JP5369296B2 - Aromatic polycarbonate resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition with less discoloration during heat melting, and hardly opacified due to heat and humidity of the molding after molding. <P>SOLUTION: The polycarbonate resin composition includes 100 pts.wt. of an aromatic polycarbonate resin represented by formula (1) having an alicyclic group at least in a side chain; 0.001-1 pt.wt. of a phosphorus-based stabilizer having a spiro structure; and 0.001-1 pt.wt. of a phenolic stabilizer. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an aromatic polycarbonate resin composition, and more particularly to an aromatic polycarbonate resin composition having a high glass transition temperature and excellent heat resistance. The present invention also relates to a molded product comprising the aromatic polycarbonate resin composition of the present invention.

  Aromatic polycarbonate resin is an engineering plastics with excellent mechanical properties, electrical properties, transparency, dimensional stability, and heat resistance. Electrical, electronic and OA equipment parts, automotive parts, precision machine parts, medical parts, building materials. Widely used as household items. As described above, the aromatic polycarbonate resin widely used at present is a resin obtained by reacting bisphenol A with a carbonate precursor. However, depending on the application, higher heat resistance is often required. Yes. For example, for the purpose of improving fuel economy by reducing the weight of automobiles, changing from high specific gravity metals and glass fiber reinforced thermosetting resins to thermoplastic resin parts, headlight lenses and inner lenses used in close proximity to heat sources When changing from inorganic glass to thermoplastic resin, higher heat resistance is required.

In response to such a demand, for example, Patent Document 1 discloses that by reacting at least one dihydric phenol having a cycloalkylidene group such as 4,4′-cyclododecylidenebisphenol with a carbonate precursor. Produced heat-resistant polycarbonate has been proposed. Patent Document 1 shows that the polycarbonate has a high glass transition point Tg and a high DTUL, which is one of heat resistance indicators.
However, the heat resistance of the resin composition is required not only from the viewpoint of DTUL but also from various viewpoints. In particular, it is desirable for molded articles for various uses to reduce discoloration such as yellow that occurs during heating and melting. Moreover, high transparency is requested | required of an optical component, and it is requested | required that transparency may not be impaired by wet heat. Patent Document 1 describes that additives such as antioxidants and coloring stabilizers can be mixed with the above heat-resistant polycarbonate resin, but there is no specific example, and of course, melt heat stability. There is no description of specific examples of additives that contribute to improvement of properties, reduction of hue of molded products, reduction of opacification of transparent molded products due to wet heat, and the like.

  Patent Document 2 discloses at least one type of polycarbonate resin having improved heat resistance, such as 1,1-bis (3,5-dibromo-4-hydroxyphenyl) cyclododecane, which has a halogen group and a cycloalkylidene group. A heat-resistant polycarbonate produced by reacting a dihydric phenol with a carbonate precursor is disclosed. However, in the polycarbonate disclosed in Patent Document 2, it is essential that at least one halogen atom is present on the aromatic ring of the dihydric phenol, and such a halogen atom is released during the melt molding of the polycarbonate. It easily causes corrosion of the barrel and screw of the molding machine and corrosion of the mold. As a result, a molded product made from the resin may be discolored such as yellowing. In addition, when the molded product is used in a high-temperature environment, there is a disadvantage that halogen atoms are detached and the discoloration of the molded product is promoted.

  Patent Document 3 discloses a heat comprising a polycarbonate containing a specific bifunctional carbonate structural unit such as 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and a specific silicon compound. A highly heat-resistant molding composition that has been stabilized to exhibit durability against deterioration and exhibits improved impact strength has been disclosed, but is easily yellowed by high-temperature hot-air treatment, and can be used in high-temperature environments. There is a limit.

  On the other hand, molded products made of an aromatic polycarbonate resin composition have a relatively low surface hardness, so that the surface of a molded product that requires scratch resistance, such as a cellular phone button or a computer keypad, is coated on the surface. A secondary processing treatment such as a hard coat treatment or a treatment with a resin having a high surface hardness and a laminate is often performed. From the viewpoint of cost and product yield, it is desired to provide a polycarbonate resin composition capable of producing a molded product having a sufficiently high surface hardness that does not require secondary processing.

