JP5927883B2 - Thermoplastic resin composition - Google Patents

Description

  The present invention comprises a polycarbonate resin and a polyester resin containing a diol unit having a cyclic acetal skeleton, and is excellent in transparency, heat resistance, chemical resistance, mechanical strength, moldability, printability, and the like. The present invention relates to a thermoplastic resin composition having excellent stability.

  Polycarbonate resin (hereinafter sometimes referred to as “PC”) has a high heat distortion temperature and excellent heat resistance, as well as excellent impact resistance and transparency. It is used in a wide range of fields such as substrates and automotive applications. However, with PC alone, the viscosity in the molten state is higher than that of other thermoplastic resins, resulting in inferior molding processability, and insufficient properties such as chemical resistance and printability. It was.

  In order to improve the chemical resistance of PC, attempts have been made to melt mix a saturated polyester resin as a modifier. For example, it has been proposed to use polyethylene terephthalate (hereinafter sometimes referred to as “PET”) as a PC modifier, but PET does not become compatible with PC, and the transparency of PC can be obtained by adding PET. Is known to be significantly impaired.

  When polybutylene terephthalate resin (hereinafter sometimes referred to as “PBT”) is used as a modifier for PC, although it is relatively transparent, it cannot be said that the transparency is sufficient. There was also a problem that it significantly decreased.

  Further, although a thermoplastic resin composition of modified PET and PC in which 40 mol% of diol units are 1,4-cyclohexanedimethanol units has been proposed (see Patent Document 1), this resin composition is transparent. Although the heat resistance is good, there is a problem that the heat resistance is lowered and the chemical resistance is not sufficient.

  Furthermore, a method has been proposed in which a copolyester containing a specific proportion of naphthalenedicarboxylic acid units in the dicarboxylic acid units in the resin is used as a PC modifier (see Patent Document 2). When a naphthalenedicarboxylic acid unit in a proportion necessary for improving the property is included, there is a problem that transparency becomes insufficient.

  On the other hand, polyester resins such as PET, PBT, polyethylene naphthalate and the like are generally superior in chemical resistance, moldability, printability, and the like compared to PC, but heat resistance, mechanical strength (particularly impact resistance) and It is inferior in transparency, and improvement of these physical properties is demanded.

  As a method for improving the heat resistance and impact resistance of a polyester resin, a thermoplastic resin composition in which PC is melt-mixed with a polyester resin has been proposed, but as described above, this resin composition is extremely inferior in transparency. Due to problems, a thermoplastic resin composition composed of PC and polyester resin, which has transparency, heat resistance, chemical resistance and mechanical strength (especially impact resistance), moldability and printability. Was not known.

  On the other hand, Patent Document 3 reinforces the properties described above by blending a polyester resin containing PC and a diol having a cyclic acetal skeleton, and has transparency, heat resistance, chemical resistance, and mechanical properties. It is disclosed that a thermoplastic resin composition excellent in strength, moldability, printability and the like can be obtained.

  However, it is known that PC and polyester resin undergo an exchange reaction by melt-kneading, and the progress of the exchange reaction is accelerated by the addition of a transesterification catalyst (see Non-Patent Document 1). Therefore, if the activity of the polymerization catalyst remains in the production of the polyester resin, foaming occurs during the molding of the resin composition and the moldability is lowered, or the color tone of the resulting resin composition is lowered. There was a problem that the appearance was easily damaged.

  In order to solve such a problem, in Patent Document 4, a resin composition comprising a polyester resin and a polycarbonate resin manufactured using about 1 to 30 ppm of a titanium catalyst has improved color tone, thermal stability, and melt stability. It is disclosed. However, as the amount of the polyester resin increases, the color tone, thermal stability, and melt stability tend to decrease, and further improvement is required.

  Patent Document 5 discloses that by blending a polyester compound with a phosphorus compound, the transesterification reaction between the polyester resin and PC can be appropriately suppressed and foaming can be prevented. However, there is no description about the thermal stability, hydrolysis resistance, volatility, etc. of the phosphorus compound itself used. For example, monophosphates typified by triphenyl phosphate have poor heat resistance and high volatility. When molded into a resin, they have problems such as smoke and mold contamination, and bleeding out. It was. Patent Documents 6 and 7 disclose the use of phosphite as a catalyst inhibitor. Generally, phosphite-based phosphorus compounds are inferior in hydrolysis resistance and absorb moisture while being stored in a warehouse or the like. However, there was a problem that the function was degraded due to hydrolysis.

  In other words, a thermoplastic resin composition that has transparency, heat resistance, chemical resistance, mechanical strength, moldability, printability, etc., and is less susceptible to foaming, coloring, mold contamination, bleedout, etc. during use. It was sought after.

JP 2000-63641 A JP 2000-103948 A JP 2003-246925 A JP-T-2005-521772 Japanese Patent No. 4612165 JP-A-11-130955 Japanese Patent No. 3217782

Edited by Kazuo Yuki, saturated polyester resin handbook, p454-456, published by Nikkan Kogyo Shimbun, 1989, December 22

  An object of the present invention is to provide a thermoplastic resin composition comprising a polycarbonate resin and a polyester resin, which is free from problems such as foaming and coloring during use, mold contamination, bleed-out, etc. .

  As a result of intensive studies to solve the above problems, the present inventors have developed a resin composition comprising a polycarbonate resin, a polyester resin containing a diol unit having a cyclic acetal skeleton, and a specific phosphorus compound. In order to complete the present invention, it is found that there are no problems such as coloring, fuming, mold contamination, bleed-out, etc., transparency, heat resistance, chemical resistance, and mechanical strength, as well as excellent moldability and printability. It came.

