in Reference Example 1 PC-3: Tufflon IB2500 (branched polycarbonate resin, manufactured by Idemitsu Petrochemical Co., Ltd., branching agent 1) , 1, 1
-Using tris (4-hydroxyphenyl) ethane, Mv
= 25,000) PC-4: Branched polycarbonate resin (component B) obtained in Reference Example 2 above, silicon-containing compound B-1: Silicon-containing polymer B-2 obtained in Reference Example 3 above: Reference above Silicon-Containing Polymer B-3 Obtained in Example 4: Silicon-Containing Polymer (C Component) Organic Alkali Metal Salt C-1 Obtained in Reference Example 5 above: C-1: C ₄ F ₉ SO ₃ K (Dainippon Ink and Chemicals) Megafac F114, manufactured by Co., Ltd. C-2: Potassium diphenylsulfonesulfonate (UC)
BSS KSS; a mixture of diphenylsulfone-3-sulfonic acid and diphenylsulfone-3,3'-sulfonic acid)

[Examples 1 to 11 and Comparative Examples 1 to 8] The components shown in Tables 1 and 2 were uniformly mixed in a blending ratio (parts by weight) shown in Tables 1 and 2 using a tumbler. After mixing, it was pelletized at a resin temperature of 260 ° C. with a twin-screw extruder with a 15 mmφ vent (KZW-15 manufactured by Technobel Co., Ltd.), and the obtained pellets were dried at 95 ° C. for 4 hours with a hot air dryer. Cylinder temperature of this pellet was 280 using an injection molding machine (J75Si manufactured by Japan Steel Works, Ltd.).
Each test piece was molded at a mold temperature of 80 ° C. Using the prepared test piece, the oxygen index, UL-94 test, haze measurement, and Izod impact strength were evaluated.

[0117]

[Table 1]

[0118]

[Table 2]

As shown in Examples 1, 6 and 8, it can be seen that the compositions obtained by kneading the silicon-containing polymer of the present invention in a polycarbonate resin have an increased oxygen index and are flame retarded. Further, as shown in Examples 2 to 5, 7, and 9 to 11, when an organic Bronsted acid alkali metal salt is used in combination, the oxygen index of the composition is further increased, and UL-94.
In the test, it can be seen that the flame retardancy of V-0 is imparted to the 1/16 inch test piece. It can be seen that the test pieces obtained in these examples all have a haze of 3 or less and are excellent in transparency. Further, it can be seen that the polycarbonate resin composition containing the silicon-containing polymer of the present invention also has improved impact resistance.

On the other hand, as shown in Comparative Examples 1 to 6, it is clear that the polycarbonate resin compositions containing no silicon-containing compound of the present invention have a low oxygen index and insufficient flame retardancy. In Comparative Example 7, it is clear that the flame retardancy is inferior because the amount of the silicon-containing compound is small. Further, in Comparative Example 8, when the content of the silicon-containing compound increases, it is clear that although the flame retardancy is excellent, the transparency deteriorates and the impact resistance decreases.

As described above, the present invention can provide a flame-retardant resin composition having excellent transparency and impact resistance, which does not produce harmful halogen compounds during combustion.

[0122]

EFFECTS OF THE INVENTION The present invention provides a polycarbonate resin composition which does not use halogen and phosphorus elements, is excellent in transparency and impact resistance, and has high flame retardancy. It is a polycarbonate-based resin composition having a low environmental load that can be used in various fields such as fields, automobile fields, and other fields, and its industrial effect is extremely large.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yutaka Takeya             1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo             Human Kasei Co., Ltd. F-term (reference) 4F071 AA50 AA67 BB05 BC07                 4J002 CG00W CG01W CP19X EG026                       EG036 EV236 EW046 EW126                       EW136 FD13X FD136                 4J035 HA02 LB20

Claims (14)