  In response to such a requirement, Patent Document 4 proposes a polycarbonate having a special repeating structure and a terminal group, and in the examples, the molded film made of the polycarbonate had a small amount of wear in a predetermined wear test. It is shown. However, it is desired that the resin material exhibits not only the surface hardness of the molded product but also various properties such as melting heat stability and the hue of the molded product not changing color as described above. Patent Document 4 describes that additives such as an antioxidant and a color stabilizer can be mixed, but there is no description of specific examples, and of course, the hue of the molded product is reduced, and the transparent molded product. There is no description at all about specific examples of additives that contribute to the reduction of opacification due to wet heat.

  Patent Document 5 proposes a polycarbonate comprising a specific repeating unit of 4,4′-dihydroxydiphenyl carbonate structure type and a specific repeating unit of bisphenol carbonate structure type as a material for a film having a particularly high surface hardness. However, as in Patent Document 4, there is no description of specific antioxidants or coloring stabilizers, and additives that contribute to reducing the hue of the molded product, reducing the opacification of the transparent molded product due to wet heat, and the like. There is no description about specific examples.

JP 59-166528 A JP-T 61-502462 Japanese Patent Laid-Open No. 5-125269 JP 7-76619 A JP-A-5-339390

On the other hand, some stabilizers added to a molded product made of a resin composition may contribute to improvement of heat resistance, but may hydrolyze by wet heat and contribute to opacification of the molded product. In some cases, it is difficult to achieve both improvement in heat resistance and suppression of opacification due to wet heat.
The present invention solves the above-mentioned problems of the prior art, has a high glass transition temperature, excellent heat resistance, excellent melting heat stability, little coloration during heating and melting, and after molding, due to the wet heat of the molded product It is an object of the present invention to provide an aromatic polycarbonate resin composition that hardly causes opacification.
Another object of the present invention is that it has excellent heat resistance, little coloration due to thermal deterioration during molding, and hardly causes opacification due to wet heat, is excellent in surface hardness and low water absorption, and has tensile strength and bending strength. Another object is to provide a molded article made of an aromatic polycarbonate resin composition having good mechanical properties such as flexural modulus.

As a result of intensive studies to achieve the above object, the present inventors have made at least a reaction between at least one dihydric phenol having a cyclododecane group and no halogen atom, and a carbonate precursor. By using a specific phosphorus-based stabilizer and a specific phenol-based stabilizer together with the obtained aromatic polycarbonate resin, the inventors have obtained knowledge that the above object can be achieved, and have completed the present invention.
That is, in order to achieve the above object, the present invention represents an aromatic polycarbonate resin containing at least a unit represented by the following formula (1); represented by the following formula (3) with respect to 100 parts by weight of the aromatic polycarbonate resin. A phosphor containing 0.001 to 1 part by weight of a phosphorus stabilizer; and 0.001 to 1 part by weight of a phenol stabilizer represented by the following formula (4) with respect to 100 parts by weight of the aromatic polycarbonate resin. A polycarbonate resin composition is provided.

（式中、Ｒ¹〜Ｒ²⁶はそれぞれ独立して、水素原子、炭素原子数１〜９のアルキル基、炭素原子数６〜１２のアリール基、炭素原子数１〜５のアルコキシ基、炭素原子数２〜５のアルケニル基又は炭素原子数７〜１７のアラルキル基を表し、これらの基は、置換基を有していてもよいが、ハロゲン原子で置換されていることはない。）

Wherein R ^{1 to} R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon atom. Represents an alkenyl group having 2 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, and these groups may have a substituent, but are not substituted with a halogen atom.