  That is, the present invention relates to a polycarbonate resin (A), a polyester resin (B) containing 20 to 60 mol% of a diol unit having a cyclic acetal skeleton in the diol unit, and a phosphorus compound represented by the general formula (1) ( C) a thermoplastic resin composition comprising a phosphorus compound (C) having a weight content of 0.0005 to 1% by weight, and a polycarbonate resin (A) and a polyester resin (B) relative to the total of the polycarbonate resin (B). This relates to a thermoplastic resin composition having a weight ratio of A) of 2 to 99.5% by weight.

（式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４はそれぞれ独立して、アリール基を表し、Ｘは炭素数６〜１５の芳香族ジヒドロキシ化合物由来の２価の基を表す。ｎは１〜５の数である。）

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represents an aryl group, X represents a divalent group derived from an aromatic dihydroxy compound having 6 to 15 carbon atoms, and n is 1. A number of ~ 5.)

  According to the present invention, a thermoplastic resin composition having excellent transparency, mechanical strength, heat resistance, chemical resistance, moldability, and printability can be obtained by foaming or coloring during molding, mold contamination, bleedout, etc. It can be produced stably without problems, can be obtained in the form of injection molded articles, sheets, films, etc. with good appearance, and can be used in a wide range of fields.

  The present invention is described in detail below. The thermoplastic resin composition of the present invention (hereinafter referred to as the thermoplastic resin composition (D)) comprises a polycarbonate resin (A), a polyester resin (B), and a phosphorus compound (C), and is a thermoplastic resin composition. The weight content of the phosphorus compound (C) in (D) is 0.0005 to 1% by weight, and the weight ratio of the polycarbonate resin (A) to the total of the polycarbonate resin (A) and the polyester resin (B) is 2 to 2. 99.5% by weight.

  The polycarbonate resin (A) used in the present invention may have a branched structure that can be obtained by reacting an aromatic dihydroxy compound or a small amount thereof with a phosgene or a carbonic acid diester. Polycarbonate polymer or copolymer.

（ただし、一般式（２）、（３）において、Ｙは炭素数１〜１５の２価の炭化水素基、または−Ｏ−，−Ｓ−，−Ｓ２−，−ＳＯ２−，−ＳＯ−，及び−ＣＯ−から選ばれる２価の基を示す。Ｒ５及びＲ６は、それぞれ独立に、ハロゲン原子、炭素数１〜１０の脂肪族炭化水素基、炭素数６〜１８のアリール基、炭素数１〜１０のオキシアルキル基、炭素数６〜１８のオキシアリール基から選ばれる。ｍ１及びｍ２はそれぞれ独立に、０〜４であり、ｊは０又は１であり、ｋは０〜５である。ｌは４又は５である。） The polycarbonate obtained from the aromatic dihydroxy compound is a polycarbonate comprising a repeating unit represented by the following general formula (2) and / or (3).

(In the general formulas (2) and (3), Y is a divalent hydrocarbon group having 1 to 15 carbon atoms, or -O-, -S-, -S2-, -SO2-, -SO-, And R 5 and R 6 each independently represent a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or 1 carbon atom. Selected from an oxyalkyl group having 10 to 10 carbon atoms and an oxyaryl group having 6 to 18 carbon atoms, m1 and m2 are each independently 0 to 4, j is 0 or 1, and k is 0 to 5. l is 4 or 5.)

  The aromatic hydroxy compound constituting the polycarbonate resin (A) used in the present invention is not particularly limited, but 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis ( 3,5-dibromo-4-hydroxyphenyl) propane (also known as tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4- Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tertiarybutyl-4-hydroxy) Phenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-) -Hydroxyphenyl) propane and the like bis (hydroxyaryl) alkanes; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1 Bis (hydroxyaryl) cycloalkanes exemplified by 1,1-bis (3,5-dibromo-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane and the like; Bis (hydroxyaryl) arylalkanes exemplified by 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) diphenylmethane and the like; 4,4′-dihydroxydiphenyl ether 4,4'-dihydroxy-3,3'-dimethyldiph Dihydroxy diaryl ethers exemplified by phenyl ether and the like; dihydroxy diaryl sulfides exemplified by 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide and the like; Dihydroxydiaryl sulfoxides exemplified by -dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide and the like; 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3 ' -Dihydroxy diaryl sulfones exemplified by dimethyldiphenyl sulfone and the like; hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like. Among these, bisphenol A is particularly preferable from the viewpoints of heat resistance, mechanical performance, economy, and the like of the thermoplastic resin composition (D), that is, the polycarbonate resin (A) is a polycarbonate ester of bisphenol A. Particularly preferred.

  The polycarbonate resin (A) of the present invention may have a branched structure. To obtain an aromatic polycarbonate resin having such a branched structure, phloroglucin, 2,6-dimethyl-2,4,6 -Tris (4-hydroxyphenyl) -3-heptene, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 1,3,5-tris (2-hydroxyphenyl) Benzol, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ′, α ″ -tris (4- Polyhydroxy compounds exemplified by hydroxyphenyl) -1,3,5-triisopropylbenzene and the like, 3,3-bis (4-hydroxyaryl) oxindole (also known as 1, Bisphenol), 5-chloro-1,3 bisphenol, 5,7-dichloro-1,3 bisphenol may be using 5-bromo-1,3-bisphenols.

