JP6519105B2 - Polycarbonate resin composition - Google Patents

Description

  The present invention relates to a thermoplastic resin composition comprising a carbonate polymer, and relates to a polycarbonate resin composition excellent in flame retardancy and transparency.

  Polycarbonate resins and acrylic resins are mentioned as materials excellent in transparency, and polycarbonate resins have excellent heat resistance, impact resistance and dimensional stability, while acrylic resins have optical properties such as low birefringence, Excellent in surface hardness and UV resistance. Therefore, these materials are used in applications such as full display panels and optical materials.

  When using these transparent resins for housing construction materials, automobiles, aircraft parts, parts for electrical / electronics, parts for OA, etc., it is necessary to provide flame retardancy and fire resistance because of safety issues in case of fire. It is. Above all, it is important to impart flame retardance etc. while maintaining the transparency without impairing the appearance and the landscape for applications such as aircraft, automobiles, window materials of houses, sound insulation walls on expressways, agricultural houses and the like.

  As a method of providing a flame retardance, the method of adding a flame retardant at the time of preparation of a resin molded product is mentioned. Examples of the flame retardant include inorganic compounds, organic phosphorus compounds, organic halogen compounds, and halogen-containing organic phosphorus compounds. Among them, bromine-containing phosphorus compounds and the like exhibit excellent flame retardant effects. However, when a bromine-containing phosphorus compound is added to an organic polymer, the processability at the time of molding is reduced, so two flame retardants of an organic phosphorus compound containing bromine and a phosphate ester containing no bromine are used. JP-A No. 2003-93118 discloses a flame retardant organic polymer which is excellent in moldability, flame retardancy and flexibility and does not cause bleeding. Further, Patent Document 2 discloses a flame retardant transparent resin composition composed of a polycarbonate resin, a halogen-containing triazine, and a fluorine resin.

Unexamined-Japanese-Patent No. 3-182556 JP, 2010-235650, A

  However, in these flame retardant formulations, a large amount of flame retardant is added, or a flame retardant component is introduced into the resin composition, and the transparency which is the inherent physical properties of the resin is impaired instead of improving the flame retardancy. It was a thing.

  Then, this invention makes it a subject to obtain the polycarbonate resin composition excellent in the balance of a flame retardance and transparency.

MEANS TO SOLVE THE PROBLEM As a result of conducting earnest examination in view of said subject, the present inventors make a polycarbonate resin containing the structural unit originating in specific ether diol as a main component, and a bromine containing phosphoric acid ester type compound and non-halogen phosphoric acid ester. It has been found that a polycarbonate resin composition obtained by containing a predetermined amount of a base compound significantly improves the flame retardancy with almost no decrease in transparency, and the present invention has been completed.
That is, the present invention is as follows.

[1] A polycarbonate resin composition comprising the following polycarbonate resin (A) as a main component and containing a flame retardant, wherein 0.1 to 20 of the bromine-containing phosphate ester (B) in the resin composition is used as the flame retardant. A polycarbonate resin composition comprising:% by mass and 0.5 to 20% by mass of a non-halogen phosphoric acid ester (C) in the resin composition.
(A) Polycarbonate resin containing a structural unit (a) derived from a dihydroxy compound represented by the following general formula (1) in part of the polymer structure

[2] The polycarbonate resin (A) further includes a structural unit (b) derived from another dihydroxy compound other than the structural unit derived from the dihydroxy compound represented by the general formula (1) The polycarbonate resin composition as described in said [1].
[3] The polycarbonate resin (A) contains 30 to 95 mol% of a structural unit (a) derived from the dihydroxy compound represented by the general formula (1) based on all structural units derived from the dihydroxy compound The polycarbonate resin composition as described in said [2] characterized by the above.
[4] The polycarbonate resin composition according to the above [2] or [3], wherein the structural unit derived from the other dihydroxy compound is 1,4-cyclohexanedimethanol.
[5] A plate having a thickness of 1.0 mm to be measured according to JIS K7136, wherein the total light transmittance is 85% or more and the total haze value is 5.0% or less. ] The polycarbonate resin composition as described in any one of the above.
[6] A molded article formed using the polycarbonate resin composition according to any one of the above [1] to [5].
[7] A window material formed using the polycarbonate resin composition according to any one of [1] to [5].

  According to the present invention, it is possible to obtain a polycarbonate resin composition excellent in balance of flame retardancy and transparency and suitable for applications such as window materials for aircraft and houses, agricultural houses, building materials such as sound insulation walls, etc. .

  The embodiment of the present invention will be described in detail below, but the description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to the following unless the gist is exceeded. The present invention is not limited to the contents of the above, and can be appropriately modified and implemented.

[Polycarbonate resin (A)]
The polycarbonate resin composition of the present invention (hereinafter, also referred to as “the present composition”) is a polycarbonate resin containing a structural unit (a) derived from a dihydroxy compound represented by the following general formula (1) in part of the structure (A) is a main component. Here, the main component means that the content is usually more than 50% by mass, preferably 70% by mass or more, and more preferably 90% by mass or more.
By using the polycarbonate resin (A) as a main component, the present composition is excellent in the balance of transparency, heat resistance, low water absorption, surface hardness, low birefringence and impact resistance.

