JPH05230145A - Thermoplastic resin and optical part comprising the same - Google Patents

Abstract

PURPOSE:To provide the subject maleimide resin comprising three kinds of specific structural units, having a high refractive index, excellent in the transparency, heat resistance, etc., having a good balance between dialysis constant and Abbe number, and useful as an optical material. CONSTITUTION:The objective resin has units of formulas I, II and III (R1 is 1-8C alkyl, 3-12C cycloalkyl; R2-R4 are H, 1-8C alkyl ; R5 is H, methyl; R6-10 are H, 1-4C alkyl, etc.; X is -O-, -S-; Y is -CH2-, -CH2CHO-; (n) is 0-4) in amounts of 20-90mol.%, 1-80mol.% and 1-40mol.%, respectively, based on the whole amount of the polymer, and has a weight-average mol.wt. of 1X10<3> to 5X10<6> expressed in terms of polystyrene. N-Methylmaleimide, etc., and isobutene are preferable as the compounds of the units I and II, respectively. Examples of the compound giving the unit of formula III include phenyl acrylate.

Description

Detailed Description of the Invention

[0001]

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

[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 been used in view of productivity, weight reduction, cost and the like.

Polymethyl methacrylate (hereinafter abbreviated as PMMA) is mainly used as such a material.

However, although PMMA has excellent optical characteristics, its glass transition temperature (Tg) is around 100 ° C., so that its heat resistance is insufficient and its use is limited.

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

The copolymer of N-alkylmaleimide and olefin is a material which is excellent in transparency, heat resistance and mechanical properties, but further higher refractive index is desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin having a high refractive index, transparency and heat resistance, and an optical component made of the resin.

[0008]

As a result of intensive studies in view of this problem, the present inventors have found that a specific N-substituted maleimide-based copolymer and an optical component comprising the same satisfy the above-mentioned object. The invention was completed.

That is, the present invention is based on the polymer 20.
To 90 mol% as a constitutional unit comprising at least one kind of the compound represented by the following general formula (I),
10 to 80 mol% of the whole is contained as a constitutional unit comprising at least one kind of the compound represented by the following general formula (II), and 1 to 40 mol% of the whole polymer is represented by the following general formula (II).
The compound represented by I) is contained as a constitutional unit consisting of at least one kind and has a polystyrene-equivalent weight average molecular weight of 1 × 10 ³ or more and 5 × 10 ⁶ or less, a high refractive index, and excellent transparency and heat resistance. The present invention relates to a resin and an optical component made of the resin.

[0010]

[Chemical 4] (Here, R ₁ represents an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms)

[0011]

[Chemical 5] (Here, R ₂ , R ₃ and R ₄ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms)

[0012]

[Chemical 6] (Here, R ₅ is hydrogen or a methyl group, R _{6 to} R ₁₀ are 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 radical copolymerization reaction of N-alkyl-substituted maleimides, olefins and (meth) acrylic acid esters.

The compounds giving the structural unit (I) are N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn.
-Butyl maleimide, N-i-butyl maleimide, N-
s-Butyl maleimide, Nt-butyl maleimide, N
-N-pentyl maleimide, N-n-hexyl maleimide, N-n-heptyl maleimide, N-n-octyl maleimide, N-lauryl maleimide, N-stearyl maleimide, N-cyclopropyl maleimide, N-cyclobutyl maleimide, N N-alkyl-substituted maleimides such as -cyclohexylmaleimide, and from the viewpoint of heat resistance, maleimides having 1 to 6 carbon atoms, particularly N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide and N-cyclohexylmaleimide are preferable. .. These can be used alone or in combination of two or more.