  The viscosity average molecular weight of the polycarbonate resin (A) used in the present invention is preferably 10,000 or more from the viewpoint of maintaining the mechanical strength, and preferably 30,000 or less from the viewpoint of moldability. Is more preferably 12,000 or more and 28,000 or less. By setting the viscosity average molecular weight within the above range, the mechanical strength and moldability of the thermoplastic resin (D) are excellent.

  There is no restriction | limiting in particular in the method of manufacturing the polycarbonate resin (A) used by this invention, A conventionally well-known method is applicable. For example, it can be obtained by reacting an aromatic dihydroxy compound and a carbonate precursor by an interfacial polymerization method or a melt polymerization method.

Ｒ９、Ｒ１０、及びＲ１１はそれぞれ独立して、炭素数が１〜１０の脂肪族炭化水素基、炭素数が３〜１０の脂環式炭化水素基、及び炭素数が６〜１０の芳香族炭化水素基からなる群から選ばれる炭化水素基を表す。一般式（４）及び（５）の化合物としては３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン、または５−メチロール−５−エチル−２−（１，１−ジメチル−２−ヒドロキシエチル）−１，３−ジオキサンが特に好ましい。 The polyester resin (B) used in the present invention is a diol unit that contains a dicarboxylic acid unit and a diol unit, and 1 to 60 mol% of the diol unit has a cyclic acetal skeleton. The diol unit having a cyclic acetal skeleton is preferably a unit derived from a compound represented by the following general formula (4) or (5).

R9, R10, and R11 are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic carbon group having 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of hydrogen groups. As the compounds of the general formulas (4) and (5), 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, or 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane is particularly preferred.

  In addition, the diol unit other than the diol unit having a cyclic acetal skeleton is not particularly limited, but ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol Aliphatic diols such as propylene glycol and neopentyl glycol; polyether diols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2- Decahydronaphthalene diethanol, 1,3-decahydronaphthalene diethanol, 1,4-decahydronaphthalene diethanol, 1,5-decahydronaphthalene diethanol, 1,6-decahydronaphthalene Cycloaliphatic diols such as dimethanol, 2,7-decahydronaphthalene diethanol, tetralin dimethanol, norbornane dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol; 4,4 ′-(1-methylethylidene ) Bisphenols such as bisphenol, methylene bisphenol (also known as bisphenol F), 4,4'-cyclohexylidene bisphenol (also known as bisphenol Z), 4,4'-sulfonyl bisphenol (also known as bisphenol S); alkylene oxide addition of the above bisphenols An aromatic dihydroxy compound such as hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylbenzophenone; Alkylene oxide adducts of the above aromatic dihydroxy compounds can be exemplified. Ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferable from the viewpoint of mechanical performance and economy of the thermoplastic resin composition of the present invention, and ethylene glycol is particularly preferable. . The exemplified diol units can be used alone or in combination.

  Further, the dicarboxylic acid unit of the polyester resin (B) used in the present invention is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, decanedicarboxylic acid, norbornanedicarboxylic acid, tricyclodecanedicarboxylic acid, pentacyclododecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, 1,4-naphthalene Examples include aromatic dicarboxylic acids such as dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetralindicarboxylic acid. From the aspects of mechanical performance and heat resistance of the thermoplastic resin composition of the present invention, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2 Aromatic dicarboxylic acids such as 1,7-naphthalenedicarboxylic acid are preferred, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, and isophthalic acid are particularly preferred. Among these, terephthalic acid is most preferable from the viewpoint of economy. The illustrated dicarboxylic acids can be used alone or in combination.

  The polyester resin (B) used in the present invention has a diol unit having a cyclic acetal skeleton in a proportion of 20 to 60 mol%, preferably 25 to 55 mol%, particularly preferably 30 to 50 mol%. When the proportion of the diol unit having a cyclic acetal skeleton is less than 20 mol%, the improvement of the transparency and heat resistance of the thermoplastic resin composition (D) becomes insufficient, and when it exceeds 60 mol%, the transparency is improved. And mechanical strength improvement is insufficient. The thermoplastic resin composition (D) using the polyester resin (B) is particularly excellent in transparency, heat resistance and mechanical strength.

  The proportion of the aromatic dicarboxylic acid unit in the dicarboxylic acid unit in the polyester resin (B) is usually preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably 100 mol%. . By setting the ratio of the aromatic dicarboxylic acid unit in the dicarboxylic acid unit in the polyester resin (B) within the above range, the thermoplastic resin composition (D) has more excellent heat resistance, mechanical strength, and chemical resistance. It will be a thing.

  In the polyester resin (B) in which the aromatic dicarboxylic acid unit in the dicarboxylic acid unit is 70 mol% or more, when the aromatic dicarboxylic acid unit further contains a terephthalic acid unit, the terephthalic acid unit in the dicarboxylic acid unit The ratio is preferably 20 to 100 mol%, more preferably 80 to 100 mol%, and particularly preferably 100 mol% from the viewpoint of economy.

  There is no restriction | limiting in particular in the method of manufacturing the polyester resin (B) of this invention, A conventionally well-known method is applicable. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, or a solution polymerization method.

The polyester resin (B) is produced in the presence of a known catalyst. Known catalysts include, for example, magnesium metal, sodium, magnesium alkoxide, zinc, lead, cerium, cadmium, manganese, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium, tin, germanium, Examples include fatty acid salts such as antimony, carbonates, phosphates, hydroxides, chlorides, oxides, etc., which may be used alone or in combination with a plurality of them. You can also.