（式中、Ｒ^1b〜Ｒ^4bはそれぞれ独立して、水素原子、水酸基、炭素原子数１〜１８のアルキル基、又は炭素原子数１〜１８のオキシアルキル基を表す。）

(In formula, R ^<1b > -R < ^4b > respectively independently represents a hydrogen atom, a hydroxyl group, a C1-C18 alkyl group, or a C1-C18 oxyalkyl group.)

（Ｙは分子内にヒドロキシ基を１〜３個有するヒドロキシ化合物の残基であるｎ価の基であり、ｎは１〜３の整数である。）

(Y is an n-valent group that is a residue of a hydroxy compound having 1 to 3 hydroxy groups in the molecule , and n is an integer of 1 to 3)

  The aromatic polycarbonate resin composition of the present invention has a high glass transition temperature, excellent heat resistance, excellent melting heat stability, and little discoloration during heating and melting. The molded article made of the aromatic polycarbonate resin composition is excellent in heat resistance, less colored due to thermal deterioration during molding, and less susceptible to opacification due to wet heat, and also excellent in surface hardness and low water absorption, and Mechanical properties such as tensile strength, bending strength, and flexural modulus are also good, and it is useful for various applications.

Hereinafter, the present invention will be described in detail. The present invention relates to an aromatic polycarbonate resin composition containing at least a predetermined aromatic polycarbonate resin, a predetermined phosphorus stabilizer, and a predetermined phenol stabilizer. Hereinafter, each component will be described in detail.
1. Aromatic polycarbonate resin The aromatic polycarbonate resin used in the present invention contains at least a unit represented by the following formula (1).

In the formula, R ^{1 to} R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or the number of carbon atoms. It represents a 2 to 5 alkenyl group or an aralkyl group having 7 to 17 carbon atoms, and these groups may have a substituent, but are not substituted with a halogen atom.
In the present specification, “alkyl group” and “alkenyl group” are used to mean any of linear, branched, and cyclic. The same applies to the alkyl group part of the “alkoxy group” and “aralkyl group”.
The alkyl group, aryl group, alkoxy group, and aralkyl group may each have one or more substituents. Preferred examples of the substituent include alkyl groups having 1 to 5 carbon atoms, and carbon. An alkoxy group having 1 to 5 atoms is included. However, it is not substituted with a halogen atom.

In the formula (1), the number of substituents of the two phenylene groups is preferably 0 to 2, that is, two or more of R ^{1 to} R ⁴ are preferably hydrogen atoms. Moreover, it is preferable that the number of substituents of the cyclododecanyl group in the said Formula (1) is 0-2.

  The structural unit of the above formula (1) is produced by a reaction between a bisphenol that induces the structural unit and a carbonate-forming compound. Examples of the bisphenols for deriving the structural unit of the formula (1) include compounds represented by the following structural formula (5).

Wherein, R ¹ to R ²⁶ are the same as each in the formula (1), and preferred ranges are also the same.

  Specific examples of the compound represented by the formula (5) include 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclododecane, 1, 1-bis (4-hydroxy-3-phenylphenyl) cyclododecane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) cyclododecane, 1,1-bis (4-hydroxy-3-sec- Butylphenyl) cyclododecane, 1,1-bis (4-hydroxy-3-allylphenyl) cyclododecane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclododecane, 7-ethyl-1, 1-bis (4-hydroxyphenyl) cyclododecane, 5,6-dimethyl-1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1 Bis (2-hydroxyphenyl) cyclododecane and the like. These can be used in combination of two or more. Among these, 1,1-bis (4-hydroxyphenyl) cyclododecane and 1,1-bis (4-hydroxy-3-methylphenyl) cyclododecane are particularly preferable.

  Moreover, the aromatic polycarbonate resin used in the present invention may contain other structural units. The other structural unit is preferably a structural unit represented by the following formula (2).

In the formula, R ^{1a to} R ^4a each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a phenyl group. These groups may have a substituent, but are preferably a substituent other than a halogen atom. The preferable example of a substituent is the same as the preferable example of the substituent which each of R < ¹ > -R < ²⁶ > in the said Formula (1) has.