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

As the compound giving the structural unit (III), phenyl acrylate, 4-methylphenyl acrylate, chlorophenyl acrylate, dichlorophenyl acrylate, trichlorophenyl acrylate, bromophenyl Acrylate, dibromophenyl acrylate, tribromophenyl acrylate, benzyl acrylate, 2- (tribromophenoxy) ethyl acrylate, phenylthiol acrylate, phenyl methacrylate, 4 -Methylphenyl methacrylate, chlorophenyl methacrylate, dichlorophenyl methacrylate, trichlorophenyl methacrylate, bromophenyl methacrylate, dibromophenyl methacrylate
And 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 preferable. If the content of the structural unit (I) exceeds 90 mol%, the resulting polymer becomes brittle and is not preferable, and if it is less than 20 mol%, the heat resistance of the resulting polymer decreases, which is not preferable.

The content of the structural unit (II) is from 10 to 80 mol% of the whole polymer, preferably from 20 to 80 mol%, particularly preferably from 50 to 75 mol%. Structural unit (II) is 80
If the amount exceeds 10% by mole, the heat resistance of the polymer decreases, and if it is less than 10% by mole, the polymer produced becomes brittle, which is not preferable.

The content of the structural unit (III) depends on the polymer.
1-40 mol% of the total, 3-30 mol%, especially 5
-25 mol% is preferable. When the constituent unit (III) exceeds 40 mol%, the Abbe number of the polymer produced is low and the polymer produced becomes brittle, which is not preferable, and when it is less than 1 mol%, the refraction of the polymer produced It is not preferable because the rate decreases.

If necessary, other vinyl monomers can be copolymerized within the range not impairing the object of the present invention. Other vinyl monomers include styrene and 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 acid esters such as cyclohexyl acrylate, vinyl acetates such as vinyl acetate and vinyl benzoate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, vinyl chloride, vinyl chloride, Vinylidene chloride, maleic anhydride, N
-Phenylmaleimide, N- (2-methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-chlorophenyl) maleimide, N-carboxyphenylmaleimide, acrylonitrile Can be mentioned.

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

Examples of the polymerization initiator include benzoylperoxide, laurylperoxide, octanoylperoxide, acetylperoxide, di-t-butylperoxide, t-butylcumylperoxide, dicumylperoxide, t-butylperoxyacetate.
, An organic peroxide such as t-butyl peroxybenzoate, perbutyl neodecaneate, 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. The azo initiators of

Solvents usable in the solution polymerization method include benzene, toluene, xylene, ethylbenzene,
Cyclohexane, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide,
Examples include isopropyl alcohol and butyl alcohol.

The polymerization temperature can be appropriately set according to the decomposition temperature of the initiator, but it is generally preferably carried out 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 residual monomer exceeds 3% by weight. In this case, the obtained polymer tends to be colored, which is not preferable.

Here, the weight average molecular weight (Mw) of the resin produced is determined by gel permeation chromatography.
(GPC). The resin of the present invention has a molecular weight of 1 × 10 ³ or more and 5 × 10 ⁶ or less, particularly 1 × 10 3.
It is preferably ⁴ or more and 5 × 10 ⁵ or less. Molecular weight is 5 ×
When it exceeds 10 ⁶ , the moldability becomes poor and 1 × 10 ³
If it is less than the range, the resin obtained tends to become brittle.

In the resin obtained in the present invention, if necessary, a heat stabilizer such as hindered phenol or organic phosphate, a benzotriazole type ultraviolet absorber, a hindered amine type ultraviolet stabilizer, Various lubricants, dyes, etc. may be added. Further, another resin compatible with this can 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.

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

When the refractive index is less than 1.53, there is a problem that the thickness of the spectacle lens for correction becomes thick, and when the Abbe number is less than 35, chromatic aberration becomes large and eyes are tired. It is not preferable because of the problem. When the glass transition temperature of the obtained polymer is less than 100 ° C., the heat resistance is insufficient and the use is limited. On the other hand, when the degree of yellowness exceeds 5, the transparency and appearance of the optical component obtained are inferior, which is not preferable.

Optical parts include spherical and aspherical lenses such as compact disc lenses, video lenses, and camera lenses, optical lenses such as spectacle lenses, optical fibers, substrates for optical disks and optical cards, and prisms. , Automotive light such as headlight lens, fog light lens, turn lens, and brake lamp lens, signal lens, and lighting parts.

