JP3284213B2 - Thermoplastic resin and optical parts made of it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin comprising an N-substituted maleimide copolymer and having excellent optical properties and heat resistance, and an optical component comprising the same.

[0002]

2. Description of the Related Art Conventionally, glass has been generally used as an optical material, but in recent years, a transparent polymer material has come to be used in view of productivity, weight reduction, cost, and the like.

[0003] As such a material, polymethyl methacrylate (hereinafter abbreviated as PMMA) is mainly used.

[0004] However, although PMMA is excellent in optical properties, its glass transition temperature (Tg) is around 100 ° C, so that its heat resistance is insufficient and its use is restricted.

[0005] Various studies have been made on maleimide copolymers because of their high heat resistance. For example, a method of copolymerizing the above methyl methacrylate with an N-aromatic substituted maleimide is disclosed in JP-B-43-9753 and JP-A-61-975.
No. 141715, JP-A-61-171708 and JP-A-62-109811 disclose a method of copolymerizing a styrene resin with an N-aromatic substituted maleimide.
JP-A-47-6891 and JP-A-61-76512.
And Japanese Patent Application Laid-Open No. 61-276807. However, the resins obtained by these methods are N
-As the content of the aromatic-substituted maleimide increases, the heat resistance becomes better, but there are problems such as brittleness, poor workability and coloring, and there is a problem in use as an optical material.

A copolymer comprising an N-alkylmaleimide and an olefin is a material excellent in transparency, heat resistance and mechanical properties, but is required to have a higher refractive index.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin excellent in high refractive index, transparency, heat resistance and the like, and an optical component comprising the same.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in view of this problem, and as a result, have found that a specific N-substituted maleimide-based copolymer and an optical component comprising the same satisfy the above objects. The invention has been completed.

That is, the present invention relates to a polymer of 20
９０90 mol% as a structural unit composed of at least one compound represented by the following general formula (I), and 10-80 mol% of the whole polymer is composed of at least one compound represented by the following general formula (II) 1 to 40 mol% of the whole polymer represented by the following general formula (II)
It has a refractive index of 1.55 or more and a polystyrene equivalent weight average molecular weight of 1 × 10 ³ or more and 5 × 10 ⁶ or more as a structural unit comprising at least one kind of the compound represented by I).
The present invention relates to a resin having the following high refractive index and excellent in transparency, heat resistance, and the like, and an optical component made of the resin.

[0010]

Embedded image (Where R ₁ represents an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms)

[0011]

Embedded image (Where R ₂ , R ₃ and R ₄ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms)

[0012]

Embedded image (Where R ₅ is hydrogen or a methyl group, R _{6 to} R ₁₀ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms or a halogen element, and X is-
O- or -S-, Y is -CH ₂ - or _-CH 2 CH
_The above resin can be obtained, for example, by a radical copolymerization reaction of N-alkyl-substituted maleimides, olefins and (meth) acrylates.

The compounds giving the structural unit (I) include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn
-Butylmaleimide, Ni-butylmaleimide, N-
s-butylmaleimide, Nt-butylmaleimide, N
-N-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N N-alkyl-substituted maleimides such as -cyclohexylmaleimide, and maleimides having 1 to 6 carbon atoms, particularly N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, and N-cyclohexylmaleimide are preferable from the viewpoint of heat resistance. . These can be used alone or in combination of two or more.

The compounds giving the structural unit (II) include ethylene, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 1-methyl-1-heptene, -Isooctene, 2-methyl-
Olefins such as 1-octene, 2-ethyl-1-pentene, 2-methyl-2-butene, 2-methyl-2-pentene and 2-methyl-2-hexene, from the viewpoint of heat resistance and mechanical properties Isobutene is preferred. These can be used alone or in combination of two or more.

Examples of the compound giving the structural unit (III) include phenyl acrylate, 4-methylphenyl acrylate, chlorophenyl acrylate, dichlorophenyl acrylate, trichlorophenyl acrylate, and bromophenyl. Acrylate, dibromophenyl acrylate, tribromophenyl acrylate, benzyl acrylate, 2- (tribromophenoxy) ethyl acrylate, phenylthiol acrylate, phenyl methacrylate, -Methylphenyl methacrylate, chlorophenyl methacrylate, dichlorophenyl methacrylate, trichlorophenyl methacrylate, bromophenyl methacrylate, dibromophenyl methacrylate
G, tribromophenyl methacrylate, pentabromophenyl methacrylate, benzyl methacrylate, phenylthiol methacrylate and the like. These can be used alone or in combination of two or more.

The content of the structural unit (I) is 20 to 90 mol% of the whole polymer, 20 to 75 mol%, especially 2
5 to 50 mol% is preferred. When the amount of the structural unit (I) exceeds 90 mol%, the formed polymer becomes brittle, which is not preferable. When the amount is less than 20 mol%, the heat resistance of the formed polymer is unfavorably reduced.