  In the formula (2), X is a single bond, or

を表し；Ｒ^5a及びＲ^6aはそれぞれ独立して、水素原子、炭素原子数１〜１０のアルキル基、又はフェニル基を表し、Ｒ^5a及びＲ^6aが結合し単環又は縮合環を形成してもよい。Ｒ^5a及びＲ^6aが単環を形成する場合の単環の例には、シクロへキサン等が含まれ、及び縮合環を形成する場合の縮合環の例には、フルオレン等が含まれる。

R ^5a and R ^6a each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and R ^5a and R ^6a are combined to form a single ring or a condensed ring. Also good. Examples of the monocycle in which R ^5a and R ^6a form a monocycle include cyclohexane and the like, and examples of the condensed ring in the case of forming a condensed ring include fluorene and the like.

  The structural unit of the above formula (2) is produced by a reaction between a bisphenol that induces the structural unit and a carbonate-forming compound. Examples of the bisphenols that derive the structural unit of the formula (2) include compounds represented by the following structural formula (6).

In formula, about R < ^1a > -R < ^4a > and X, it is synonymous with each in the said Formula (2), and its preferable range is also the same.

  Examples of bisphenols that can be used as the raw material monomer together with the bisphenols of the formula (5) include various bisphenols in addition to the compound represented by the formula (6). Specifically, 4,4′-biphenyldiol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) ) Sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4 -Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis 4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3) -Allylphenyl) propane, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-2-methyl-5-tert-butylphenyl) -2 -Methylpropane, 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene , Α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethyldiphenyl random copolymer siloxane α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 4,4 ′-[1,3 -Phenylenebis (1-methylethylidene)] bisphenol and the like are exemplified. These can be used in combination of two or more. Of these, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, and 1,1-bis (4-hydroxyphenyl) cyclohexane are particularly selected. It is preferable that

  The aromatic polycarbonate resin may be produced using only the bisphenol represented by the formula (5) as the bisphenol. On the other hand, in an embodiment including a structural unit derived from other bisphenols (preferably bisphenols represented by the formula (6)), the bisphenols represented by the formula (5) are all bisphenols used. Of these, 5 mol% to 95 mol% is preferable, 10 mol% to 90 mol% is preferable, and 20 mol% to 80 mol% is preferable. Further, the other bisphenols (preferably bisphenols represented by the formula (6)) is preferably 95 mol% to 5% of all bisphenols used, and preferably 90 mol% to 10 mol. %, More preferably 80 mol% to 20 mol%.

  The aromatic polycarbonate resin is obtained by a reaction between a bisphenol represented by the formula (5) and, if desired, a bisphenol represented by the formula (6) and at least one carbonate-forming compound. Can be manufactured. The production method is not particularly limited, and various methods used in producing a polycarbonate derived from bisphenol A, such as a direct reaction between bisphenols and phosgene (phosgene method), and bisphenols and bisaryl carbonates. A method such as a transesterification reaction (transesterification method) can be employed.

  Examples of carbonic acid ester forming compounds that can be used include phosgene; bisaryl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate; . Two or more of these compounds can be used in combination.

  In the phosgene method, phosgene is usually reacted with the bisphenol of formula (5) and other bisphenols in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and the like. Examples of the solvent include methylene chloride and chloroform. Furthermore, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt can be used to accelerate the condensation polymerization reaction. Moreover, it is preferable to use monofunctional compounds, such as a phenol, p-tert-butylphenol, p-cumylphenol, and a long-chain alkyl substituted phenol, for polymerization degree adjustment (molecular weight adjustment). If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite, or a branching agent such as phloroglucin or isatin bisphenol may be added. The reaction usually proceeds at a temperature of 0 to 150 ° C, preferably 5 to 40 ° C. While the reaction time depends on the reaction temperature, it is generally 0.5 min-10 hr, preferably 1 min-2 hr. Further, during the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

  On the other hand, in the transesterification method, bisphenol of the formula (5) or other bisphenols and bisaryl carbonate are mixed and reacted at high temperature under reduced pressure. The reaction usually proceeds at 150 to 350 ° C and preferably proceeds at 200 to 300 ° C. Further, the degree of vacuum is finally reduced to 1 mmHg or less, and phenols derived from the bisaryl carbonate produced by the transesterification reaction are distilled out of the system. The reaction time depends on the reaction temperature, the degree of vacuum, etc., but is usually about 1 to 4 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, and the reaction may be carried out by adding a molecular weight regulator, an antioxidant or a branching agent as desired.

