JP2012001609A - Polycarbonate resin composition, method for producing polycarbonate resin molded product, and polycarbonate resin molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition that suppresses sublimation of an ultraviolet absorber included therein even during high-temperature molding applied to the polycarbonate resin composition and provides a molded product having further excellent weather resistance, strength, etc. by inhibiting staining of a mold and the molded product resulting from the sublimation, a method for producing a polycarbonate resin molded product using the same, and the polycarbonate resin molded product obtained by the production method.SOLUTION: A cyclic imino ester represented by chemical formula is used in a proportion of 0.05-5 pts.mass per 100 pts.mass of a polycarbonate resin. In the formula, Ris a residue obtained by eliminating n hydrogen atoms from a hydrocarbon compound having one or two aromatic rings in the molecule; and n is 2 or 3.

Description

  The present invention relates to a polycarbonate resin composition, a method for producing a polycarbonate resin molded body, and a polycarbonate resin molded body. More specifically, by using a specific cyclic imino ester, contamination of a mold or a molded body can be prevented even in high temperature molding. The present invention relates to a polycarbonate resin composition capable of obtaining a molded article having excellent weather resistance, strength, and the like, a method for producing a polycarbonate resin molded article using the same, and a polycarbonate resin molded article obtained by the production method.

  A molded article of a polycarbonate resin composition using an ultraviolet absorber or the like for a polycarbonate resin is used in a wide range of fields such as transportation equipment such as aircraft and automobiles, optical equipment and medical equipment. Examples of such polycarbonate resin compositions include those using benzoxazine-based UV absorbers (for example, see Patent Document 1), examples using benzotriazole-based (for example, Patent Document 2), and benzotriazine-based compositions. An example using a material (for example, see Patent Document 3), an example using a benzophenone-based material (for example, see Patent Document 4), and the like are known. However, since these conventional polycarbonate resin compositions have insufficient heat resistance of the ultraviolet absorbers used, a large amount of sublimation occurs during high-temperature molding applied to the polycarbonate resin composition, so There is a problem that it is soiled and the weather resistance is insufficient. In order to improve such a problem, a method of lowering the molding temperature by using a fluidizing agent in the polycarbonate resin is generally known (see, for example, Patent Document 5), but in this case, the strength of the obtained molded product is lowered. There is a problem of doing.

JP 2003-155468 A JP-A-51-21587 JP-A-10-067758 JP 58-110535 A JP 54-40854 A

  The problem to be solved by the present invention is to suppress sublimation of the UV absorber contained in the high temperature molding applied to the polycarbonate resin composition, and to prevent the mold and molded body from being soiled by sublimation. The present invention provides a polycarbonate resin composition capable of obtaining a molded article having weather resistance, strength, and the like, a method for producing a polycarbonate resin molded article using the same, and a polycarbonate resin molded article obtained by the production method.

  As a result of studies to solve the above problems, the present inventors have found that a polycarbonate resin composition in which a specific cyclic imino ester is contained in a polycarbonate resin in a predetermined ratio is correctly suitable.

  That is, the present invention relates to a polycarbonate resin composition comprising 0.05 to 5 parts by mass of a cyclic imino ester represented by the following chemical formula 1 per 100 parts by mass of a polycarbonate resin. Moreover, this invention concerns on the manufacturing method of a polycarbonate resin molding characterized by shape | molding this polycarbonate resin composition at the shaping | molding temperature of 320-400 degreeC. Furthermore, the present invention relates to a polycarbonate resin molded article obtained by such a production method.

In chemical formula 1,
R ¹ : a residue obtained by removing n hydrogen atoms from a hydrocarbon compound having one or two aromatic rings in the molecule n: 2 or 3

First, the polycarbonate resin composition according to the present invention (hereinafter referred to as the composition of the present invention) will be described. The composition of the present invention comprises a polycarbonate resin containing a cyclic imino ester represented by Chemical Formula 1 in a predetermined ratio. R ^{1 in} Chemical Formula ¹ is a residue obtained by removing n hydrogen atoms from a hydrocarbon compound having one or two aromatic rings in the molecule, and n is 2 or 3. Among them, in the cyclic imino ester represented by Chemical Formula 1, R ^{1 in} Chemical Formula ¹ is a residue obtained by removing n hydrogen atoms from a hydrocarbon compound having (4-n) aromatic rings in the molecule. , N is preferably 2 or 3, wherein R ^{1 in} Chemical Formula ¹ is a residue obtained by removing three hydrogen atoms from a hydrocarbon compound having one aromatic ring in the molecule, and n is The case of 3 is more preferable. Specifically, R ^{1 in} Chemical Formula ¹ includes 1) a residue obtained by removing two hydrogen atoms from benzene, a residue obtained by removing two hydrogen atoms from naphthalene, and two hydrogen atoms removed from biphenyl In the case where n is 2, such as a residue, 2) a residue obtained by removing 3 hydrogen atoms from benzene, a residue obtained by removing 3 hydrogen atoms from naphthalene, and 3 hydrogen atoms from biphenyl Examples include residues where n is 3, such as 3) residues obtained by removing 2 hydrogen atoms from naphthalene, and residues n by removing 2 hydrogen atoms from biphenyl. 4) The case where n of a residue obtained by removing 3 hydrogen atoms from benzene is 3 is preferable, and the case where n of a residue obtained by removing 3 hydrogen atoms from benzene is 3 The case where is is more preferable.

