JPH1036596A - Synthetic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a synthetic resin composition excellent in transparency, heat resistance, fluidity and weather resistance and suitable for optical materials, etc., by including a synthetic resin and a copolymer obtained by copolymerizing with a monomer component containing a specific vinylcycloalkane and an unsaturated dicarboxylic acid derivative. SOLUTION: This resin composition comprises (A) a synthetic resin such as polymethyl methacrylate or polystyrene and (B) a copolymer obtained by copolymerizing a monomer component containing a vinylcycloalkane of the formula [R1 is H or methyl; R2 is a (substituted) >=3C cycloalkyl], e.g. vinylcyclopropane and an unsaturated dicarboxylic acid derivative such as N-phenylmaleimide. Furthermore, a blend ratio of these components A/B is preferably (10/90) to (90/10) and a ratio of vinylcycloalkane in the monomer component is preferably 10-75wt.% and a ratio of an unsaturated dicarboxylic acid derivative therein is preferably 25-90%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin composition suitable as, for example, an optical material for an optical lens or an optical disk substrate.

[0002]

2. Description of the Related Art Conventionally, various thermoplastic resin compositions (synthetic resin compositions) suitable as optical materials for optical lenses, optical disk substrates and the like have been proposed. For example, JP-A-63-43910 and JP-A-64-1706 disclose molding materials such as an optical disk substrate made of a vinylcyclohexane polymer obtained by hydrogenating polystyrene. JP-A-1-132603 discloses a vinylcyclohexane-based copolymer obtained by hydrogenating a copolymer of maleic anhydride and styrene, and a copolymer of methyl methacrylate, styrene and maleimide. An optical material comprising a vinylcyclohexane-based copolymer obtained by hydrogenation is disclosed.

[0003]

However, the above-mentioned conventional thermoplastic resin composition has a problem that the transparency, heat resistance, fluidity and weather resistance required when used as an optical material are insufficient. Have. Therefore, a thermoplastic resin composition excellent in transparency, heat resistance, fluidity, and weather resistance, that is, a synthetic resin composition, is required.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has as its object to provide excellent transparency, heat resistance, fluidity, and weather resistance, for example, as an optical material for an optical lens or an optical disk substrate. It is to provide a suitable synthetic resin composition.

[0005]

In general, it is very rare that different polymers are mixed at a molecular level to form a transparent mixture (composition), that is, compatible. Therefore, conventionally, only a specific combination of polymers has been found. On the other hand, the present inventors have found that a copolymer obtained by copolymerizing a monomer component containing a vinylcycloalkane and an unsaturated dicarboxylic acid derivative,
It was found that the composition was excellent in compatibility with the synthetic resin, and the resulting composition was excellent in transparency, heat resistance, fluidity, and weather resistance.

In other words, the present inventors have conducted intensive studies on synthetic resin compositions in order to solve the above-mentioned conventional problems, and as a result, have found that synthetic resins and vinylcycloalkanes and unsaturated dicarboxylic acid derivatives having specific structures have been synthesized. Synthetic resin composition containing a copolymer obtained by copolymerizing a monomer component containing, transparency, heat resistance, fluidity and weather resistance is found to be excellent, to complete the present invention Reached.

That is, in order to solve the above problems, the synthetic resin composition of the present invention comprises a synthetic resin and a compound represented by the general formula (1):

[0008]

Embedded image

Wherein R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a cycloalkyl group having 3 or more carbon atoms which may have a substituent; And a copolymer obtained by copolymerizing a monomer component containing an unsaturated dicarboxylic acid derivative.

According to the above construction, the synthetic resin composition comprises:
It contains a copolymer obtained by copolymerizing a monomer component containing a vinylcycloalkane having a specific structure and an unsaturated dicarboxylic acid derivative. Thereby, a synthetic resin composition having excellent transparency, heat resistance, fluidity, and weather resistance can be provided. The above synthetic resin composition can be suitably used, for example, as an optical material for an optical lens, an optical disk substrate, various optical components, and the like.

Hereinafter, the present invention will be described in detail. The synthetic resin composition according to the present invention is a copolymer obtained by copolymerizing a synthetic resin and a monomer component containing a vinylcycloalkane represented by the general formula (1) and an unsaturated dicarboxylic acid derivative (hereinafter, referred to as a copolymer). Simply referred to as a copolymer).