[Claims] 1. A silicon-containing polymer (component B) comprising 100 parts by weight of (A) a polycarbonate resin (component A) and (B) a structural unit [1] represented by the following formula [1].
A polycarbonate resin composition comprising 0.1 to 20 parts by weight. [Chemical 1] (In the structural unit [1], R ¹ is the structural unit [2] represented by the following formula [2], the structural unit [3-I] represented by the following formula [3-I], and the following formula [3-II] Of the structural unit [3-II], and the ratio of the structural unit [2] and the structural unit [3-I] + the structural unit [3-II] is 100: 0 to 20:80 in a molar ratio. The range is R ² , R ^3.
Is at least one group selected from the group consisting of a hydrogen atom, a saturated alkyl group having 1 to 12 carbon atoms, an unsaturated alkyl group having 2 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 5 to 16 carbon atoms. , Some of the hydrogen atoms may be replaced by fluorine atoms. j and k are 0 or 1, and m is a positive number of 1 to 10. ) [Chemical 2] (R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen atom, fluorine atom, nitro group, saturated alkyl group having 1 to 12 carbon atoms, unsaturated alkyl group having 2 to 12 carbon atoms and carbon It is at least one group selected from the group consisting of substituted or unsubstituted aryl groups of the formulas 5 to 16, and some hydrogen atoms thereof may be replaced by fluorine atoms, and Q is an oxygen atom or —NR ¹⁰ -(However, R ¹⁰ is a hydrogen atom, having 1 to
It is at least one group selected from the group consisting of a saturated alkyl group having 12 carbon atoms, an unsaturated alkyl group having 2 to 12 carbon atoms and a substituted or unsubstituted aryl group having 5 to 16 carbon atoms, and some of the hydrogen atoms are It may be substituted with a fluorine atom. ) And Z is -C (= O)-or-
SO ₂ −. ) [Chemical 3] [Chemical 4] (In the formula, X is a single bond, -C (R ¹⁷ ) (R ¹⁸ )-, -C
(= O) -, - SO 2 -, - S -, - O-, the following formula [4
-I] and at least one group selected from the group consisting of groups represented by the following formula [4-II]. R ¹¹ , R
¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ are hydrogen atoms,
Fluorine atom, nitro group, saturated alkyl group having 1 to 12 carbon atoms, unsaturated alkyl group having 2 to 12 carbon atoms and 5 carbon atoms
Is at least one group selected from the group consisting of substituted or unsubstituted aryl groups of ˜16, and some of the hydrogen atoms may be substituted with fluorine atoms. p is an integer of 0-2. ) [Chemical 5] [Chemical 6] (In the formula, R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ ,
R ²⁶ , R ²⁷ and R ²⁸ are a hydrogen atom, a fluorine atom, a nitro group,
At least 1 selected from the group consisting of a saturated alkyl group having 1 to 12 carbon atoms, an unsaturated alkyl group having 2 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 5 to 16 carbon atoms.
One group may have a part of hydrogen atoms thereof replaced by a fluorine atom. ) 2. The flame-retardant polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (component A) has a viscosity average molecular weight of 10,000 to 40,000. 3. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (component A) has a structural viscosity index of 1.36 or more. 4. A polycarbonate resin (component A) is
(A-1) Viscosity average molecular weight 10,000 to 40,000
65 to 95 wt% of the polycarbonate resin (A-1 component) and (A-2) viscosity average molecular weight 70,000 to 25
10,000 high molecular weight polycarbonate resin (A-2
Component) 5 to 35% by weight, The polycarbonate resin composition according to claim 1. 5. The polycarbonate resin (component A) comprises:
(A-3) 0 to 95% by weight of a linear polycarbonate resin (A-3 component) and (A-4) 5 to 100% by weight of a branched polycarbonate resin (A-4 component). The polycarbonate-based resin composition described. 6. A linear polycarbonate resin (A-3
Component) has a viscosity average molecular weight of 10,000 to 40,000
The polycarbonate resin composition according to claim 5, which is 7. A branched polycarbonate resin (A-4
The polycarbonate resin composition according to claim 5, wherein the component) has a viscosity average molecular weight of 4,000 to 40,000. 8. The polycarbonate resin composition according to claim 1, wherein the silicon-containing polymer (component B) has a number average molecular weight of 2,000 to 200,000. 9. In the silicon-containing polymer (component B),
The structural unit [2] has R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ thereof.
Is a hydrogen atom, Q is an oxygen atom, and Z is a silicon-containing polymer represented by -C (= O)-. 10. In the silicon-containing polymer (component B), the structural unit [3-I] has R ¹¹ , R ¹² , R ¹³ and R.
The polycarbonate resin composition according to claim 1, wherein ¹⁴ is a hydrogen atom, X is -C (CH ₃ ) _2- , and p is a silicon-containing polymer represented by 1. 11. In the silicon-containing polymer (component B), in the structural unit [1], R ² and R ³ are each a hydrogen atom, a methyl group, an ethyl group, a propyl group, a vinyl group, a butyl group and a phenyl group. The polycarbonate-based resin composition according to claim 1, which is a silicon-containing polymer in which m is 1 and j and k are 0, which is at least one group selected from the group consisting of: 12. In the silicon-containing polymer (component B), the structural unit [1] is a silicon-containing polymer in which R ² and R ³ are methyl groups, m is 1 and j and k are 0. The polycarbonate resin composition according to claim 1, which is a united body. 13. A polycarbonate resin (A
The component according to claim 1, which contains 0.01 to 1 part by weight of (C) an alkali or alkaline earth metal salt of an organic Bronsted acid having 1 or more carbon atoms (component C) per 100 parts by weight of the component). Polycarbonate resin composition. 14. A molded product formed from the resin composition according to claim 1.