Examples of the dihydroxy compound represented by the general formula (1) include isosorbide, isomannide and isoidide which are in a stereoisomer relationship. One of these may be used alone, or two or more of these may be used in combination.
Since these dihydroxy compounds do not have a phenolic hydroxyl group, they are usually difficult to polymerize by the interfacial method, and the polycarbonate resin (A) according to the present invention is usually produced by transesterification using a diester of carbonic acid .

  Among these dihydroxy compounds, among others, isosorbide obtained by dehydration condensation of sorbitol which is abundant as a plant-derived resource and is produced from various starches which are easily available is easy to obtain and manufacture, light resistant The most preferable in view of the properties, optical properties, moldability, heat resistance and carbon neutrality.

  Structural units (b) derived from other dihydroxy compounds other than the structural units derived from the dihydroxy compound represented by the general formula (1) in the polycarbonate resin (A) for imparting the flexibility of the polycarbonate resin (A), etc. When the component (a) is introduced, the polycarbonate resin (A) used in the present invention has a structural unit (a) derived from the dihydroxy compound represented by the general formula (1) with respect to all structural units derived from the dihydroxy compound In general, the content is preferably 30 mol% or more, more preferably 35 mol% or more, and particularly preferably 40 mol% or more. Also, it is usually preferable to contain 95 mol% or less, more preferably 85 mol% or less, and particularly preferably 75 mol% or less.

  If the ratio of the structural unit (a) derived from the dihydroxy compound represented by the general formula (1) to the total structural units derived from the dihydroxy compound is 30 mol% or more, the present composition is excellent in heat resistance and surface hardness It is preferable because it becomes a thing. On the other hand, if it is 95 mol% or less, the water absorption rate of the present composition becomes low, and deterioration due to heat decreases, which is preferable.

  As a structural unit (b) derived from other dihydroxy compounds other than the structural unit (a) derived from the dihydroxy compound represented by the said General formula (1) introduce | transduced into polycarbonate resin (A), an aliphatic dihydroxy compound And structural units derived from alicyclic dihydroxy compounds. Specific examples of the aliphatic dihydroxy compound and the alicyclic dihydroxy compound include the following.

<Aliphatic dihydroxy compounds>
As aliphatic dihydroxy compounds, for example, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-ethyl -1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol and the like.

  In addition, the said exemplary compound is an example of the aliphatic dihydroxy compound which can be used for this invention, Comprising: It is not limited to these at all. One of these aliphatic dihydroxy compounds may be used alone, or two or more thereof may be mixed and used.

  In the polycarbonate resin (A) used in the present invention, the molar ratio between the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the aliphatic dihydroxy compound can be selected in any ratio. However, by adjusting the molar ratio, it is possible to balance rigidity and impact resistance and to design appropriate formability.

<Alicyclic dihydroxy compound>
Although it does not specifically limit as an alicyclic dihydroxy compound, Usually, the compound containing a 5-membered ring structure or a 6-membered ring structure is mentioned. When the alicyclic dihydroxy compound has a 5- or 6-membered ring structure, the heat resistance of the resulting polycarbonate resin (A) tends to be high. The six-membered ring structure may be fixed in a chair or cage shape by a covalent bond. The carbon number contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, more preferably 30 or less. An alicyclic dihydroxy compound having 70 or less carbon atoms is preferable because it is easy to synthesize and purify, and inexpensive and easy to obtain.

Specific examples of the alicyclic dihydroxy compound containing a 5- or 6-membered ring structure include alicyclic dihydroxy compounds represented by the following general formula (I) or (II).
HOCH ₂ -R ₉ -CH ₂ OH (I)
HO-R ₁₀ -OH (II)
(However, in Formula (I) and Formula (II), R ₉ and R ₁₀ each independently represent a substituted or unsubstituted divalent group having a C 4 to C 20 cycloalkyl structure. )

As cyclohexanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I), in the general formula (I), R ₉ is a group represented by the following general formula (Ia) (wherein, R ₁₁ is a hydrogen atom, or And various isomers represented by the substituted or unsubstituted C.sub.1-C.sub.12 alkyl group). As such a thing, a 1, 2- cyclohexane dimethanol, a 1, 3- cyclohexane dimethanol, a 1, 4- cyclohexane dimethanol etc. are mentioned specifically ,.

As tricyclodecane dimethanol which is an alicyclic dihydroxy compound represented by said general formula (I), and pentacyclopentadecane dimethanol, in General formula (I), R ₉ is the following general formula (Ib) , N represents 0 or 1.) includes various isomers represented by

As decalin dimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I) or tricyclotetradecane dimethanol, in the general formula (I), R ₉ is the following general formula (Ic) (wherein m represents 0 or 1.) includes various isomers represented by). As such a thing, a 2, 6- decalin dimethanol, a 1, 5- decalin dimethanol, a 2, 3- decalin dimethanol etc. are mentioned specifically ,.