  Among the above-mentioned catalysts, titanium-containing compounds (ortho titanate, titanium carboxylate, alkali metal titanate, titanium halide, titanium dioxide) are preferable catalysts used in the production of the polyester resin (B). Is mentioned. In the thermoplastic resin composition (D), foaming, fuming, mold contamination caused by blending the phosphorus compound (C) with the polyester resin (B) produced in the presence of the above preferred catalyst, The suppression effect of bleed out is remarkable.

  The phosphorus compound (C) used in the present invention is represented by the following formula (1). These can be used alone or in combination of two or more.

  In the general formula (1), R1, R2, R3, and R4 each independently represent an aryl group. Examples of the aryl group include phenyl, cresyl, xylenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl Octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, p-cumylphenyl, dinonylphenyl, α-naphthyl, β-naphthyl and the like. Of these, phenyl, cresyl, and xylenyl are preferable, and xylenyl is particularly preferable.

  In the general formula (1), X represents a divalent group derived from an aromatic dihydroxy compound having 6 to 15 carbon atoms. Examples of the group X include groups derived from resorcin, catechol, hydroquinone, bisphenol A, bisphenol F, and biphenol. Among them, a group derived from resorcin, hydroquinone and bisphenol A is preferable, and a group derived from resorcin is particularly preferable. n represents a number of 1 to 5, preferably 1 to 3, particularly preferably 1.

  The phosphorus compound (C) is preferably excellent in thermal stability. The temperature is raised from 40 ° C. to 500 ° C. at a nitrogen flow rate of 50 ml / min and a heating rate of 10 ° C./min, and the weight loss rate with respect to the initial weight is 10%. The temperature is preferably 300 ° C. or higher, more preferably 330 ° C. or higher.

  The melting point of the phosphorus compound (C) is preferably 50 ° C. or higher and 150 ° C. or lower. When it is within the above range, when mixed with the polycarbonate resin (A) and the polyester resin (B), or mixed with the polyester resin (B), the handling becomes easy and it is melted at the time of molding, and the mixing with the resin is improved. Appearance defects of the molded body are less likely to occur.

  The phosphorus element content in the phosphorus compound (C) is preferably 6% by weight or more, and more preferably 8.5% by weight or more. When the phosphorus content is less than the above, the effect of suppressing foaming or coloring during the molding process of the thermoplastic resin composition (D) tends to decrease.

  Specific examples of the phosphorus compound represented by the general formula (1) include, for example, 1,3-phenylenebis (diphenylphosphate), 1,4-phenylenebis (diphenylphosphate), 1,3-phenylenebis (phenylcresate). Zylphosphate), 1,4-phenylenebis (phenylcresylphosphate), 1,3-phenylenebis (dixylenylphosphate), 1,4-phenylenebis (dixylenylphosphate), 1,3-phenylene Examples thereof include bis (dicresyl phosphate), 1,4-phenylene bis (dicresyl phosphate), bisphenol A bis (diphenyl phosphate), and bisphenol A bis (dicresyl phosphate). 1,3-phenylenebis (dixylenyl phosphate) is excellent in thermal stability and hydrolysis resistance, low volatility, hardly disturbing the transparency of the resin, and easy to handle with powder. Particularly preferred.

  The weight content of the phosphorus compound (C) in the thermoplastic resin composition (D) of the present invention is preferably 0.0005 to 1% by weight, more preferably 0.001 to 0.5% by weight, More preferably, it is 0.005-0.2 weight%. When the amount is less than 0.0005% by weight, foaming or coloring tends to occur during the melt-kneading of the polycarbonate resin (A) and the polyester resin (B). When the amount exceeds 1% by weight, the resulting thermoplastic resin composition (D) Mechanical strength may decrease.

When producing the thermoplastic resin composition (D), the phosphorus compound (C) may be mixed simultaneously with the polycarbonate resin (A) and the polyester resin (B). The polyester resin (B) and the phosphorus compound (C) may be mixed in advance. After mixing, polycarbonate resin (A) may be mixed into these mixtures, but problems such as foaming can be prevented by mixing polyester resin (B) and phosphorus compound (C) in advance. The latter is preferred because it becomes easier.

  The method of mixing the phosphorus compound (C) with the polycarbonate resin (A) and the polyester resin (B) is not particularly limited, but is a method of dry blending the pelletized polycarbonate resin (A) and the polyester resin (B). A method of melt-kneading the dry blended product with an extruder or the like is employed.

  The method of mixing the polyester resin (B) and the phosphorus compound (C) in advance is not particularly limited, but the polyester resin (B) is pelletized and then dry blended, and the dry blended material is melt kneaded with an extruder or the like. And a method of adding to the melted polyester resin (B) using an extruder or the like is employed.

  In addition, when mixing the phosphorus compound and / or resin, a known apparatus can be used, for example, a tumbler, a high-speed mixer, a nauter mixer, a ribbon blender, a mixing roll, a kneader, an intensive mixer, a single screw extruder, Examples thereof include a mixing and kneading apparatus such as a twin screw extruder. Moreover, liquid mixing apparatuses, such as a gate mixer, a butterfly mixer, a universal mixer, a dissolver, and a static mixer, can also be used.

  When the polyester resin (B) is melt kneaded with the polycarbonate resin (A), the moisture content in the resin is desirably 300 ppm or less, preferably 100 ppm or less. By making a moisture content into the said range, deterioration of the polyester resin (B) at the time of melt-kneading with a polycarbonate resin (A) can be prevented.