  The aromatic polycarbonate resin used in the present invention preferably has a desirable intrinsic viscosity in the range of 0.3 to 2.0 dl / g from the viewpoint of mechanical strength and moldability, and more preferably 0.35 to 1. The range is preferably 5 dl / g. When the intrinsic viscosity is less than 0.3 dl / g, the mechanical strength is low, and when the intrinsic viscosity exceeds 2.0 dl / g, the fluidity is lowered and the moldability is deteriorated.

2. Stabilizer The aromatic polycarbonate resin composition of the present invention comprises at least one phosphorus stabilizer represented by the following formula (3) and at least one phenol stabilizer represented by the following formula (4). contains. These stabilizers contribute to improvement in heat resistance, particularly improvement in melting stability, and reduction in discoloration during heat melting. Some stabilizers contribute to the improvement of heat resistance, but are poor in hydrolysis resistance and hydrolyze by moist heat to cause the molded product to become opaque. In the present invention, since the specific phosphorus stabilizer and phenol stabilizer are used together with the aromatic polycarbonate resin having a low water absorption rate, the hydrolyzability of these stabilizers is suppressed, and the wet heat of the molded product is reduced. Opacification can be suppressed. As a result, it is possible to achieve both improvement in heat resistance, which has been difficult in the past, and suppression of opacification due to wet heat.

2. -1 Phosphorus stabilizer

In the formula, R ^{1b to} R ^4b each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, or an oxyalkyl group having 1 to 18 carbon atoms. R ^{1b to} R ^4b may be the same or different.
The number of substituents of the two phenyl groups may be any of 0 to 4, but is preferably 2 or 3.

  As a phosphorus stabilizer represented by the above formula (3), for example, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is a product name of “ADK STAB PEP-24G” and bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available from Asahi Denka Kogyo Co., Ltd. under the trade name “ADK STAB PEP-36”.

2. -2 Phenolic stabilizer

In the above formula, Y is an n-valent group, and n is an integer of 1 to 3. Y is the residue of a hydroxy compound having 1-3 hydroxyl groups in the molecular.
As the phenol-based stabilizer represented by the above formula (4), for example, triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] is “Adeka Stab AO-70”. , 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8 , 10-tetraoxaspiro [5,5] undecane is commercially available from Asahi Denka Kogyo Co., Ltd. under the trade name “ADK STAB AO-80”.

  The blending amount of the heat stabilizer is 0.001 to 1 part by weight of the phosphorus stabilizer represented by the above formula (3) and 100 parts by weight of the aromatic polycarbonate resin and the above formula (4). The phenol-based stabilizer to be added is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, and more preferably 0.03 to 0.3 part by weight. If the phosphorus stabilizer and the phenol stabilizer are each less than 0.001 part by weight, the effect of improving the thermal stability is insufficient, and if it exceeds 1 part by weight, a mold deposit may occur.

4). Other Additives The heat-resistant aromatic polycarbonate resin composition of the present invention has an ultraviolet absorber, a fluorescent whitening agent, a light stabilizer, and a release agent that impart desired characteristics without departing from the spirit of the present invention. , Lubricants, flame retardants, flame retardant aids, impact modifiers, antistatic agents, plasticizers, compatibilizers, colorants (pigments such as carbon black and titanium oxide, dyes such as bluing agents), glass fibers Glass beads, glass flakes, carbon fibers, fibrous magnesium, potassium titanate whiskers, ceramic whiskers, mica, talc, clay, calcium silicate and other reinforcing agents, fillers, one of various additives such as other polymers or Two or more kinds may be added.