As the norbornanedimethanol which is an alicyclic dihydroxy compound represented by the general formula (I), in the general formula (I), the various isomers which R ₉ is represented by the following general formula (Id) Include. As such a thing, a 2, 3- norbornane dimethanol, a 2, 5- norbornane dimethanol etc. are mentioned specifically ,.

The adamantane dimethanol is an alicyclic dihydroxy compound represented by formula (I), in formula (I), encompasses various isomers which R ₉ is represented by the following general formula (Ie). As such a thing, a 1, 3- adamantane dimethanol etc. are specifically mentioned.

Moreover, in General Formula (II), R ₁₀ is a group represented by the following General Formula (IIa) (wherein, R ₁₁ is a hydrogen atom, or And various isomers represented by the substituted or unsubstituted alkyl group having 1 to 12 carbon atoms). Specific examples thereof include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol and the like.

As tricyclodecanediol which is an alicyclic dihydroxy compound represented by the said general formula (II), and pentacyclopentadecanediol, in General formula (II), R ₁₀ is the following general formula (IIb) (In the Formula, n And 0 represents 1 or 0.) includes various isomers represented by).

As decalin diol which is an alicyclic dihydroxy compound represented by the above general formula (II) or tricyclotetradecane diol, in the general formula (II), R ₁₀ is a group represented by the following general formula (IIc) (wherein m is It includes various isomers represented by 0 or 1.). As such a thing, a 2, 6- decalin diol, a 1, 5- decalin diol, a 2, 3- decalin diol etc. are mentioned specifically ,.

The norbornane diol which is an alicyclic dihydroxy compound represented by the general formula (II), in the general formula (II), includes various isomers where R ₁₀ is represented by the following general formula (IId). As such a thing, a 2, 3- norbornane diol, a 2, 5- norbornane diol etc. are mentioned specifically ,.

The adamantane diol which is an alicyclic dihydroxy compound represented by the general formula (II), in the general formula (II), includes various isomers where R ₁₀ is represented by the following general formula (IIe). As such a thing, a 1, 3- adamantanediol etc. are mentioned specifically ,.

  Among the specific examples of the above-mentioned alicyclic dihydroxy compounds, cyclohexanedimethanols, tricyclodecanedimethanols, adamantanediols and pentacyclopentadecanedimethanols are preferable, and they are easy to obtain and easy to handle. From the viewpoint, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecanedimethanol are more preferable, and 1,4-cyclohexanedimethanol is particularly preferable.

  In addition, the said exemplary compound is an example of the alicyclic dihydroxy compound which can be used for this invention, Comprising: It is not limited to these at all. One of these alicyclic dihydroxy compounds may be used alone, or two or more thereof may be mixed and used.

  In the polycarbonate resin (A) used in the present invention, the molar ratio between the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound is selected at an arbitrary ratio. Although it is possible, by adjusting the molar ratio, the impact strength (for example, notched Charpy impact strength) may be improved, and it is possible to obtain the desired glass transition temperature of the polycarbonate resin.

The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 90 ° C. to 160 ° C., more preferably 100 ° C. to 150 ° C., still more preferably 110 ° C. to 145 ° C., and 115 ° C. to 143 ° C. Particularly preferred. When the glass transition temperature of the polycarbonate resin (A) is 90 ° C. or more, the present composition is excellent in heat resistance. On the other hand, when the glass transition temperature of the polycarbonate resin (A) is 160 ° C. or less, the present resin composition is excellent in moldability and transparency.
Further, since the dihydroxy compound represented by the general formula (1) is generally easily thermally decomposed even in an inert atmosphere, the glass transition temperature may be set in the relevant range to eliminate the need to set the molten resin temperature excessively high. If possible, it is preferable because the possibility of causing significant thermal decomposition is small.

  The glass transition temperature is a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC 220, manufactured by SII Nano Technology Inc.) in accordance with JIS-K7121 (2012). Refers to the extrapolated glass transition temperature to be measured.

  In the polycarbonate resin (A) used in the present invention, the molar ratio of the structural unit derived from the dihydroxy compound represented by the general formula (1) and the structural unit derived from the alicyclic dihydroxy compound is 95: 5 to 30. It is preferably 70, and more preferably 75:25 to 40:60. When the molar ratio is within the above range, coloring caused by thermal retention is unlikely to occur in the polycarbonate resin (A), and improvement in heat resistance can be achieved by increasing the molecular weight, improving the impact strength, and maintaining the glass transition temperature. It is preferable because

  In the polycarbonate resin (A) used in the present invention, a structural unit derived from the dihydroxy compound represented by the general formula (1), a structural unit derived from an aliphatic dihydroxy compound, as long as the effects of the present invention are not inhibited In addition to structural units derived from alicyclic dihydroxy compounds, structural units derived from other dihydroxy compounds may further be included. As other dihydroxy compounds, dihydroxy compounds having a portion represented by the following general formula (3) in a part of the structure other than the dihydroxy compound represented by the above general formula (1), an aromatic dihydroxy compound, etc. Can be mentioned.

(However, the site represented by the general formula (3) unless a part of _-CH 2 -O-H.)

