JP2017039850A - Copolymer, copolymer production method, resin composition, molded article, and vehicle - Google Patents

Abstract

The present invention provides a copolymer excellent in heat resistance of a molded article to be obtained. Provided is a method for producing a copolymer which is excellent in productivity and excellent in heat resistance of a molded article to be obtained. A copolymer comprising a repeating unit (A) derived from methyl methacrylate, a repeating unit (B) represented by the general formula (1) and a repeating unit (C) represented by the general formula (2). A method for producing a copolymer, wherein the copolymer containing the unit (A) and the unit (B) is heated to obtain a copolymer containing the unit (A), the unit (B) and the unit (C). . A resin composition containing the copolymer. A molded article obtained by molding the resin composition. A vehicle including the molded body. [Selection figure] None

Description

  The present invention relates to a copolymer, a method for producing the copolymer, a resin composition, a molded body, and a vehicle.

Polymethyl methacrylate and polycarbonate are widely used in various fields such as optical materials, vehicle parts, lighting materials, and building materials because of their excellent transparency and dimensional stability.
In recent years, molded products of polymethylmethacrylate and polycarbonate have been required to have higher performance as the parts are made thinner and finer. One of the performances is heat resistance. In particular, vehicle parts such as tail lamps and head lamps are required to have better heat resistance because vehicles such as automobiles are used even under high temperature and high humidity.

  However, although polymethylmethacrylate has excellent transparency and weather resistance, its heat resistance is not sufficient. Polycarbonate has excellent heat resistance and impact resistance, but has a large birefringence, which is an optical distortion, and causes optical anisotropy in the molded product. In addition, it has molding processability, scratch resistance, and oil resistance. Remarkably inferior.

  Therefore, studies for improving the heat resistance of polymethyl methacrylate have been conducted. For example, Patent Document 1 proposes a method in which methyl methacrylate and methacrylamide are copolymerized, and the resulting copolymer is heated to form an imide ring structure.

JP 2009-227973 A

  However, since the method proposed in Patent Document 1 uses methacrylamide whose terminal is a primary amine, the toxicity of the raw material is high, and there is a concern about the safety when remaining in a copolymer or a molded product. Have.

  Then, the objective of this invention is providing the copolymer excellent in the heat resistance of the molded object obtained. Moreover, the objective of this invention is providing the manufacturing method of the copolymer which is excellent in productivity and excellent in the heat resistance of the molded object obtained.

  The present invention relates to a copolymer comprising a repeating unit (A) derived from methyl methacrylate, a repeating unit (B) represented by the following general formula (1) and a repeating unit (C) represented by the following general formula (2). About.

In general formulas (1) and (2), R ¹ , R ³ and R ⁴ are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms. In General Formulas (1) and (2), R ² is a branched or cyclic hydrocarbon group having 3 or more carbon atoms.

Moreover, this invention heats the copolymer containing the said unit (A) and the said unit (B), and obtains the copolymer containing the said unit (A), the said unit (B), and the said unit (C). And relates to a method for producing the copolymer according to claim 1.
Moreover, this invention relates to the resin composition containing the said copolymer.
Moreover, this invention relates to the molded object obtained by shape | molding the said resin composition.
Furthermore, this invention relates to the vehicle containing the said molded object.

The copolymer of this invention is excellent in the heat resistance of the molded object obtained.
Moreover, the manufacturing method of the copolymer of this invention is excellent in productivity, and is excellent in the heat resistance of the molded object obtained from the copolymer obtained.
Moreover, the thermoplastic resin composition of the present invention is excellent in the heat resistance of the obtained molded article.
Moreover, the molded object of this invention is excellent in heat resistance.
Furthermore, the vehicle of the present invention is excellent in heat resistance.

  The copolymer of the present invention comprises a methyl methacrylate-derived repeating unit (A) (hereinafter sometimes simply referred to as “unit (A)”), a repeating unit (B) represented by the following general formula (1) ( Hereinafter, it may be simply referred to as “unit (B)”) and a repeating unit (C) represented by the following general formula (2) (hereinafter also referred to simply as “unit (C)”).

In general formulas (1) and (2), R ¹ , R ³ and R ⁴ are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms. In General Formulas (1) and (2), R ² is a branched or cyclic hydrocarbon group having 3 or more carbon atoms.

  Since the method for producing a copolymer containing the unit (A), the unit (B) and the unit (C) is excellent in productivity, the copolymer containing the unit (A) and the unit (B) is obtained by heating. The method is preferred.

  The copolymer containing the unit (A) and the unit (B) can be obtained by copolymerizing a monomer composition containing methyl methacrylate and a monomer for constituting the unit (B).