The melt viscosity of the polyester resin (B) used in the present invention is preferably in the range of 500 to 2000 Pa · s when measured at a measurement temperature of 240 ° C. and a shear rate of 100 s ⁻¹ . When the melt viscosity is in the above range, it is possible to obtain a thermoplastic resin composition (D) excellent in transparency, mechanical strength, and moldability because of good mixing at the time of melt kneading with the polycarbonate resin (A). it can.

  The intrinsic viscosity of the polyester resin (B) used in the present invention (value measured at 25 ° C. in a mixed solvent in which the mass ratio of phenol / 1,1,2,2-tetrachloroethane is 6/4) is particularly high. Although there is no restriction | limiting, Usually, it is desirable that it is 0.3-2.0d1 / g, Preferably it is 0.4-1.8d1 / g. Since the molecular weight of the polyester resin (B) is sufficiently high when the intrinsic viscosity is 0.3 or more, the molded article made of the thermoplastic resin composition (D) obtained by using the polyester resin (B) has particularly excellent mechanical strength. Have

  The molecular weight distribution of the polyester resin (B) is preferably 2.5 to 12.0, and more preferably 2.5 to 8.0. When the molecular weight distribution is as described above, the film, sheet, thin-walled hollow container and the like are particularly excellent in moldability. Here, the molecular weight distribution refers to the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

  In the thermoplastic resin composition (D) of the present invention, the weight ratio of the polycarbonate resin (A) to the total of the polycarbonate resin (A) and the polyester resin (B) is 2 to 99.5% by weight. It is preferably 0% by weight, more preferably 5 to 95.0% by weight, and even more preferably 10 to 95% by weight.

In the thermoplastic resin composition (D) of the present invention, the weight ratio of the polycarbonate resin (A) to the total of the polycarbonate resin (A) and the polyester resin (B) is 99.5% by weight or less, and the weight of the polyester resin (B). When the ratio is 0.5% by weight or more, the chemical resistance is greatly improved with respect to the polycarbonate resin, and the moldability and printability are also improved. Even when the thermoplastic resin composition (D) contains the polyester resin (B) in an amount of 0.3% by weight or more, the chemical resistance improving effect on the polycarbonate resin is exhibited. When the weight ratio of the polycarbonate resin (A) to the total of the polycarbonate resin (A) and the polyester resin (B) in the thermoplastic resin composition (D) is 2% by weight or more, it is mechanical to the polyester resin (B). Strength (especially impact resistance) and heat resistance are improved.

  From the viewpoint of transparency, the total light transmittance of the thermoplastic resin composition (D) having a thickness of 3.2 mm is preferably 87% or more, more preferably 88% or more, and particularly preferably 89% or more. On the other hand, the haze is preferably 4% or less, more preferably 3% or less, and particularly preferably 2% or less.

  The glass transition temperature measured by a differential scanning calorimeter of the thermoplastic resin composition (D) is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, and particularly preferably 130 ° C. or higher. Heat resistance becomes especially favorable because the glass transition temperature of a thermoplastic resin composition (D) is the said range.

  The impact strength in the notched Izod impact test of the 3.2 mm-thick injection molded article of the thermoplastic resin composition (D) is preferably 30 J / m or more, more preferably 50 J / m or more, from the viewpoint of impact resistance. / M or more is particularly preferable.

  A solution (solution temperature: 75 parts by weight of carbon tetrachloride / 25 parts by weight of n-butanol in a state where a 3.2 mm-thick injection molded article of the thermoplastic resin composition (D) is strained with a deformation rate of 1%. From the viewpoint of chemical resistance, the time until a crack is generated when immersed in (25 ° C.) is preferably 5 seconds or more, more preferably 7 seconds or more, and particularly preferably 10 seconds or more.

  An extruded sheet of a thermoplastic resin composition (D) having a thickness of 1.0 mm is coated with ink (made by Teikoku Ink Manufacturing Co., Ltd., 13-00215 white slow-drying D3N25-P) and solvent (made by Teikoku Ink Manufacturing Co., Ltd.) Z -603) (ink / solvent weight ratio: 100/30) was applied to a thickness of 60 μm, air-dried for 10 minutes, and then further dried at 80 ° C. for 10 minutes. From the viewpoint of printability, 20% or less is preferable, and 0% is more preferable.

  The melt viscosity of the thermoplastic resin composition (D) is preferably in the range of 300 to 5000 Pa · s, more preferably in the range of 500 to 2000 Pa · s, when measured at a temperature of 240 ° C. and a shear rate of 100 s −1. When the melt viscosity of the thermoplastic resin composition (D) is in the above range, moldability, particularly injection moldability, extrusion moldability, and foam moldability are improved. In addition, the molded product obtained from the thermoplastic resin composition (D) has good shapeability and deep drawability in vacuum / pressure forming, and secondary workability such as cold bending, drilling, punching, etc. Becomes better.

  The thermoplastic resin composition (D) has the characteristics described in the following (I) to (III) depending on the constituent ratio of the polycarbonate resin (A) and the polyester resin (B).

(I) When the resin composition in the thermoplastic resin composition (D) is composed of a large amount of the polycarbonate resin (A) and a small amount of the polyester resin (B), that is, preferably the polycarbonate resin (A) and the polyester resin. When the weight ratio of the polycarbonate resin (A) to the total of (B) is 60 to 99.5% by weight, more preferably 70 to 95% by weight, the polyester resin (B) is not included in the resin composition. Improvements in chemical resistance, moldability, and printability are significant without impairing transparency, mechanical strength, and heat resistance (when the resin composition is the polycarbonate resin (A) alone).

  Therefore, the thermoplastic resin composition (D) having the above-described composition is particularly excellent in heat resistance, transparency, chemical resistance and mechanical strength, and is also excellent in moldability and printability.