  Specific examples of the dihydroxy compound having a portion represented by the general formula (3) in a part of the structure other than the dihydroxy compound represented by the general formula (1) include diethylene glycol, triethylene glycol, tetra Oxyalkylene glycols such as ethylene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4 -(2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- ( -Hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3 5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2) And dihydroxy compounds such as, 2-dimethylpropoxy) phenyl) fluorene and the like, which have an aromatic group in the side chain and the ether group bonded to the aromatic group in the main chain is a moiety represented by the general formula (3) Be In addition, a part of heterocyclic groups such as compounds having a cyclic ether structure such as spiro glycol represented by compounds represented by the following general formula (4a) and compounds represented by the following general formula (4b) The dihydroxy compound which is a site | part represented by General formula (3) is mentioned.

  The "cyclic ether structure" of the above "compound having a cyclic ether structure" means a structure having an ether group in the cyclic structure and having a structure in which carbon constituting the cyclic chain is aliphatic carbon. . Among these, those having a plurality of ether groups are preferable, those having a plurality of cyclic ether structures are more preferable, and those having two cyclic ether structures are particularly preferable.

(In the above general formula (4a), R _{a to} R _d are each independently an alkyl group having 1 to 3 carbon atoms.)

  As the dihydroxy compound represented by the above general formula (4a), 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (Conventional name: spiro glycol), 3,9-bis (1,1-diethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis ( 1,1-dipropyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, dioxane glycol and the like.

  Examples of aromatic dihydroxy compounds include bisphenol compounds (including substituted and unsubstituted ones). Specifically, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1 1,1-Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane 1,1-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) ) 3-Methylbutane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) hexene , 3,3-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1- Bisphenol compounds having no substituent on an aromatic ring such as bis (4-hydroxyphenyl) cyclohexane; bis (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) ) Having an aryl group as a substituent on an aromatic ring such as ethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) propane and 2,2-bis (3-phenyl-4-hydroxyphenyl) propane Bisphenol compounds; bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methyl) Phenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-) Methylphenyl) cyclohexane, bis (4-hydroxy-3-ethylphenyl) methane, 1,1-bis (4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (4-hydroxy-3-ethylphenyl) Propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 1,1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-isopropylphenyl) ) Propane, 2,2-bis (4-hydroxy-3- (sec-butyl) phenyl) propane, bis (4-hydroxy-3,5-di) Methylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4 -Hydroxy-3,5-dimethylphenyl) cyclohexane, bis (4-hydroxy-3,6-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,6-dimethylphenyl) ethane, 2,2- Bis (4-hydroxy-3,6-dimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) methane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) ) Ethane, 2,2-bis (4-hydroxy-2,3,5-trimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphene) ) Aromatics such as phenylmethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) phenylethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane and the like Bisphenol compounds having an alkyl group as a substituent on the ring; bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) A bisphenol compound in which a divalent group linking an aromatic ring such as -1-phenylpropane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) dibenzylmethane has an aryl group as a substituent; 4'-dihydroxydiphenyl ether, 3,3 ', 5,5'-tetramethyl-4, Bisphenol compounds in which an aromatic ring such as '-dihydroxydiphenyl ether is linked by an ether bond; 4,4'-dihydroxydiphenyl sulfone, 3,3', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfone, etc. Bisphenol compound in which aromatic ring is connected by sulfone bond; 4,4′-dihydroxydiphenyl sulfide, sulfide bond of aromatic ring such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide The bisphenol compound etc. which were connected by these, etc. are mentioned, Preferably 2,2-bis (4-hydroxyphenyl) propane (another name: bisphenol-A) is mentioned.

Generally, the dihydroxy compound represented by the above general formula (1) is inclined in the direction in which the polymerization reaction proceeds with polymerization as compared with aromatic dihydroxy compounds such as bisphenol-A, and heating or phenol removal is When it volatilizes, the polymerization reaction tends to be rapid, making it difficult to control the reaction.
For this reason, if a small amount of the aromatic dihydroxy compound is added at the final stage of the polymerization reaction, the polymerization end is blocked by the aromatic dihydroxy compound, and even if heating or phenol devolatization occurs, the polymerization reaction is rapid. You can expect an effect that you do not need to

  However, if the polycarbonate resin (A) contains a large amount of structural units derived from the aromatic dihydroxy compound, birefringence of the present composition increases, or heat resistance and surface hardness of the present composition decrease. Besides, there is a possibility that yellowing may occur due to ultraviolet absorption when the composition is used outdoors. Therefore, the structural unit derived from the aromatic dihydroxy compound may be contained in the minimum necessary range, but preferably not contained.

  The above-mentioned other dihydroxy compounds may be used alone or in combination of two or more.

<Carbon diester>
The polycarbonate resin (A) used in the present invention can be obtained by polycondensation by transesterification using a dihydroxy compound containing a dihydroxy compound represented by the above-mentioned general formula (1) and a carbonic diester as raw materials.