  The monomer for constituting the unit (B) is represented by the following general formula (3).

In General Formula (3), R ¹ is a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms. In general formula (3), R ² is a linear, branched or cyclic hydrocarbon group having 2 or more carbon atoms.
Note that the ^{R 1} in ^{R 1} of the general formula (1) (3) are identical. Further, the ^{R 2} of the ^{R 2} of the general formula (1) (3) are identical.

R ¹ is a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms, and is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom because of excellent polymerizability.

R ² is a branched or cyclic hydrocarbon group having 3 or more carbon atoms, but is preferably a branched or cyclic hydrocarbon group having 3 or more carbon atoms because of excellent heat resistance of the molded article. A branched hydrocarbon group of ˜5 is more preferred, and an isopropyl group is more preferred.

Specific examples of the monomer for constituting the unit (B) include, for example, N-isopropyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyl ( And (meth) acrylamide. As the monomer for constituting these units (B), one type may be used alone, or two or more types may be used in combination. Among the monomers for constituting these units (B), N-isopropyl (meth) acrylamide is preferable and N-isopropylacrylamide is more preferable because of excellent heat resistance.
In the present specification, (meth) acryl represents acryl, methacryl or both.

  The content of methyl methacrylate is preferably 50 mol% to 99 mol%, more preferably 55 mol% to 98 mol%, in 100 mol% of the monomer composition. When the content of methyl methacrylate is 50 mol% or more, the original performance of the acrylic resin is not impaired. Moreover, it is excellent in heat resistance in the content rate of methyl methacrylate being 99 mol% or less.

  The content of the monomer for constituting the unit (B) is preferably 1 mol% to 50 mol%, more preferably 2 mol% to 45 mol%, in 100 mol% of the monomer composition. When the content of the monomer for constituting the unit (B) is 1 mol% or more, the heat resistance is excellent. Further, if the content of the monomer for constituting the unit (B) is 50 mol% or less, the original performance of the acrylic resin is not impaired.

  The monomer composition may contain other monomers in addition to the monomers for constituting methyl methacrylate and the unit (B).

  Examples of other monomers include, for example, methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec -Butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate , Tridecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycy (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetracyclododecanyl (meth) Acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybuty (Meth) acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, 2- (meth) acryloyloxymethyl-2-methylbicycloheptane, 4- (meth) (Meth) acrylate compounds such as acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane; styrene; aromatic vinyl compounds such as α-methylstyrene; vinyl ether compounds such as vinyl methyl ether, vinyl ethyl ether and 2-hydroxyethyl vinyl ether; vinyl carboxylates such as vinyl acetate and vinyl butyrate; ethylene, propylene, butene, Olefin compounds such as Sobuten like. These other monomers may be used individually by 1 type, and may use 2 or more types together. Among these other monomers, methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferable, and methyl acrylate and ethyl acrylate are preferable because of excellent appearance and thermal stability of the molded body.

  The content of other monomers is preferably 20 mol% or less, more preferably 10 mol% or less, in 100 mol% of the monomer composition, because the original performance of the acrylic resin is not impaired.

  Examples of the polymerization method of the monomer composition containing methyl methacrylate and the monomer for constituting the unit (B) include a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method. . Among these polymerization methods, the polymerization method and the post-treatment are easy, and the bulk polymerization method and the suspension polymerization method are preferable, and the continuous bulk polymerization method is more preferable because of excellent productivity.

  The polymerization conditions of the monomer composition containing the monomer for constituting the methyl methacrylate and the unit (B) such as polymerization temperature, polymerization initiator type, polymerization initiator amount, chain transfer agent type, chain transfer agent amount, etc. It may be set as appropriate so as to obtain a desired copolymer.

  Examples of the method for heating the copolymer containing the unit (A) and the unit (B) for obtaining a copolymer containing the unit (A), the unit (B) and the unit (C) include extrusion molding and heat drying. Examples include holding in a vessel, heating in an ampule tube, heating in an autoclave, and the like. These heating methods may be used individually by 1 type, and may use 2 or more types together. Among these heating methods, because of excellent reaction uniformity, extrusion molding and heating in an autoclave are preferable, and extrusion molding is more preferable.

  The heating temperature of the copolymer containing the unit (A) and the unit (B) for obtaining a copolymer containing the unit (A), the unit (B) and the unit (C) is preferably 150 ° C. to 300 ° C., 160 to 290 degreeC is more preferable. When the heating temperature is 150 ° C. or higher, the production of the unit (C) is promoted and the heat resistance is excellent. Moreover, thermal decomposition can be suppressed as heating temperature is 300 degrees C or less.