5. Preparation method of aromatic polycarbonate resin composition There is no restriction | limiting in particular about the preparation method of the aromatic polycarbonate resin composition of this invention. At any stage until immediately before the final molded product is melt-molded, the aromatic polycarbonate resin is added to the phosphorus-based stabilizer of the formula (3), the phenol-based heat stabilizer of the formula (4), and as necessary. It can be prepared by adding additives such as a release agent and a flame retardant and kneading. The addition can be performed by, for example, a method using a tumbler, a Henschel mixer, a super mixer, or the like, a method of quantitatively feeding to an extruder hopper using a feeder, and mixing. The kneading can be performed using a single screw extruder, a twin screw extruder or the like. The temperature condition for kneading is generally about 260 to 340 ° C, preferably about 270 to 320 ° C.

6). Molded Article The present invention also relates to a molded article comprising the aromatic polycarbonate resin composition of the present invention. The molded article of the present invention can be produced by various molding methods. Specifically, molding methods such as injection molding, injection compression molding, extrusion molding, hollow molding, rotational molding, and compression molding can be used. From the viewpoint of productivity, it is preferable that a pellet made of the aromatic polycarbonate resin composition is once produced and a molded product is produced from the pellet using the molding method. Furthermore, once a sheet-like molded body is obtained by extrusion molding, a target molded product can be manufactured by vacuum molding, pressure molding, or the like.

The molded product of the present invention is excellent in heat resistance, hardly undergoes discoloration due to thermal deterioration during heat melting, and is less likely to become opaque due to wet heat after molding. Moreover, since it is excellent in surface hardness and low water absorption, and also has various mechanical properties, it can be used in various applications. Some examples will be given below, but the present invention is not limited to these examples.
6). -1 Optical molded product The molded product of the present invention is excellent in heat resistance, has no discoloration caused by heat melting during molding, has high transparency, and is less likely to become opaque due to wet heat after molding. . Since it is excellent in surface hardness and low water absorption, and has various mechanical properties, it is useful as an optical molded article. For example, it can be used as a member such as an image display device or a solar cell, and more specifically, as an optical film, a flat panel display substrate, a solar cell substrate, an organic EL display substrate, or an electronic paper substrate. Used for.

6). -2 Abrasion Resistant Molded Article The molded article of the present invention is excellent in surface hardness as compared with a molded article made of a conventional aromatic polycarbonate resin composition. Therefore, there is no need for secondary processing such as hard coating or lamination with a hard resin layer even when used for parts that require scratch resistance, such as parts for mobile phone buttons and keypads. This is advantageous in terms of cost and product yield. However, as a matter of course, as long as it is a molded article made of the aromatic polycarbonate resin composition of the present invention, it goes without saying that a molded article subjected to secondary processing is also included in the scope of the present invention.

6). -3 Vehicle Lamp Molded Product The molded product of the present invention is excellent in heat resistance, and is useful, for example, as a part used at a position close to a heat source. For example, it is useful as a vehicle lamp molded product such as a head lamp, a rear lamp, a cover lamp such as a fog lamp for a vehicle (for example, an automobile), a lens such as a projector lens, and a lamp reflector.

  In addition, the molded article of the present invention can be expected to be used in a wide range of applications such as electrical / electronic / OA equipment parts, precision machine parts, medical parts, building / building materials, household goods, and the like.