The content of the structural unit (II) is 10 to 80 mol% of the whole polymer, preferably 20 to 80 mol%, particularly preferably 50 to 75 mol%. Structural unit (II) is 80
If it exceeds mol%, the heat resistance of the polymer will be reduced, and if it is less than 10 mol%, the resulting polymer will be brittle, which is not preferable.

The content of the structural unit (III) is determined based on the polymer
1 to 40 mol% of the whole, and 3 to 30 mol%, particularly 5
~ 25 mol% is preferred. If the constitutional unit (III) exceeds 40 mol%, the resulting polymer has a low Abbe number and the resulting polymer becomes brittle. If it is less than 1 mol%, the formed polymer is refracted. This is not preferable because the rate decreases.

If necessary, other vinyl monomers can be copolymerized as long as the object of the present invention is not impaired. Other vinyl monomers include styrene, α
-Methylstyrene, methylstyrene, chlorostyrene,
Styrene derivatives such as bromostyrene, 1,3-butadiene, isoprene and halogen-substituted derivatives thereof, methacrylates such as methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate , Acrylic esters such as cyclohexyl acrylate, vinyl esters such as vinyl acetate and vinyl benzoate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether, vinyl chloride, Vinylidene chloride, maleic anhydride, N
One or more compounds selected from -phenylmaleimide, N- (2-methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-chlorophenyl) maleimide, N-carboxyphenylmaleimide, and acrylonitrile Are listed.

For the polymerization of these monomers, any of known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be employed.

Examples of the polymerization initiator include benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-tert-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, and t-butyl peroxyacetate.
Or an organic peroxide such as t-butyl peroxybenzoate, perbutyl neodecane, or 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′
-Azobis (2-butyronitrile), 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (cyclohexane-1-carbonitrile), etc. Azo-based initiators.

Solvents usable in the solution polymerization method include benzene, toluene, xylene, ethylbenzene,
Cyclohexane, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide,
Isopropyl alcohol, butyl alcohol and the like can be mentioned.

The polymerization temperature can be appropriately set in accordance with the decomposition temperature of the initiator, but is generally preferably in the range of 40 to 150 ° C.

The amount of residual maleimide monomer contained in the polymer is 3% by weight or less, preferably 1% by weight or less, particularly preferably 0.1% by weight or less, and the amount of residual monomer exceeds 3% by weight. In this case, the obtained polymer tends to be undesirably colored.

Here, the weight average molecular weight (Mw) of the produced resin is determined by gel permeation chromatography.
(GPC). The molecular weight of the resin of the present invention is 1 × 10 ³ or more and 5 × 10 ⁶ or less, particularly 1 × 10 3
Those having ^{4 to} 5 × 10 ⁵ are preferred. 5 × molecular weight
If it exceeds 10 ⁶ , the moldability will be poor and 1 × 10 ³
If it is less than 3, the obtained resin tends to be brittle.

The resin obtained in the present invention may contain, if necessary, a heat stabilizer such as hindered phenol or an organic phosphate, a benzotriazole type ultraviolet absorber, a hindered amine type ultraviolet stabilizer, Various lubricants, dyes and the like may be added. Further, another resin compatible with the resin may be mixed.

The resin of the present invention is excellent in high refractive index, transparency and heat resistance, and is useful as various optical parts.

Particularly, the resin used for the optical component has a light transmittance of 85% or more, particularly 90% or more, and a refractive index of 1.5 or more.
3 or more, preferably 1.55 or more, and an Abbe number of 3
5 or more, preferably 38 or more, having a glass transition temperature of 100 ° C. or more, preferably 120 ° C. or more;
Polymers having a yellowness of 5 or less, preferably 4 or less, as measured by a computer (Suga Test Instruments Co., Ltd .; reflection method) are preferred.

When the refractive index is less than 1.53, there is a problem that, for example, the thickness of the corrective spectacle lens becomes large. When the Abbe number is less than 35, chromatic aberration increases, eyes become tired, and the like. Is not preferable because of the problem described above. If the glass transition temperature of the obtained polymer is less than 100 ° C., its use is limited due to insufficient heat resistance. On the other hand, if the yellowness exceeds 5, the resulting optical parts are inferior in transparency and appearance.

The optical components include spherical and aspherical lenses such as compact disk lenses, video lenses, and camera lenses, optical lenses such as eyeglass lenses, optical fibers, substrates for optical disks and optical cards, and prisms. Automotive lenses such as headlight lenses, fog light lenses, turn lenses, and brake lamp lenses, signal lenses, lighting components, and the like.

Examples of the method for molding the resin of the present invention include ordinary molding methods such as injection molding, extrusion molding, compression molding, and spin coating.

[0032] Hard coating,
Processing such as anti-reflection coating can also be performed.

[0033]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples.

The molecular weight of the produced polymer was determined by GPC (Toso
It was determined in terms of polystyrene by using HLC-802A manufactured by Co., Ltd.).

The Tg of the produced polymer was measured by using DSC200 manufactured by Seiko Electronics Co., Ltd.

The light transmittance was measured according to ASTM 1746. The refractive index and Abbe number were measured using an Abbe refractometer.