Specifically, the thermoplastic resin composition (D) having the above composition has the following physical properties (1) to (4).
(1) Heat resistance: Glass transition temperature measured with a differential scanning calorimeter is 130 ° C. or higher.
(2) Impact resistance: Impact strength is 100 J / m or more in a notched Izod impact test.
(3) Chemical resistance: Time until a crack occurs in an injection-molded product when an injection-molded product to which strain of 1% is applied is immersed in a mixed solution consisting of 75 parts by weight of carbon tetrachloride / 25 parts by weight of n-butanol. Is more than 5 seconds.
(4) Transparency: The total light transmittance of an injection molded product having a thickness of 3.2 mm is 87% or more and the haze value is 4% or less.

(II) When the resin composition in the thermoplastic resin composition (D) is composed of the same amount of polyester resin (B) as the polycarbonate resin (A), that is, preferably the polycarbonate resin (A) and the polyester resin When the weight ratio of the polycarbonate resin (A) to the total of (B) is 30 to 70% by weight, more preferably 40 to 60% by weight, when the polyester resin (B) is not included in the resin composition (above When the resin composition is a polycarbonate resin (A) alone), the chemical composition is particularly excellent in chemical resistance, moldability, and printability, and the polycarbonate resin (A) is not included in the resin composition (the resin described above). Especially when the composition is the polyester resin (B) alone, the heat resistance, mechanical strength, and particularly impact resistance are excellent.

Accordingly, the thermoplastic resin composition (D) having excellent heat resistance, mechanical strength, chemical resistance, moldability, and printability without impairing the transparency of each of the polycarbonate resin (A) and the polyester resin (B). Can be obtained. Specifically, the thermoplastic resin composition (D) having the above composition has the following physical properties (1) to (4).
(1) Heat resistance: Glass transition temperature measured with a differential scanning calorimeter is 100 ° C. or higher.
(2) Impact resistance: Impact strength in an impact drilling test of a film having a thickness of 50 μm is 50 kgf · cm / cm or more.
(3) Chemical resistance: time until an injection molded body is cracked when an injection molded body with a strain of 1% is immersed in a solution consisting of 75 parts by weight of carbon tetrachloride / 25 parts by weight of n-butanol. 7 seconds or more.
(4) Transparency: The total light transmittance of an injection molded product having a thickness of 3.2 mm is 87% or more and the haze value is 4% or less.

(III) When the resin composition in the thermoplastic resin composition (D) is composed of a small amount of the polycarbonate resin (A) and a large amount of the polyester resin (B), that is, preferably the polycarbonate resin (A) and the polyester resin When the weight ratio of the polycarbonate resin (A) to the total of (B) is 0.5 to 40% by weight, more preferably 5 to 30% by weight, the polycarbonate resin (A) is not included in the resin composition. Compared to the case where the resin composition is the polyester resin (B) alone, the heat resistance, mechanical strength, and particularly the impact resistance are improved.

Therefore, without impairing the transparency of the polyester resin (B), it is possible to improve the heat resistance and mechanical strength and obtain a thermoplastic resin composition (D) having excellent chemical resistance, moldability and printability. . Specifically, the thermoplastic resin composition (D) having the above composition has the following physical properties (1) to (4).
(1) Heat resistance: Glass transition temperature measured by a differential scanning calorimeter is 90 ° C. or higher.
(2) Impact resistance: Impact strength in notched Izod impact test is 30 J / m or more.
(3) Chemical resistance: time until an injection molded body is cracked when an injection molded body with a strain of 1% is immersed in a solution consisting of 75 parts by weight of carbon tetrachloride / 25 parts by weight of n-butanol. 10 seconds or more.
(4) Transparency: The total light transmittance of an injection molded product having a thickness of 3.2 mm is 87% or more and the haze value is 4% or less.

  In addition to the above A, B, and C components, other resins and various additives may be contained within a range not impairing the object of the present invention. These may be added alone or in combination of two or more.

Examples of other resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, isophthalic acid-modified polyethylene terephthalate, 1,4-cyclohexanedimethanol-modified polyethylene terephthalate, polyarylate and other polyester resins, polycarbonate resins, and acrylonitrile-styrene. Polymer, acrylonitrile-butadiene-styrene copolymer, styrene resin such as polystyrene, polyolefin resin such as polyethylene and polypropylene, vinyl chloride resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, polyphenylene ether resin, acrylic Resins, phenol resins, epoxy resins and the like can be mentioned.

Examples of the various additives include antistatic agents, flame retardants, lubricants, antioxidants, light stabilizers, ultraviolet absorbers, mold release agents, dyes and pigments, and inorganic fillers.

When molding using the thermoplastic resin composition of the present invention, conventionally known molding methods can be used, and are not particularly limited. For example, injection molding, extrusion molding, calendar molding, extrusion foaming Examples thereof include molding, extrusion blow molding, injection blow molding and the like.

  The thermoplastic resin composition of the present invention can be used in various applications such as injection molded articles, extruded molded articles, sheets, sheet molded articles, unstretched films, stretched films, injection blow bottles, direct blow bottles, and foams.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by these examples.

The raw materials used in the examples and comparative examples are shown below.
[Polycarbonate resin]
(A-1) Product name: Iupilon E-2000 (Mitsubishi Engineering Plastics Co., Ltd.)
(A-2) Product name: Iupilon S-3000 (Mitsubishi Engineering Plastics Co., Ltd.)
[Phosphorus compounds]
(C-1) Product name: PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.)
(C-2) Triphenyl phosphate (trade name: TPP (manufactured by Daihachi Chemical Industry Co., Ltd.))
(C-3) Tris (2,4-di-tert-butylphenyl) phosphite (trade name: IRGAFOS168 (manufactured by BASF Japan Ltd.))