Hereinafter, the present invention will be described by way of examples. In the examples, “%” and “part” mean “% by weight” or “part by weight” unless otherwise specified.
1. Measurement and Evaluation of Physical Properties Measurement and evaluation of physical properties of samples prepared in the following examples and comparative examples were performed by the following methods.
(1) Flexural modulus and bending strength: A three-point bending test was performed according to a bending test method according to ISO178.
(2) DTUL (deflection temperature under load): Measured under conditions (method A) under a load of 1.80 MPa according to ISO75-1 & 2.
(3) Glass transition temperature (Tg): In accordance with JIS K7121, DSC (manufactured by Seiko Co., Ltd., model: SSC-5000) was used to raise the temperature of the aromatic polycarbonate resin from room temperature at a rate of 10 ° C./min in a nitrogen stream. The inflection point was measured as the glass transition temperature.
(4) L value, a value, b value, YI value: According to JIS K7105, a 1 mm-thick flat plate is used as a test piece, and measured by a transmission method using a SE2000 type spectrocolorimeter manufactured by Nippon Denshoku Industries Co., Ltd. did.
(5) Pencil hardness: According to JIS K5400, the scratch was evaluated 5 times on a 1 mm thick flat plate to evaluate the hardness.
(6) Water absorption: According to JIS K7209, the test piece was immersed in pure water at 23 ° C., and the rate of increase in weight was measured.
(7) Moisture and heat resistance test: Using a pressure cooker tester (manufactured by Hirayama Seisakusho Co., Ltd., HAESTEST, MODEL PC-SIII), the test piece is in a steam atmosphere at 120 ° C., a gauge pressure of 1 kg / cm ² , and a humidity of 100%. The haze value before and after this treatment was measured according to JIS K7136, and the change was calculated as Δhaze, which was used as an index for hydrolysis resistance.
(8) Stability heat stability test: Injection molding is performed with a desktop injection molding machine (HAAKE, minijet) under conditions of a cylinder temperature of 350 ° C. and a mold temperature of 120 ° C. with a melting time of 15 minutes. A change in hue between a test piece having a thickness of 1 mm for 3 minutes and a molded piece having a melting time of 15 minutes was calculated as ΔE and used as an index of heat resistance.
ΔE = ((L ₁₅ −L ₃ ) ² + (a ₁₅ −a ₃ ) ² + (b ₁₅ −b ₃ ) ² ) ^1/2
(L ₁₅ , a ₁₅ , b ₁₅ : L value, a value, b value of a test piece having a melting time of 15 minutes. L ₃ , a ₃ , b ₃ : L value, a value of a test piece having a melting time of 3 minutes, b value.)

2. Resin production example 1:
1,1-bis (4-hydroxyphenyl) cyclododecane (hereinafter abbreviated as “BPCD” manufactured by Taoka Chemical Co., Ltd.) and 2,2-bis (4-hydroxyphenyl) propane (5% aqueous sodium hydroxide solution) Hereinafter, “BPA” (abbreviation: Mitsui Chemical Co., Ltd.) was added so that the molar ratio of BPCD to BPA was 30:70, and hydrosulfite was simultaneously dissolved.
Methylene chloride was added to this, and while stirring, phosgene was blown in while maintaining the temperature at 15 ° C.
After completion of phosgene blowing, p-tert-butylphenol (hereinafter abbreviated as “PTBP” as a molecular weight regulator) was added and stirred vigorously to emulsify the reaction solution. After emulsification, triethylamine was added, The mixture was stirred at 20 to 25 ° C. for about 1 hour for polymerization.
After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the previous solution (aqueous phase) became 10 μS / cm or less. The obtained polymer solution was dropped into warm water maintained at 45 ° C., and the solvent was removed by evaporation to obtain a white powdery precipitate.
The obtained precipitate was filtered and dried at 105 ° C. for 24 hours to obtain a polymer powder.
The intrinsic viscosity at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent of this polymer was 0.49 dl / g. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, it is polycarbonate resin having a carbonate bond Was confirmed.

Production Example 2:
In Production Example 1, white polymer powder was obtained in the same manner as in Production Example 1, except that only “BPCD” was used instead of “BPCD” and “BPA”.
The intrinsic viscosity at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent of this polymer was 0.48 dl / g.

Production Example 3:
A white polymer powder was obtained in the same manner as in Production Example 1, except that only “BPA” was used in place of “BPCD” and “BPA” in Production Example 1.
The intrinsic viscosity at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent of this polymer was 0.48 dl / g.