  As a carbonic acid diester to be used, what is normally represented by following General formula (5) is mentioned. One of these carbonic acid diesters may be used alone, or two or more thereof may be mixed and used.

However, in the above general formula (5), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group .

  Examples of the carbonic acid diester represented by the formula (5) include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate. Is a diaryl carbonate such as diphenyl carbonate and diphenyl carbonate having a substituent, and among the diaryl carbonates, diphenyl carbonate is preferable.

  The carbonic acid diester may contain impurities such as chloride ions, and these impurities may inhibit the polymerization reaction or may deteriorate the hue of the obtained polycarbonate resin (A). Accordingly, it is preferable to use one purified by distillation or the like.

<Transesterification catalyst>
The polycarbonate resin (A) used in the present invention is obtained by transesterification between a dihydroxy compound containing a dihydroxy compound represented by the above general formula (1) and a carbonic acid diester as described above. More specifically, it is obtained by transesterification and removal of by-produced monohydroxy compounds etc. out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.

  The transesterification reaction catalyst (hereinafter, may be simply referred to as “catalyst” or “polymerization catalyst”) that can be used in the production of the polycarbonate resin (A) used in the present invention has a light transmittance or a yellow index (in particular YI) May affect the value.

  As the catalyst to be used, those which can satisfy the light resistance of the polycarbonate resin (A) to be obtained, that is, the YI value described later can be made equal to or less than a predetermined value are preferable. For example, Group 1 or 2 in the long period periodic table And basic compounds such as metal compounds of basic groups (hereinafter simply referred to as “group 1” and “group 2”), basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine compounds and the like. Among these, preferably at least one of Group 1 metal compound and Group 2 metal compound is used.

  It is also possible to additionally use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound and the like together with at least one of the group 1 metal compound and the group 2 metal compound. It is particularly preferred to use at least one of Group 1 metal compounds and Group 2 metal compounds.

  In addition, at least one of the Group 1 metal compound and the Group 2 metal compound is usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt, but is easily available. From the viewpoint of ease of handling, hydroxides, carbonates and acetates are preferred, and from the viewpoint of hue and polymerization activity, acetates are preferred.

  The amount of the polymerization catalyst used is preferably 0.1 to 300 μmol, more preferably 0.5 to 100 μmol, per mol of all the dihydroxy compounds used. Among them, when using at least one metal compound selected from the group consisting of lithium and a metal of long period periodic table group 2, particularly, at least one metal compound selected from the group consisting of a magnesium compound and a calcium compound is used In this case, the amount of metal is preferably 0.1 to 20 μmol, more preferably 0.5 to 10 μmol, and particularly preferably 0.7 to 3 μmol, per mol of all dihydroxy compounds used.

  If the amount of the polymerization catalyst used is 0.1 μmol or more, the polymerization rate will be a certain level or more, and therefore, it is not necessary to raise the polymerization temperature when trying to obtain a polycarbonate resin having a desired molecular weight, The hue or light resistance of the resin may be deteriorated, or the unreacted raw material may be volatilized during polymerization to change the molar ratio of the dihydroxy compound containing the dihydroxy compound represented by the general formula (1) to the carbonic diester. It is preferable because the possibility of not reaching the molecular weight is small. On the other hand, it is preferable that the use amount of the polymerization catalyst is 300 μmol or less, since the possibility of deterioration of the color of the obtained polycarbonate resin and the light resistance of the polycarbonate resin is small. Moreover, it is preferable because the possibility of reaching a target molecular weight without sufficiently reducing the pressure in the polymerization reactor and the possibility of not sufficiently degassing the remaining monomer are small.

  In addition, Group 1 metals, in particular, lithium, sodium, potassium and cesium, if contained in a large amount in the polycarbonate resin, may adversely affect the hue, and the metal is not only from the catalyst used, but also the raw material or reactor May contaminate from Therefore, the total amount of these compounds in the polycarbonate resin is preferably 1 mass ppm or less, more preferably 0.8 mass ppm or less, and still more preferably 0.7 mass ppm or less in terms of metal amount. is there.

  The amount of metal in the polycarbonate resin can be measured using a method such as atomic emission, atomic absorption or inductively coupled plasma (ICP) after recovering the metal in the polycarbonate resin by a method such as wet ashing.

<Method of producing polycarbonate resin (A)>
The polycarbonate resin (A) used in the present invention is a transesterification of a dihydroxy compound containing a dihydroxy compound represented by the general formula (1) and a carbonic diester represented by the general formula (5) in the presence of a catalyst It can be obtained by polycondensation by reaction.
At this time, the raw material dihydroxy compound and the carbonic diester may be uniformly mixed before the transesterification reaction, or may be simultaneously introduced into the polymerization tank without being mixed, but it is preferable to uniformly mix.

  The mixing temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and the upper limit thereof is usually 250 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 150 ° C. or lower. is there. Among them, 100 ° C. or more and 120 ° C. or less are preferable. If the temperature of mixing is 80 ° C. or higher, the dissolution rate is increased, which is preferable because it is less likely to cause operation problems such as solidification due to insufficient solubility. In addition, if the mixing temperature is 250 ° C. or less, the possibility of thermal degradation of the dihydroxy compound is small, and the hue and light resistance of the obtained polycarbonate resin are favorable, which is preferable.