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

Hard coating was applied to the obtained molded product.
It is also possible to carry out a treatment such as an antireflection coat.

[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 is GPC (Tohso
It calculated | required by polystyrene conversion using (Co., Ltd. product HLC-802A).

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

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

The obtained polymer was pelletized by Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) and a test piece was molded by using a small injection molding machine (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 reflection plate x: 79.44, y). : 8
2.22, z: 94.51).

Example 1 N-methylmaleimide (392 g) and trichlorophenylmethacrylate (9) were added to a 10 l autoclave equipped with a stirrer, a nitrogen inlet pipe, an isobutene inlet pipe, a thermometer and a degassing pipe.
After 37 g, perbutyl neodecane 3 g and dioxane 5 l were charged and purged several times with nitrogen, liquefied isobutene 2.8 l was charged and reacted at 60 ° C. for 5 hours.

The reaction contents were poured into ethanol and polymerized.
Was deposited. The obtained polymer was purified by reprecipitation with chloroform-ethanol and then 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, the maleimide unit in the produced polymer was 42.3 mol%, the trichlorophenyl methacrylate unit was 7.9 mol%, and the isobutene unit was Is 49.8 mol%
Met. The obtained polymer has a molecular weight (Mw) of 5300.
It was 0. The characteristic evaluation results are shown in Table 1.

Example 2 N-methylmaleimide 392 was placed in the same apparatus as in Example 1.
g, 1408 g of tribromophenyl methacrylate, 3 g of perbutyl neodecane and 5 l of dioxane were charged and purged several times with nitrogen, and then liquefied isobutene 2.8.
1 was charged and the reaction was carried out at 60 ° C. for 5 hours.

The reaction contents were poured into ethanol and polymerized.
Was deposited. The obtained polymer was purified by reprecipitation with chloroform-ethanol and then 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, the maleimide unit in the produced polymer was 32.7 mol%, the tribromophenyl methacrylate unit was 21.5 mol%, and isobutene was The unit was 45.8 mol%. The obtained polymer has a molecular weight (Mw) of 540.
It was 00. The characteristic evaluation results are shown in Table 1.

Example 3 An N-methylmaleimide 314 was placed in the same apparatus as in Example 1.
g, tribromophenyl methacrylate 782 g, per
Butyl neodecaneate (1.5 g) and dioxane (5 l) were charged, and after purging with nitrogen several times, liquefied isobutene was added.
3 l was charged and the reaction was carried out at 60 ° C. for 5 hours.

The reaction contents were poured into ethanol and polymerized.
Was deposited. The obtained polymer was purified by reprecipitation with chloroform-ethanol and then 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, the maleimide unit in the produced polymer was 38.5 mol%, the tribromophenyl methacrylate unit was 11.6 mol%, and isobutene was The unit was 49.9 mol%. The obtained polymer has a molecular weight (Mw) of 540.
It was 00. The characteristic evaluation results are shown in Table 1.

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.)
The same measurement was performed by using.

[0049]

[Table 1]

[0050]

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

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G02B 1/04 7132-2K

Claims (2)

[Claims] 1. A polymer comprising 20 to 90 mol% of the whole polymer as a constitutional unit comprising at least one kind of a compound represented by the following general formula (I), and 10 to 80 mol% of the whole polymer of the following general formula ( II) as a constitutional unit consisting of at least one kind of the compound,
To 40 mol% as a constitutional unit consisting of at least one kind of the compound represented by the following general formula (III), and having a polystyrene-equivalent weight average molecular weight of 1 × 10 ³ or more and 5 × 1.
0 ⁶ or less thermoplastic resin. [Chemical 1] (Here, R ₁ represents an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms) (Here, R ₂ , R ₃ and R ₄ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms) (Here, R ₅ is hydrogen or a methyl group, R _{6 to} R ₁₀ are 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
₂ O-, n is an integer of 0 to 4) 2. An optical component made of the resin according to claim 1.