[Production of polyester resins (B-1) and (B-2)]
Charged terephthalic acid and ethylene glycol in the amounts shown in Table 1 into a 150 liter polyester resin production system equipped with a packed column rectification column, a partial condenser, a full condenser, a cold trap, a stirrer, a superheater, and a nitrogen introduction pipe The esterification reaction was carried out by a conventional method. Ethylene glycol for depolymerization and germanium dioxide in the amounts shown in Table 1 were added to the obtained ester, and depolymerization was performed at 225 ° C. under a nitrogen stream. After reacting for 3 hours while distilling off the water produced, ethylene glycol was distilled off at 215 ° C. and 13.3 kPa. Tetra-n-butyl titanate, potassium acetate, triethyl phosphate, and SPG described in Table 1 were added to the obtained ester, and the reaction was performed at 225 ° C. and 13.3 kPa for 3 hours. The resulting ester is heated and depressurized, and finally subjected to a polycondensation reaction at 270 ° C. and high vacuum (300 Pa or less). When the predetermined melt viscosity is reached, the reaction is terminated to obtain a polyester resin (B). It was.
In addition, the meaning of the abbreviation in a table | surface is as follows.
PTA: terephthalic acid SPG: 3,9-bis (1,1-dimethyl-2-hydroxyethethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane EG: ethylene glycol GeO ₂ : germanium dioxide • TBT: tetra-n-butyl titanate • AcOK: potassium acetate • TEP: triethyl phosphate

The evaluation methods of the polyester resins (B-1) and (B-2) are as follows.
(1) Ratio of diol units having a cyclic acetal skeleton The ratio of diol units having a cyclic acetal skeleton in a polyester resin is calculated from ¹ H-NMR measurement and peak area ratio by dissolving 20 mg of a polyester resin in 1 g of heavy chloroform. did. The measuring apparatus used JNM-AL400 by JEOL Co., Ltd., and measured it at 400 MHz.
(2) Glass transition temperature The glass transition temperature of the polyester resin is DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is placed in an aluminum non-sealed container, and the temperature rising rate in a nitrogen gas (30 ml / min) airflow is 20 The glass transition temperature was measured at a temperature of ° C / min and the temperature changed by ½ of the difference in baseline before and after the transition of the DSC curve.
(3) Molecular weight (number average molecular weight Mn, weight average molecular weight Mw, molecular weight distribution Mw / Mn)
2 mg of the polyester resin was dissolved in 20 g of chloroform, measured by gel permeation chromatography (GPC), and calibrated with standard polystyrene as Mn and Mw / Mn. GPC was measured by connecting TOSOH 8020 manufactured by Tosoh Corporation with two columns GMHHR-L manufactured by Tosoh Corporation and one TSK G5000HR and measuring the column temperature at 40 ° C. As an eluent, chloroform was flowed at a flow rate of 1.0 ml / min, and measurement was performed with a UV detector.
(4) Melt Viscosity Measuring equipment is Capirograph 1C (Capillograph) manufactured by Toyo Seiki, temperature: 240 ° C., preheating time: 1 min, nozzle diameter: 1 mm, nozzle length: 10 mm, shear rate: 100 (1 / sec) went.

[Examples 1-8, Comparative Examples 1-7]
(1) Production of thermoplastic resin composition (D) Polyester resin (B) and phosphorus compound (C) were dry-mixed by a tumbler at the ratios shown in Tables 2 to 5 below, and a twin-screw extruder (Toshiba Machine Co., Ltd.) Melting and kneading were performed under the conditions of a cylinder temperature of 210 to 240 ° C., a die temperature of 240 ° C., and a screw rotation speed of 100 rpm using a company TEM37BS) to obtain a pellet-shaped polyester resin (B) containing a phosphorus compound (C). The pellet-like resin and the polycarbonate resin (A) are dry-mixed by a tumbler, and are subjected to conditions of a cylinder temperature of 210 to 280 ° C., a die temperature of 240 to 275 ° C., and a screw rotation speed of 100 rpm using a twin screw extruder (TEM37BS manufactured by Toshiba Machine Co., Ltd.). The mixture was melt kneaded to obtain a pellet-shaped thermoplastic resin composition (D).
(2) Production of injection-molded body The thermoplastic resin composition (D) was subjected to a cylinder temperature of 260 to 280 ° C. and a mold temperature of 35 ° C. using a screw-type injection molding machine (screw diameter: 32 mm, mold clamping force: 9.8 kN). Various test pieces having a thickness of 3.2 mm were molded under the conditions described above.
(3) Production of Sheet The thermoplastic resin composition (D) is 1.0 mm under the conditions of a cylinder temperature of 240 to 280 ° C., a T die temperature of 240 to 275 ° C., and a screw rotation speed of 50 rpm by a T-die method using a twin-screw extruder. A thick sheet was produced.
(4) Production of film The thermoplastic resin composition (D) was 50 μm thick under the conditions of a cylinder temperature of 240 to 280 ° C., a T die temperature of 240 to 275 ° C., and a screw rotation speed of 50 rpm by a T-die method using a single screw extruder. A film was prepared.