  The polycarbonate resin (A) used in the present invention is usually solidified by cooling after polycondensation as described above, and is pelletized by a rotary cutter or the like.

  The method of pelletizing is not limited, for example, a method of extracting in the molten state from the final polymerization reactor, cooling and solidifying it in the form of a strand and pelletizing it, or uniaxially or in the molten state from the final polymerization reactor The resin was supplied to a twin-screw extruder, melted and extruded, and then solidified by cooling and pelletized, or it was extracted from the final polymerization reactor in the molten state, cooled and solidified in the form of strands and pelletized once After that, the resin is again supplied to a single-screw or twin-screw extruder, and after melt-extruding, it is cooled and solidified to pelletize it.

  At that time, in the extruder, degassing the remaining monomer under reduced pressure, or generally known, thermal stabilizers, neutralizing agents, UV absorbers, mold release agents, coloring agents, antistatic agents, lubricants, lubricants It is also possible to add and knead plasticizers, compatibilizers or flame retardants.

  The melt-kneading temperature in the extruder depends on the glass transition temperature or molecular weight of the polycarbonate resin, but is preferably 150 to 300 ° C., more preferably 200 to 270 ° C., still more preferably 230 to 260 ° C. is there. By setting the melt-kneading temperature to 150 ° C. or higher, the melt viscosity of the polycarbonate resin is reduced, the load on the extruder is reduced, and the productivity is improved. Further, by setting the melt-kneading temperature to 300 ° C. or less, it is possible to suppress the thermal deterioration of the polycarbonate resin and to prevent the reduction of the mechanical strength due to the reduction of the molecular weight and the generation of coloring or gas.

In the extruder, the vent pressure in the case of vacuum degassing is preferably 0.001 kPa to 5 kPa, more preferably 0.005 kPa to 3 kPa, and still more preferably 0.007 kPa to 2 kPa.
If the vent pressure is in the above-mentioned range, it is possible to sufficiently degas the remaining monomer and generated gas, and when extruding in the form of a strand, the strand may be cut, or the polymerization reaction or decomposition of the polycarbonate resin in the extruder. Is preferable because it is unlikely to progress.
A uniform resin can be obtained by making the amount of resin fed into the extruder, the number of revolutions of the extruder, the barrel temperature, and the vent pressure as constant as possible.
Further, by keeping the temperature of the vent and the piping after the vent at 40 ° C. or higher, the vented monomer can be maintained at a uniform vent pressure without solidifying in the vent and the piping after the vent.

[Bromine-Containing Phosphate Compound (B)]
It is important that the present composition contains a bromine-containing phosphoric acid ester compound (B) having bromine in its structure as a flame retardant. The bromine-containing phosphate ester compound is compatible with the polycarbonate resin (A), so that a transparent molded article can be obtained. In addition, active hydroxyl groups and hydrogen radicals are trapped during combustion, and the hydrogen halide produced is nonflammable and exhibits excellent flame retardance from the dilution effect and the oxygen blocking effect.

  Examples of the bromine-containing phosphoric acid ester compounds used in the present invention include tris (tribromoneopentyl) phosphate, bis (tribromoneopentyl) dichloropropyl phosphate, bis (tribromoneopentyl) chloropropyl phosphate, bis (tribromo) Neopentyl) methyl phosphate, bis (tribromoneopentyl) ethyl phosphate, bis (tribromoneopentyl) phenyl phosphate, bis (tribromoneopentyl) cresyl phosphate, bis (tribromoneopentyl) tribromophenyl phosphate, bis (Dichloropropyl) tribromoneopentyl phosphate, bis (chloropropyl) tribromoneopentyl phosphate, bis (chloroethyl) tribromoneopentyl phosphate, dime Le tribromoneopentyl phosphate, diethyl tribromoneopentyl phosphate, diphenyl tribromoneopentyl phosphate, dicresyl tribromoneopentyl phosphate, and bis (tri-bromophenyl) tribromoneopentyl phosphate.

  The proportion of the bromine-containing phosphorus compound (B) in the resin composition is 0.1 to 20% by mass, preferably 0.2 to 10% by mass, and more preferably 0.5 to 5.0% by mass. If it is less than 0.1% by mass, the flame retardancy of the composition is reduced. On the other hand, when it exceeds 20 mass%, the heat resistance and transparency fall by excess addition.

[Non-halogen phosphate ester compound (C)]
The composition further contains a non-halogen phosphate compound (C) in the structure as a flame retardant.
Examples of non-halogen phosphate compounds used in the present invention include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di 2,6-xylenyl phosphate and the like. And phosphoric acid ester compounds such as 1,3-phenylenebis (2,6-dimethylphenyl) phosphate, tetraphenyl (m-phenylene) bisphosphate, and condensed phosphorus such as bis (ditolyl) isopropylidene-di-p-phenylene phosphate Examples thereof include acid ester compounds, phosphoric acid ester amide compounds such as 4,4'-bis (diphenylphosphorylamidophenyl) methane, and phosphazene compounds such as phosphonitrilic acid phenyl ester. Among these, it is preferable to use a condensed phosphoric acid ester-based compound or a phosphazene-based compound from the viewpoint of flame retardancy and hydrolysis resistance.