The above synthetic resin is not particularly limited, and all conventionally known synthetic resins, that is, thermoplastic resins and thermosetting resins can be employed. As the thermoplastic resin, specifically, for example, polymethyl methacrylate, polystyrene, AS (acrylonitrile-styrene) resin, polycarbonate and the like are particularly suitable. As the thermosetting resin, specifically, for example, an epoxy resin, an unsaturated polyester resin, an alkyd resin, a polyurethane or the like is suitable. In addition, only one type of synthetic resin may be used, or two or more types may be used in combination.

In the vinylcycloalkane represented by the general formula (1), the substituent represented by R ₁ is a hydrogen atom or a methyl group, and the substituent represented by R ₂ is further substituted. Any cycloalkyl group having 3 or more carbon atoms which may have a substituent may be used, and is not particularly limited.
Compounds having 8 or less carbon atoms in the cycloalkyl group are more preferred.

Specific examples of the vinylcycloalkane include, for example, vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, isopropenylcyclohexane,
Each isomer of vinylmethylcyclohexane, each isomer of vinylbutylcyclohexane, each isomer of vinyldimethylcyclohexane, each isomer of vinylchlorocyclohexane, and the like. One of these vinylcycloalkanes may be used alone, or two or more thereof may be used in combination. Among the compounds exemplified above, vinylcyclohexane is more preferred. The proportion of vinylcycloalkane in the monomer component is preferably in the range of 5% by weight to 95% by weight, and more preferably in the range of 10% by weight to 75% by weight. If the proportion of vinylcycloalkane is out of the above range, it is not preferable because a synthetic resin composition having excellent transparency, heat resistance, fluidity and weather resistance cannot be obtained.

The above unsaturated dicarboxylic acid derivatives include maleic anhydride and maleimide monomers. As the maleimide-based monomer, specifically,
For example, maleimide; N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (methylphenyl) maleimide,
N-substituted maleimides such as N- (methoxyphenyl) maleimide, N- (carboxyphenyl) maleimide, N-cyclohexylmaleimide, N- (chlorophenyl) maleimide, and N- (bromophenyl) maleimide;

One of these unsaturated dicarboxylic acid derivatives may be used alone, or two or more of them may be used in combination. Among the compounds exemplified above, N-phenylmaleimide and N-cyclohexylmaleimide are more preferable from the viewpoints of availability, economy, and the like. The proportion of the unsaturated dicarboxylic acid derivative in the monomer component is from 5% by weight to 9% by weight.
Preferably in the range of 5% by weight, 25% to 90% by weight
Is more preferable. When the proportion of the unsaturated dicarboxylic acid derivative is outside the above range, transparency, heat resistance,
It is not preferable because a synthetic resin composition having excellent fluidity and weather resistance cannot be obtained.

The above monomer component may contain a vinylcycloalkane and an unsaturated dicarboxylic acid derivative. If necessary, other vinyl monomers which can be copolymerized with these monomers may be used. (Hereinafter, referred to as a vinyl monomer). As the vinyl monomer, specifically, for example, acrylic acid, methacrylic acid, itaconic acid, acrylonitrile, methacrylonitrile; methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate,
Alkyl acrylates such as cyclohexyl acrylate, methyl cyclohexyl acrylate, tert-butylcyclohexyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, Alkyl methacrylates such as methylcyclohexyl methacrylate and t-butylcyclohexyl methacrylate; α-olefins such as ethylene, propylene, isobutene and 4-methyl-1-pentene; diolefins such as butadiene and isoprene; However, there is no particular limitation. One of these vinyl monomers may be used alone, or two or more thereof may be used in combination. The type and amount of the vinyl monomer may be appropriately set according to the desired physical properties and the like of the synthetic resin composition to be obtained.

The method of copolymerizing the monomer components is not particularly limited, and conventionally known polymerization methods, for example,
Bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like can be employed.