〔Evaluation method〕
Glass transition temperature The glass transition temperature of the thermoplastic resin composition (D) is DSC / TA-50WS manufactured by Shimadzu Corporation, and about 10 mg of sample is placed in an aluminum non-sealed container, and in a nitrogen gas (30 ml / min) stream The glass transition temperature was measured at a rate of temperature increase of 20 ° C./min, and the temperature changed by ½ of the difference in baseline before and after the transition of the DSC curve.
-Melt Viscosity Using Toyo Seiki Capirograph 1C (capillograph), temperature: 240 ° C, preheating time: 1 min, nozzle diameter: 1 mm, nozzle length: 10 mm, shear rate: 100 (1 / sec) .
-Total light transmittance, haze value A film having a thickness of 50 µm was used, and the measurement was performed according to JIS K7105 and ASTM D1003. The measuring apparatus used is a fog value measuring apparatus (model: COH-300A) manufactured by Nippon Denshoku Industries Co., Ltd.
-Impact resistance A film having a thickness of 50 µm was used, and the impact drilling strength was measured using a film impact tester IFT-60 manufactured by Tosoh Seimitsu Kogyo Co., Ltd. with a sample clamp diameter of 50 mm and a hammer lifting angle of 90 ° C.
・ Chemical resistance 1
A test chemical was applied to a bending test piece (injection molded product) having a thickness of 3.2 mm in a state where a strain with a deformation rate of 0.5% was applied, and the time until a crack occurred on the surface at a temperature of 25 ° C. was measured.
Dioctyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the test chemical.
・ Chemical resistance 2
In a mixed solution (solution temperature: 25 ° C.) consisting of 75 parts by weight of carbon tetrachloride / 25 parts by weight of n-butanol in a state in which a bending test piece (injection molded body) having a thickness of 3.2 mm was strained with a deformation rate of 1%. The time until immersion and cracking occurred was measured (test number: 5).
-Printability 100: 30 (weight) of ink (Teikoku Manufacturing Co., Ltd., 13-00215 White Slow Dry D3N25-P) and solvent (Teikoku Manufacturing Co., Ltd. Z-603) on a 1.0 mm thick sheet Ratio) was applied to a thickness of 60 μm with an applicator, and when it was air-dried for 10 minutes and further dried at 80 ° C. for 10 minutes, the crack generation ratio of the ink part of the sample was measured (test number 5).
Extrusion stability The presence or absence of foaming, mold contamination, fuming, etc. when a film having a thickness of 50 μm was formed was evaluated visually.

[Examples 1-8, Comparative Examples 1-7]
The evaluation results are shown in Tables 2-5.

The thermoplastic resin composition of the present invention is excellent in transparency, heat resistance, chemical resistance and mechanical strength, moldability, printability, and excellent stability during use.For example, a container such as a bottle, It can be stably manufactured in the form of injection moldings, foams, packaging materials such as films and sheets, and electrical / electronic devices such as OA equipment, information / communication equipment, home appliances, automotive field, food field It can be widely used in various fields such as the construction field.

Claims (10)

A thermoplastic resin comprising a polycarbonate resin (A), a polyester resin (B) containing 20 to 60 mol% of a diol unit having a cyclic acetal skeleton in the diol unit, and a phosphorus compound (C) represented by the general formula (1) A resin composition, wherein the phosphorus compound (C) has a weight content of 0.0005 to 1% by weight, and the weight ratio of the polycarbonate resin (A) to the total of the polycarbonate resin (A) and the polyester resin (B) is The thermoplastic resin composition which is 2-99.5 weight%.

(In the formula, R1, R2, R3 and R4 each independently represents an aryl group, X represents a divalent group derived from an aromatic dihydroxy compound having 6 to 15 carbon atoms, and n represents a number of 1 to 5. .) The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin (A) is a polycarbonate resin composed of repeating units represented by the general formula (2) and / or (3).

(In the above general formulas (2) and (3), Y represents a divalent hydrocarbon group having 1 to 15 carbon atoms, or -O-, -S-, -S2-, -SO2-, -SO-, and R 5 and R 6 each independently represent a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or 1 to C carbon atoms. It is selected from 10 oxyalkyl groups and oxyaryl groups having 6 to 18 carbon atoms, m1 and m2 are each independently 0 to 4, j is 0 or 1, and k is 0 to 5. Is 4 or 5.) The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin (A) is a bisphenol A polycarbonate. The diol unit having the cyclic acetal skeleton is represented by the general formula (4):

(In the formula, R9 and R10 are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of hydrocarbon groups.)
Or general formula (5):

(Wherein R9 is the same as above, R11 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic having 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups.)
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a diol unit derived from a diol represented by the formula:   A diol unit having the cyclic acetal skeleton derived from 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, The thermoplastic resin according to any one of claims 1 to 3, which is a diol unit derived from 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane. Composition.   Diol derived from one or more diols selected from the group consisting of ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol, other than the diol unit having a cyclic acetal skeleton It is a unit, The thermoplastic resin composition in any one of Claims 1-5.   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the polyester resin (B) is a polyester resin containing 70 mol% or more of an aromatic dicarboxylic acid unit in the dicarboxylic acid unit.   1 wherein the aromatic dicarboxylic acid unit is selected from the group consisting of terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid. The thermoplastic resin composition according to claim 7, which is a dicarboxylic acid unit derived from at least one kind of dicarboxylic acid.   The thermoplastic resin composition according to claim 1, wherein the phosphorus compound (C) has a melting point of 50 ° C. or higher and 150 ° C. or lower. The method for producing a thermoplastic resin composition according to any one of claims 1 to 9, wherein the polyester resin (B) is produced in the presence of a titanium-containing compound.