  These compounds form a carbonized layer (char) by promoting the dehydration reaction, and exhibit an air blocking effect and a heat insulating effect. Although low molecular type phosphate ester compounds such as triphenyl phosphate (TPP) may be used, transparency, impact resistance, heat resistance can be obtained by containing the polycarbonate resin (A) and the condensed phosphate ester compound according to the invention. It is possible to impart the self-extinguishing property (flame retardancy) at the time of resin burning without substantially reducing the property. Further, by using a predetermined amount of the halogen-containing flame retardant, in particular, a phosphoric acid ester compound containing bromine in the structure in combination, the flame retardancy at the time of resin burning can be further improved while maintaining the transparency.

  The proportion of the non-halogen phosphate compound (C) is 0.5 to 20% by mass, preferably 1.0 to 10% by mass, and more preferably 1.5 to 5.0% by mass in the resin composition. is there. If it is less than 0.5% by mass, the flame retardancy of the composition is reduced. On the other hand, when it exceeds 20 mass%, the heat resistance and transparency fall by excess addition.

[Flame retardant aid]
The present resin composition can contain a flame retardant auxiliary as long as the effects of the present invention are not impaired. Among them, a drip inhibitor which is made of a fluorine resin and improves melt tension of the resin by fibrillation at the time of combustion, and an antimony compound which exhibits a synergistic effect by being used in combination with a halogen type flame retardant is suitably used.

  Further, the resin composition of the present invention may be a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antibacterial / antifungal agent, an antistatic agent, a lubricant, a pigment, a dye, etc. insofar as the effects of the present invention are not impaired. Additives can be contained.

<Method of manufacturing plate>
Another subject matter of the present invention is a plate (hereinafter referred to as "the plate") using the present composition. The method for producing the plate is not particularly limited. For example, polycarbonate resins, flame retardants, flame retardant aids and, if necessary, other resins / additives are melt-kneaded using a single- or twin-screw extruder etc. and heat-pressed those obtained by injection molding or compound molding Can be produced by

<Thickness of plate>
Although the thickness of the plate is not particularly limited, for example, in consideration of processability and practicability, it is preferably 0.5 mm or more and 3.0 mm or less, and is 1.0 mm or more and 3.0 mm or less Is more preferred. When the thickness of the present plate is 1.0 mm or more, suitable rigidity of the plate is developed, and the processability and the curling resistance are excellent.

<Physical value of the present resin composition>
(1) Flame Retardancy The present composition is excellent in flame retardancy, and is self-extinguishing instantly when burned due to a fire or the like. It is also important that when the molten resin drips (drips) at the time of combustion, the burning of the dripping material self-extinguishes instantly.

(2) Transparency The present composition is excellent in transparency, and is a single-plate main plate which is measured based on JIS K 7136-1 (1997) from the viewpoint of designability, visibility of contents and the like. The total light transmittance at a thickness of 1.0 mm is preferably 85% or more, more preferably 88% or more, and particularly preferably 90% or more. Moreover, it is preferable that the total haze value in thickness 1.0mm of this plate of a single layer measured based on JISK7136 (2000) is 5.0% or less, and is 3.0% or less More preferably, it is particularly preferably 1.0% or less. The lower limit of the total haze value is not particularly limited, and is preferably as small as possible. If the total haze value and the total light transmittance are in the relevant range, the present composition is particularly excellent in transparency.

<Use of this resin composition>
The molded article of the present invention formed as a film, sheet or plate is excellent in transparency and flame retardancy. Therefore, although it is not particularly limited in the present invention, it can be used, for example, as housing materials, window materials for aircrafts and automobiles, sound insulation walls, electronic members, household appliance members, OA equipment members and the like.

  The polycarbonate resin composition of the present invention can be used as a forming film, a sheet, a plate or the like to perform various secondary processing, and can also be made into a thermoformed article by thermoforming. It does not specifically limit as a method of thermoforming, Well-known shaping | molding methods, such as blister shaping | molding, vacuum formation, pressure forming, can be utilized.

  Although an example is shown below, the present invention is not restricted at all by these. In addition, the various measured values and evaluation about the raw material and test piece displayed in this specification were performed as follows.

<Various evaluation methods>
(1) Flame retardancy (combustion test)
In the combustion test, a test specimen of 100 mm long × 13 mm wide and 1.0 mm thick was placed vertically from the bottom to a height of 30 cm and lengthwise, and indirectly flamed from the bottom of the test specimen by a gas burner for 10 seconds. The subsequent (i) burning time and (ii) the burning time of the dripping material due to flame contact were measured. The combustion after removing the flame was extinguished in 5 seconds or less, and the burning time of the dripping material by the combustion was 3 seconds or less.
(2) Transparency (total light transmittance, total haze)
The total haze value was measured based on JIS K7136 (2000), for a sample having a thickness of 1.0 mm.