  Examples of the cyclic imino ester used in the resin composition of the present invention include 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) and 2,2′-m-phenylenebis (3,1- Benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6 or 1,5-naphthalene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2 -Nitro-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 '-(2-chloro-p-phenylene) bis (3,1-benzoxazin-4-one), 1 , 3,5-tri (3,1-benzoxazin-4-one-2- ) Benzene, 1,3,5-tri (3,1-benzoxazin-4-one-2-yl) naphthalene, 2,4,6-tri (3,1-benzoxazin-4-one-2-) Yl) naphthalene, among others, 2,2'-p-phenylenebis (3,1-benzoxazin-4-one), 2,2'-m-phenylenebis (3,1-benzoxazine- 4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6 or 1,5-naphthalene) bis ( 3,1-benzoxazin-4-one), 1,3,5-tri (3,1-benzoxazin-4-one-2-yl) benzene are preferred, and 1,3,5-tri (3,1 -Benzoxazin-4-one-2-yl) benzene is more preferred.

  In the composition of the present invention, the cyclic imino ester is used so as to have a ratio of 0.05 to 5 parts by mass per 100 parts by mass of the polycarbonate resin, and in particular, a ratio of 0.1 to 0.5 parts by mass is used. It is preferable to use it.

  In the composition of the present invention, the polycarbonate resin is generally obtained by reacting a dihydric phenol and a carbonate precursor, and usually has a mass average molecular weight (polystyrene conversion value by gel permeation chromatography analysis, below) The same) 13000 to 100,000 is used. 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is a typical example of the dihydric phenol used as the raw material, and phosgene and diphenyl carbonate are typical examples of the carbonate precursor. There is no restriction | limiting in the manufacturing method of polycarbonate resin, Any conventionally well-known arbitrary methods can be used. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. In producing the polycarbonate resin, a catalyst, a terminal terminator, an antioxidant and the like can be used as necessary. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or may be a polycarbonate resin copolymerized with an aromatic or aliphatic bifunctional carboxylic acid. A mixture of seeds or more may be used.

  In preparing the resin composition of the present invention, various additives can be contained depending on the purpose within a range not impairing the effects of the present invention. Examples of such additives include 1) fiber reinforcing agents such as glass fibers, metal fibers, aramid fibers, ceramic fibers, and carbon fibers, and 2) inorganic fillers such as talc, mica, clay, calcium carbonate, barium sulfate, and titanium oxide. 3) Thermal stabilizers such as phosphate esters and phosphites, as well as fluidizing agents, bluing agents, impact resistance improvers, antistatic agents, light stabilizers, flame retardants, plasticizers, etc. Is mentioned.

  Next, a method for producing a polycarbonate resin molded body according to the present invention (hereinafter referred to as the production method of the present invention) will be described. The production method of the present invention is characterized by molding the above-described composition of the present invention at a molding temperature of 320 to 400 ° C. The molding temperature is 320 to 400 ° C, and 330 to 380 ° C is particularly preferable.

  Finally, the polycarbonate resin molded body according to the present invention (hereinafter referred to as the molded body of the present invention) will be described. The molded body of the present invention is obtained by the production method of the present invention described above.

  According to the composition of the present invention, even at the time of high temperature molding applied to the polycarbonate resin composition, the sublimation of the UV absorber contained therein is suppressed, and the mold and the molded body are prevented from being soiled by sublimation, and have excellent weather resistance. There exists an effect that the molded object which has property, intensity | strength, etc. can be obtained.

  Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.

Test category 1 (Synthesis of cyclic imino ester)
-Synthesis | combination of cyclic | annular imino ester (P-1) 46.0 g of isatoic anhydride and 500 ml of pyridines were added to the 1L flask provided with the reflux condenser and the stirring apparatus, and it stirred at normal temperature. Thereto, 25.0 g of benzene tricarboxylic acid chloride was added over 1 hour. After heating and refluxing for 3 hours, the reaction slurry was cooled, and the precipitated crystals were separated by filtration and washed with 300 g of water. The crystal washed with water was dried at 145 ° C. for 3 hours to obtain 44.5 g of a cyclic imino ester (P-1).