3. Material (A-1) Aromatic polycarbonate resin: Polymer obtained in Production Example 1 (A-2) Aromatic polycarbonate resin: Polymer obtained in Production Example 2 (A-3) Aromatic polycarbonate resin : Polymer (B-1) obtained in Production Example 3 Phosphorus stabilizer: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, manufactured by Asahi Denka Kogyo Co., Ltd. "Product name: ADK STAB PEP-36"
(B-2) Phosphorus stabilizer: bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, manufactured by Asahi Denka Kogyo Co., Ltd. “trade name: ADK STAB PEP-24G”
(B-3) Phosphorus stabilizer: Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by Asahi Denka Kogyo Co., Ltd. “Product Name: ADK STAB 2112”
(C-1) Phenol-based stabilizer: triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], manufactured by Asahi Denka Kogyo Co., Ltd. “trade name: ADK STAB AO -70 "
(C-2) Phenol stabilizer: 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2 4,8,10-tetraoxaspiro [5,5] undecane, manufactured by Asahi Denka Kogyo Co., Ltd. “trade name: ADK STAB AO-80”
(C-3) Phenol stabilizer: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals, Inc., “trade name: Irganox 1010 "

4). Examples 1-3 and Comparative Examples 1 and 2
Aromatic polycarbonate resin and various additives are blended in the proportions shown in Table 1, mixed with a tumbler for 20 minutes, and then cylindered with a single screw extruder with a screw diameter of 40 mm (“SV-40” manufactured by Isuzu Chemical Industries). The mixture was kneaded at a temperature of 320 ° C. and a screw rotation speed of 70 rpm, and the extruded strand was cut to produce pellets.
The pellets obtained were dried at 120 ° C. for 5 hours, and then injection molding machine (manufactured by Sumitomo Heavy Industries, Psycap M-2, clamping force 75T), cylinder temperature 320 ° C., mold temperature 80 ° C., molding cycle. Injection molding was carried out under the condition of 50 seconds to produce an ISO multipurpose test piece. In addition, injection molding was performed on a table-top injection molding machine (manufactured by HAAKE, minijet) under the conditions of a cylinder temperature of 350 ° C., a mold temperature of 120 ° C., and a melting time of 3 minutes to produce a flat plate having a thickness of 1 mm. Evaluation was performed using the molded product produced by such a method as a test piece for evaluation by the above-described method.

Claims (6)

An aromatic polycarbonate resin containing at least a unit represented by the following formula (1); 0.001 to 1 weight of phosphorus stabilizer represented by the following formula (3) with respect to 100 parts by weight of the aromatic polycarbonate resin A polycarbonate resin composition comprising 0.001 to 1 part by weight of a phenol-based stabilizer represented by the following formula (4) with respect to 100 parts by weight of the aromatic polycarbonate resin.

Wherein R ^{1 to} R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon atom. This represents an alkenyl group having 2 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms, and these groups may have a substituent but are not substituted with a halogen atom.

(In formula, R ^<1b > -R < ^4b > respectively independently represents a hydrogen atom, a hydroxyl group, a C1-C18 alkyl group, or a C1-C18 oxyalkyl group.)

(In the formula, Y is an n-valent group that is a residue of a hydroxy compound having 1 to 3 hydroxy groups in the molecule , and n is an integer of 1 to 3). The aromatic polycarbonate resin contains 5 to 95 mol% of a unit represented by the formula (1) and 95 to 5 mol% of a unit represented by the following formula (2). The aromatic polycarbonate resin composition described in 1.

(Wherein R ^{1a to} R ^4a each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a phenyl group; X is a single bond, Or

Wherein R ^5a and R ^6a each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and R ^5a and R ^6a are combined to form a single ring or a condensed ring. May be. ) A molded product obtained by molding the aromatic polycarbonate resin composition according to claim 1. The molded article according to claim 3, which is an optical molded article. The molded article according to claim 3, wherein the molded article is a vehicle lamp molded article. 4. The molded article according to claim 3, wherein the molded article is a scratch-resistant molded article.