The obtained polymer was pelletized by Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.), and a test piece was formed using a small injection molding machine (manufactured by Panajection Matsushita Electric Industrial Co., Ltd.). Flexural strength was evaluated according to ASTM D790.

The yellowness of the produced polymer is measured according to JIS K54.
In accordance with No. 01, a 0.8 mm press test piece was used to evaluate with a color computer (manufactured by Suga Test Instruments Co., Ltd.) (reflection method; tristimulus value of reflector x: 79.44, y) : 8
2.22, z: 94.51).

Example 1 392 g of N-methylmaleimide and 9 parts of trichlorophenyl methacrylate were placed in a 10-liter autoclave equipped with a stirrer, a nitrogen inlet tube, an isobutene inlet tube, a thermometer and a degassing tube.
After 37 g, 3 g of perbutyl neodecaneate and 5 l of dioxane were charged and purged several times with nitrogen, 2.8 l of liquefied isobutene was charged and reacted at 60 ° C. for 5 hours.

The reaction content was poured into ethanol and the polymer
Was precipitated. The obtained polymer was purified by reprecipitation with chloroform-ethanol, and dried under reduced pressure at 60 ° C. for 24 hours. The yield was 610 g.

From the results of ¹ H-NMR measurement and elemental analysis of the obtained polymer, 42.3 mol% of maleimide units, 7.9 mol% of trichlorophenyl methacrylate units and 7.9 mol% of isobutene units in the resulting polymer were obtained. Is 49.8 mol%
Met. The obtained polymer had a molecular weight (Mw) of 5300.
It was 0. Table 1 shows the characteristic evaluation results.

Example 2 N-methylmaleimide 392 was added to the same apparatus as in Example 1.
g, 1408 g of tribromophenyl methacrylate, 3 g of perbutyl neodecaneate and 5 l of dioxane, and after purging several times with nitrogen, liquefied isobutene 2.8 was obtained.
and the reaction was carried out at 60 ° C. for 5 hours.

The reaction content was poured into ethanol and the polymer
Was precipitated. The obtained polymer was purified by reprecipitation with chloroform-ethanol, and dried under reduced pressure at 60 ° C. for 24 hours. The yield was 370 g.

From the results of ¹ H-NMR measurement and elemental analysis of the obtained polymer, 32.7 mol% of maleimide units, 21.5 mol% of tribromophenyl methacrylate units and 21.5 mol% of isobutene in the resulting polymer were obtained. The unit was 45.8 mol%. The obtained polymer has a molecular weight (Mw) of 540.
00. Table 1 shows the characteristic evaluation results.

Example 3 An N-methylmaleimide 314 was added to the same apparatus as in Example 1.
g, 782 g of tribromophenyl methacrylate,
After 1.5 g of butyl neodecaneate and 5 l of dioxane were charged and purged several times with nitrogen, liquefied isobutene was added.
3 l were charged and reacted at 60 ° C. for 5 hours.

The content of the reaction was poured into ethanol, and the polymer was
Was precipitated. The obtained polymer was purified by reprecipitation with chloroform-ethanol, and dried under reduced pressure at 60 ° C. for 24 hours. The yield was 350 g.

From the results of ¹ H-NMR measurement and elemental analysis of the obtained polymer, 38.5 mol% of maleimide units, 11.6 mol% of tribromophenyl methacrylate units and 11.6 mol% of isobutene were contained in the resulting polymer. The unit was 49.9 mol%. The obtained polymer has a molecular weight (Mw) of 540.
00. Table 1 shows the characteristic evaluation results.

Comparative Examples 1 and 2 As Comparative Example 1, an acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd.)
Acrypet VH) and polycarbonate resin as Comparative Example 2 (Panlite K1300 manufactured by Teijin Chemicals Ltd.)
Was used for the same measurement.

[0049]

[Table 1]

[0050]

As is clear from the examples, according to the present invention, it is possible to obtain a resin having excellent optical properties, particularly excellent transparency, a well-balanced refractive index and Abbe number, and excellent heat resistance. These are useful as optical materials.

Claims (2)

(57) [Claims] (1) 20 to 90 mol% of the whole polymer is contained as a constitutional unit composed of at least one compound of the following general formula (I), and 10 to 80 mol% of the whole polymer is the following general formula (II) And at least one of the compounds represented by
Comprises 40 mol% structural units of at least one compound represented by the following formula (III), the refractive
A thermoplastic resin having a ratio of 1.55 or more and a polystyrene equivalent weight average molecular weight of 1 × 10 ³ or more and 5 × 10 ⁶ or less. Embedded image (Where R ₁ represents an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms) (Wherein, R ₂ , R ₃ and R ₄ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms). (Where R ₅ is hydrogen or a methyl group, R _{6 to} R ₁₀ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, 1 carbon atom
To 4 alkoxyl groups or halogen elements, X is -O-
Or -S-, Y is -CH ₂ - or -CH ₂ CH ₂ O
-, N represents an integer of 0 to 4) 2. An optical component comprising the resin according to claim 1.