<Material used>
[Polycarbonate resin (PC)]
PC-1: Polycarbonate resin (manufactured by Mitsubishi Chemical Corporation): Structural unit derived from isosorbide / structural unit derived from 1,4-cyclohexanedimethanol = 50/50 mol%
PC-2: Polycarbonate resin (manufactured by Mitsubishi Chemical Corporation): Structural unit derived from isosorbide / structural unit derived from 1,4-cyclohexanedimethanol = 70/30 mol%
[Halogen based flame retardant (HX)]
HX-1: Bromine-containing phosphoric acid ester compound (manufactured by Daihachi Chemical Industry Co., Ltd., CR-900, tris (tribromoneopentyl) phosphate)
HX-2: Tetrabromobisphenol A oligomer (manufactured by Teijin Limited, Fireguard-7500)
[Non-halogen phosphoric acid ester compound (FP)]
FP-1: Condensed phosphoric acid ester (manufactured by Daihachi Chemical Industry Co., Ltd., PX-200)
FP-2: aromatic phosphoric acid ester (manufactured by Marubishi Yuka Kogyo Co., Ltd., Nonnen 73)

Example 1
Weigh PC-1, HX-1 and FP-1 at a mixing mass ratio of 90: 5: 5, and test them at a test temperature of 230 ° C and rotational speed of 80 rpm with a Labo Plastomill manufactured by Toyo Seiki Seisakusho Co., Ltd. After kneading for 5 minutes, a plate of 1.0 mm thickness was obtained using an electrothermal press set to a temperature of 230.degree. Each measurement of the obtained plate was evaluated. The results are shown in Table 1.

(Example 2)
A plate was prepared and evaluated in the same manner as in Example 1 except that PC-1, HX-1 and FP-1 were kneaded at a mixing mass ratio of 93: 2: 5. The results are shown in Table 1.

(Example 3)
A plate was prepared and evaluated in the same manner as in Example 1 except that PC-1, HX-1 and FP-2 were kneaded at a mixing mass ratio of 90: 5: 5. The results are shown in Table 1.

(Example 4)
A plate was prepared and evaluated in the same manner as in Example 1 except that PC-1, HX-1 and FP-2 were mixed at a mixing mass ratio of 93: 2: 5. The results are shown in Table 1.

(Example 5)
A plate was prepared and evaluated in the same manner as in Example 1 except that PC-2, HX-1 and FP-1 were mixed at a mixing mass ratio of 90: 5: 5. The results are shown in Table 1.

(Comparative example 1)
The preparation and evaluation of the plate were carried out in the same manner as in Example 1 using PC-1 alone. The results are shown in Table 1.

(Comparative example 2)
A plate was prepared and evaluated in the same manner as in Example 1 except that PC-1 and HX-1 were kneaded at a mixing mass ratio of 90:10. The results are shown in Table 1.

(Comparative example 3)
A plate was prepared and evaluated in the same manner as in Example 1 except that PC-1 and FP-1 were kneaded at a mixing mass ratio of 95: 5. The results are shown in Table 1.

(Comparative example 4)
A plate was prepared and evaluated in the same manner as in Example 1 except that PC-1 and FP-1 were kneaded at a mixing mass ratio of 90:10. The results are shown in Table 1.

(Comparative example 5)
A plate was prepared and evaluated in the same manner as in Example 1 except that PC-1, HX-2 and FP-1 were mixed at a mixing mass ratio of 90: 5: 5. The results are shown in Table 1.

  The polycarbonate resin films described in Examples 1 to 5 were particularly excellent in flame retardancy while dramatically suppressing the decrease in transparency due to the flame retardant. On the other hand, the sheets described in Comparative Examples 1 to 5 were inferior to Examples in flame retardancy and transparency.

  Although the present invention is not particularly limited, it is expected to be developed in various applications such as window materials for automobiles, trains, aircrafts, etc., sound insulation walls, housing materials, building materials, household appliance materials, agricultural houses, and the like.

Claims (4)

A polycarbonate resin composition containing a flame retardant as a main component of the following polycarbonate resin (A),
The flame retardant contains 0.1 to 20% by mass of bromine-containing phosphoric acid ester (B) in the resin composition and 0.5 to 20% by mass of non-halogenated phosphoric acid ester (C) in the resin composition. Polycarbonate resin composition characterized in that.
(A) A structural unit (a) derived from a dihydroxy compound represented by the following general formula (1) in part of the polymer structure, and 1,4-cyclohexanediyl as a structural unit (b) derived from another dihydroxy compound contains a structural unit derived from methanol, the molar ratio of the structural units (a) and the structural unit (b) is 95: 5-30: 70 der Ru polycarbonate resin
The polycarbonate resin composition according to claim 1, wherein the total light transmittance of the plate having a thickness of 1.0 mm to be measured is 85% or more and the total haze value is 5.0% or less based on JIS K7136. . A molded article formed using the polycarbonate resin composition according to claim 1 or 2 . A window material formed using the polycarbonate resin composition according to claim 1 or 2 .