The content of the unit (A) in the copolymer containing the unit (A), the unit (B) and the unit (C) is 100 mol of the copolymer containing the unit (A), the unit (B) and the unit (C). %, 50 mol% to 99 mol% is preferable, and 55 mol% to 98 mol% is more preferable. When the content of the unit (A) is 50 mol% or more, the original performance of the acrylic resin is not impaired. Moreover, it is excellent in heat resistance in the content rate of a unit (A) being 99 mol% or less.
In this specification, the copolymer composition is a value calculated from ¹ H-NMR measurement.

  The content of the unit (B) in the copolymer containing the unit (A), the unit (B) and the unit (C) is 100 mol of the copolymer containing the unit (A), the unit (B) and the unit (C). %, 0.5 mol% to 10 mol% is preferable, and 1 mol% to 7.5 mol% is more preferable. Productivity is excellent in the content rate of a unit (B) being 0.5 mol% or more. Moreover, the original performance of an acrylic resin is not impaired as the content rate of a unit (B) is 10 mol% or less.

  The content of the unit (C) in the copolymer containing the unit (A), the unit (B) and the unit (C) is 100 mol of the copolymer containing the unit (A), the unit (B) and the unit (C). %, 0.5 mol% to 40 mol% is preferable, and 1 mol% to 37.5 mol% is more preferable. When the content of the unit (C) is 0.5 mol% or more, the heat resistance is excellent. Moreover, the original performance of an acrylic resin is not impaired as the content rate of a unit (C) is 50 mol% or less.

The copolymer containing the unit (A), the unit (B) and the unit (C) may contain repeating units derived from other monomers in addition to the unit (A), the unit (B) and the unit (C). Good.
Examples of the other monomer include the other monomers described above.

  Since the content of the repeating unit derived from another monomer in the copolymer containing the unit (A), the unit (B) and the unit (C) does not impair the original performance of the acrylic resin, the unit (A) , 20 mol% or less is preferable in 100 mol% of the copolymer containing the unit (B) and the unit (C), and 10 mol% or less is more preferable.

1,000-1,000,000 are preferable and, as for the mass average molecular weight of the copolymer containing a unit (A), a unit (B), and a unit (C), 10,000-300,000 are more preferable. When the mass average molecular weight is 1,000 or more, the molded article has excellent mechanical properties. Further, when the mass average molecular weight is 1,000,000 or less, the fluidity is excellent.
In this specification, the mass average molecular weight is a value measured using gel permeation chromatography using standard polystyrene as a standard sample.

  The Vicat softening temperature of the copolymer containing the unit (A), the unit (B) and the unit (C) is preferably 110 ° C to 300 ° C, more preferably 115 ° C to 200 ° C. When the Vicat softening temperature is 110 ° C. or higher, the molded article has excellent heat resistance. Moreover, it is excellent in the productivity of the copolymer containing a unit (A), a unit (B), and a unit (C) as the Vicat softening temperature is 300 degrees C or less.

  The resin composition of the present invention contains the copolymer of the present invention.

The resin composition of the present invention may contain other additives in addition to the copolymer of the present invention.
Examples of other additives include a colorant such as an ultraviolet absorber, an antioxidant, and a pigment. These other additives may be used alone or in combination of two or more. It is preferable to include an ultraviolet absorber in the resin composition because deterioration due to ultraviolet rays can be suppressed.
The content of the other additive is preferably 5% by mass or less, more preferably 1% by mass or less, in 100% by mass of the resin composition because the original performance of the acrylic resin is not impaired.

  The molded product of the present invention is obtained by molding the resin composition of the present invention.

Examples of the molding method for obtaining the molded body include injection molding, extrusion molding, and pressure molding. Further, the obtained molded body may be further subjected to secondary molding such as pressure molding or vacuum molding.
What is necessary is just to set suitably molding conditions, such as molding temperature and molding pressure.

Since the molded body of the present invention is excellent in heat resistance, it can be used for optical materials, vehicle parts, lighting materials, building materials, and the like, and is particularly suitable for automotive vehicle parts.
Examples of automotive vehicle parts include a rear lamp outer cover, an optical member inside the rear lamp, an inner lens for a headlight (sometimes referred to as a projector lens or a PES lens), a meter cover, a door mirror housing, a pillar cover ( Sash cover), license garnish, front grille, fog garnish, emblem and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

(Mass average molecular weight)
10 mg of the copolymer / polymer obtained in Examples and Comparative Examples was dissolved in 10 ml of N, N-dimethylformamide, respectively, and filtered through a 0.5 μm membrane filter to obtain a sample solution. About the obtained sample solution, the mass average molecular weight was measured using the gel permeation chromatography (model name "HLC-8020", Tosoh Corporation make). Two separation columns, “TSKgel SuperHZM-H” (trade name, manufactured by Tosoh Corporation, inner diameter 4.6 mm × length 15 cm), N as a solvent containing lithium chloride at 0.01 mol / l, N-dimethylformamide, a differential refractometer as a detector, standard polystyrene as a standard sample, a flow rate of 0.6 ml / min, a measurement temperature of 40 ° C., and an injection amount of 0.1 ml were used.