Synthesis of cyclic imino ester (P-2, P-3 and R-1 to R-13) In the same manner as cyclic imino ester (P-1), cyclic imino ester (P-2, P-3 and R- 1-R-13). The cyclic iminoesters synthesized above are summarized in Tables 1 and 2.

・ Cyclic imino ester (synthesis of R-14)
In a 2 L flask equipped with a reflux condenser and a stirrer, a mixture of 2,5-diaminoterephthalic acid and 4,6-diaminoisophthalic acid {J. Polym. Sei. 87 g manufactured according to 60ISSUE169.60 (1962)} and 1.5 L of acetic anhydride were added, and the mixture was heated to reflux for 1 hour with stirring. Thereafter, the reaction slurry is cooled, and the precipitated crystals are separated by filtration and recrystallized from o-dichlorobenzene to give 2-8-dimethyl-4H, 6H-benzo [1,2-d: 5,4-d. '] Bis [1,3] -oxazine-4,6-dione (R-15) and 2-7-dimethyl-4H, 9H-benzo [1,2-d: 4,5-d'] bis- [ 58 g of a mixture with 1,3] -oxazine-4,9-dione was obtained.

Synthesis of cyclic imino ester (R-15 to R-18) In the same manner as cyclic imino ester (R-14), the corresponding diaminodicarboxylic acid was used, and cyclic imino ester (R-15, R-17, R -18) was obtained. The cyclic imino ester (R-16) was synthesized by reacting 3,3′-dicarboxy-4,4′-diaminophenylmethane with benzoyl chloride in pyridine. The cyclic iminoesters synthesized above are summarized in Table 3.

Test category 2 (evaluation of cyclic imino ester)
The ultraviolet absorptivity (maximum absorption wavelength, absorbance) and sublimation resistance (heat loss) of the cyclic iminoester synthesized in Test Category 1 were evaluated by the following methods. The results are summarized in Table 4.

Evaluation of UV absorption ability 1
Using tetrachloroethane as a solvent, measuring the maximum absorption wavelength (λmax) using a trade name 330 type self spectrophotometer manufactured by Hitachi, with a concentration of 5 × 10 ⁻⁴ g / 100 ml and an optical path length of 1 cm, the following criteria It was evaluated with.
Evaluation criteria A: Particularly excellent in ultraviolet absorption ability when λmax is 300 nm or more and 330 nm or less ○: Excellent in ultraviolet absorption ability when λmax is 275 nm or more and less than 300 nm or more than 330 nm and 355 nm or less Δ: When λmax is 250 nm or more and less than 275 nm or more than 355 nm and 380 nm or less Inferior in ultraviolet absorptivity x: Remarkably inferior in ultraviolet absorptivity when λmax is less than 250 nm or more than 380 nm

Evaluation of UV absorption capacity 2
Using tetrachloroethane as the solvent, measuring the absorbance (E ^1% _{1 cm} ) using a trade name 330 type self-spectrophotometer manufactured by Hitachi as a concentration of 5 × 10 ⁻⁴ g / 100 ml and an optical path length of 1 cm. Evaluated by criteria.
Evaluation criteria A: E ^1% _{1 cm} is 700 or more and particularly excellent in ultraviolet absorbing ability ○: E ^1% _{1 cm} is 600 or more and less than 700 and excellent in ultraviolet absorbing ability ×: E ^1% _{1 cm} is less than 600 and inferior in ultraviolet absorbing ability

Evaluation of sublimation resistance Using Seiko's trade name TG-DTA6200, thermogravimetric weight up to 20 to 400 ° C-
The suggested heat (TG-DTA) was measured, and the heat loss (%) at 350 ° C. was evaluated according to the following criteria.
Evaluation criteria ◎: Sublimation resistance is particularly excellent when heat loss is less than 5% ○: Sublimation resistance is excellent when heat loss is 5% or more and less than 10% ×: Sublimation resistance is poor when heat loss is 10% or more

Test category 3 (Preparation of polycarbonate resin composition and production of polycarbonate resin molding)
Example 1
100 parts of polycarbonate resin (trade name Iupilon S-3000F manufactured by Mitsubishi Engineer Plastics, mass average molecular weight 50000), 0.3 part of cyclic imino ester (P-1) synthesized in Test Category 1 and bluing agent master chip ( A-1) 0.1 parts (a master chip containing 0.1% of the trade name “Plast Blue 8580” manufactured by Arimoto Chemical Industry Co., Ltd.) was dry blended and kneaded at a temperature of 280 ° C. using a biaxial extruder. The strand extruded from the extruder was cooled with water at 20 ° C. and then cut to prepare polycarbonate resin composition pellets. The prepared pellets of the polycarbonate resin composition were dried at 120 ° C. for 5 hours, and then subjected to an injection molding machine to form a flat plate {100 mm (vertical) × 100 mm (horizontal) × 2 mm (molding temperature 350 ° C., mold temperature 80 ° C. Thickness)} and Izod test pieces (IZOD test pieces, test pieces based on JIS-K7110, with notches).