(composition)
The copolymer / polymer obtained in Examples / Comparative Examples was dissolved in heavy dimethyl sulfoxide, respectively, and ¹ H-NMR (manufactured by varian, 270 MHz) was measured to determine the unit of each unit in the copolymer / polymer. The molar ratio was calculated.

(Heat-resistant)
Each of the copolymers / polymers obtained in Examples and Comparative Examples was molded using a small injection molding machine (model name “MODEL CS-183MMX”, manufactured by Custom Scientific Instruments) with a molding temperature of 255 ° C. Injection molding was performed under the conditions to obtain a molded body (10 mm × 20 mm × 2 mm).
Each of the obtained molded bodies was subjected to a Vicat softening temperature test using an HDT / VICAT testing machine (model name “No. 148-HAD heat distortion tester”, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) to determine the Vicat softening temperature. It was measured.

[Example 1]
A 300 ml glass beaker was charged with 40.0 g of methyl methacrylate, 10.0 g of N-isopropylacrylamide, and 0.10 g of 2,2-azobis (2-methylvaleronitrile) as a polymerization initiator, and stirred in an environment of 25 ° C. The mixture was degassed for 15 minutes using an aspirator while stirring. The monomer solution after the treatment was supplied to the polymerization bag, the air was removed, and it was sealed with a heat sealer.
The polymerization bag was then placed in a 75 ° C. water bath and held for 3 hours. Thereafter, the polymerization bag was placed in an inert oven at 120 ° C. and held for 2 hours. After cooling to 25 ° C., the solid matter was taken out from the polymerization bag, and the obtained solid matter was pulverized with a stamp mill to obtain a copolymer.
Table 1 shows the evaluation results of the obtained copolymer.

[Example 2]
A copolymer was obtained in the same manner as in Example 1 except that 35.0 g of methyl methacrylate and 15.0 g of N-isopropylacrylamide were changed.
Table 1 shows the evaluation results of the obtained copolymer.

[Comparative Example 1]
A copolymer was obtained in the same manner as in Example 1 except that 50.0 g of methyl methacrylate and 0 g of N-isopropylacrylamide were changed.
Table 1 shows the evaluation results of the obtained copolymer.

In Examples 1 and 2, a copolymer can be obtained by a simple process without using a highly toxic monomer, and the obtained copolymer was excellent in heat resistance.
On the other hand, Comparative Example 1 was inferior in heat resistance.

Since the molded body of the present invention is excellent in heat resistance, it can be used for optical materials, vehicle parts, lighting materials, building materials, and the like, and is particularly suitable for automotive vehicle parts.

Claims (11)

A copolymer comprising a repeating unit (A) derived from methyl methacrylate, a repeating unit (B) represented by the following general formula (1), and a repeating unit (C) represented by the following general formula (2).


(In the general formulas (1) and (2), R ¹ , R ³ and R ⁴ are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms. In formulas (1) and (2), R ² is a branched or cyclic hydrocarbon group having 3 or more carbon atoms. The copolymer according to claim 1, wherein R ² is a branched hydrocarbon group having 3 to 5 carbon atoms. The copolymer according to claim 1 or 2, wherein R ² is an isopropyl group.   The unit (A) is 50 mol% to 99 mol%, the unit (B) is 0.5 mol% to 10 mol%, and the unit (C) is 0.5 mol% to 40 mol%. The copolymer described in 1.   The copolymer in any one of Claims 1-4 whose mass mean molecular weight is 1,000-1,000,000.   The copolymer containing said unit (A) and said unit (B) is heated, and the copolymer containing said unit (A), said unit (B), and said unit (C) is obtained. The manufacturing method of the copolymer in any one of.   The manufacturing method of the copolymer of Claim 6 whose heating temperature is 150 to 280 degreeC.   The resin composition containing the copolymer in any one of Claims 1-5.   Furthermore, the resin composition of Claim 8 containing a ultraviolet absorber.   The molded object obtained by shape | molding the resin composition of Claim 8 or 9. A vehicle comprising the molded body according to claim 10.