-Examples 2-7 and Comparative Examples 1-23
Using the cyclic imino ester synthesized in Test Category 1, the pellets of the polycarbonate resin compositions of Examples 2 to 7 and Comparative Examples 1 to 23 were prepared in the same manner as in Example 1 to produce flat plates and Izod test pieces. did.

Test category 4 (evaluation of molded polycarbonate resin)
The flat plate and the Izod test piece prepared in Test Category 3 were evaluated for sublimation resistance, weather resistance, moldability, and strength by the following methods, and the results are summarized in Table 4.

Evaluation of sublimation resistance The adhesion on the surface of the flat plate produced in Test Category 3 and the adhesion on the mold surface after injection molding were visually observed and evaluated according to the following criteria.
Evaluation criteria ◎: No deposits observed, particularly excellent in sublimation resistance ○: A trace amount of deposits was observed, but negligible and excellent in sublimation resistance △: Deposits were slightly recognized, and regular cleaning Is necessary and is inferior in sublimation resistance. X: A large amount of deposits are observed, adversely affecting operation and extremely inferior in sublimation resistance.

Evaluation of weather resistance The flat plate produced in Test Category 3 was irradiated with a product name Accelerated Weathering Tester lamp UVB-313 manufactured by Q-PANNEL Company, and the YI value of the flat plate after 100 hours was measured using a color difference meter manufactured by Minolta. Measured with CR-300 and evaluated according to the following criteria.
Evaluation criteria A: YI value is 15 or less and particularly excellent in weather resistance B: YI value is more than 15 and 17.5 or less, and weather resistance is excellent Δ: YI value is more than 17.5 and 20 or less, and weather resistance is inferior ×: YI Value is over 20 and weather resistance is remarkably inferior

Evaluation of formability The shapes of the flat plate and Izod test piece prepared in Test Category 3 were visually observed, and the presence or absence of chipping, cracking and distortion was evaluated according to the following criteria.
Evaluation criteria A: Excellent in formability without chipping, cracking and distortion X: Inferior in moldability with chipping, cracking and distortion

Evaluation of Strength The Izod impact value of the Izod test piece prepared in Test Category 3 was measured by a method according to JIS-K7110 (1999), and evaluated according to the following criteria.
Evaluation criteria A: Excellent in strength when the Izod impact value is 80 kJ / m ² or more ×: Inferior in strength when the Izod impact value is less than 80 kJ / m ²

In Table 4,
P-1 to P-3, R-1 to R-18: Cyclic imino ester synthesized in Test Category 1 A-1: Blueing agent master chip (trade name Plast Blue 8580 manufactured by Arimoto Chemical Co., Ltd. is 0.1 % Content)
A-2: Fluidizer (trade name TPP (triphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd.)

  As is clear from the results in Table 4, according to the polycarbonate resin composition of the present invention, even during high-temperature molding applied to the polycarbonate resin composition, the sublimation of the UV absorber contained therein is suppressed, and the die by sublimation is used. In addition, it is possible to obtain a molded article having excellent weather resistance, strength and the like by preventing the molded article from being soiled.

Claims (6)

A polycarbonate resin composition comprising 0.05 to 5 parts by mass of a cyclic imino ester represented by the following chemical formula 1 per 100 parts by mass of a polycarbonate resin.

(In chemical formula 1,
R ¹ : a residue obtained by removing n hydrogen atoms from a hydrocarbon compound having one or two aromatic rings in the molecule n: 2 or 3) 2. The cyclic imino ester is one in which R ^{1 in} Chemical Formula ¹ is a residue obtained by removing n hydrogen atoms from a hydrocarbon compound having (4-n) aromatic rings in the molecule. The polycarbonate resin composition as described. The cyclic imino ester is a residue in which R ^{1 in} Chemical Formula ¹ is a residue obtained by removing three hydrogen atoms from a hydrocarbon compound having one aromatic ring in the molecule, and n is 3. The polycarbonate resin composition according to claim 1 or 2.   The polycarbonate resin composition according to any one of claims 1 to 3, wherein the cyclic imino ester represented by Chemical Formula 1 is contained at a ratio of 0.1 to 0.5 parts by mass per 100 parts by mass of the polycarbonate resin.   A method for producing a polycarbonate resin molded article, comprising molding the polycarbonate resin composition according to any one of claims 1 to 4 at a molding temperature of 320 to 400 ° C.   A polycarbonate resin molded article obtained by the production method according to claim 5.