When copolymerizing the monomer components, a solvent can be used if necessary. The solvent is not particularly limited as long as it is a compound capable of dissolving the monomer component. As the solvent, specifically, for example, saturated hydrocarbons such as hexane, heptane, octane, and cyclohexane; butyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol,
Alcohols such as decyl alcohol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and ethyl benzene;
Halogenated hydrocarbons such as chloroform and carbon tetrachloride; and the like. These solvents may be used alone or as a mixture of two or more. Among the solvents exemplified above, aromatic hydrocarbons are more preferred. The amount of the solvent used may be appropriately set according to the composition of the monomer component, the reaction conditions, and the like, and is not particularly limited.

When copolymerizing the monomer components, a polymerization initiator is used. As the polymerization initiator, specifically, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, p-menthane hydroperoxide, lauroyl peroxide, benzoyl peroxide,
t-butyl peroxy isopropyl carbonate,
1,1-bis (t-butylperoxy) -3,3,5-
Organic peroxides such as trimethylcyclohexane, di-t-butylperoxy hexahydroterephthalate, t-butylperoxy-2-ethylhexanoate; ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, etc. Inorganic peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-
Radical polymerization initiators such as 2,4-dimethylvaleronitrile), azo compounds such as 1,1′-azobis (cyclohexane-1-carbonitrile) and azobenzene; and the like, but are not particularly limited. One of these polymerization initiators may be used alone, or two or more thereof may be used in combination. Further, the peroxide, a sulfite,
A redox initiator can also be used in combination with a reducing agent such as bisulfite, thiosulfate, formamidine sulfinic acid, and ascorbic acid. The amount of the polymerization initiator to be used may be appropriately set according to the composition of the monomer component, the reaction conditions, and the like, and is not particularly limited.

The reaction conditions for copolymerizing the monomer component may be appropriately set according to the composition of the monomer component and the like.
Although not particularly limited, the reaction temperature is 90 ° C.
A temperature in the range of 150 ° C. is preferred. The reaction time may be appropriately set according to the composition of the monomer components, the amount of the polymerization initiator used, the reaction temperature, and the like, but is preferably about 1 hour to 24 hours. In order to remove the copolymer from the solvent, that is, the reaction solution, for example, the reaction solution is poured into a large excess of alcohol to precipitate the copolymer, a so-called alcohol coagulation method; A so-called desolvation method;

The copolymer according to the present invention is obtained by copolymerizing the above monomer components. The obtained copolymer has a glass transition temperature (Tg) of preferably 120 ° C.
-250 ° C, more preferably 150 ° C-220 ° C, and is compatible with the synthetic resin. That is, the copolymer has compatibility with the synthetic resin. The weight average molecular weight (Mw) of the copolymer is preferably in the range of 1,000 to 500,000, and more preferably in the range of 1,000 to 100,000. If the weight average molecular weight is outside the above range, it is not preferable because a synthetic resin composition having excellent transparency, heat resistance, fluidity and weather resistance cannot be obtained.

The synthetic resin composition contains the above synthetic resin and a copolymer. That is, the synthetic resin composition according to the present invention can be obtained by mixing the synthetic resin and the copolymer. The method of mixing the synthetic resin and the copolymer is not particularly limited.For example, after dissolving the synthetic resin and the copolymer in an appropriate solvent, the solution is poured into a large excess of alcohol. In this case, a so-called alcohol coagulation method in which a mixture is precipitated by mixing the mixture, a so-called kneading method in which a synthetic resin and a copolymer are kneaded using an extruder, and the like may be used. Since the synthetic resin and the copolymer are compatible,
By forming the mixture, the two are uniformly mixed.

The solvent is not particularly limited as long as it is a compound capable of dissolving the synthetic resin and the copolymer. Specific examples of the solvent include the solvents exemplified above. The weight ratio of the synthetic resin to the copolymer (synthetic resin / copolymer) is from 1/99 to 99.
/ 1, preferably in the range of 10/90 to 90/10. If the weight ratio is outside the above range, it is not preferable because a synthetic resin composition having excellent transparency, heat resistance, fluidity and weather resistance cannot be obtained.

In addition, the synthetic resin composition may be used, if necessary,
It may contain various additives such as an antioxidant, a release agent, a plasticizer, a fluidity improver, a heat stabilizer, a light fastness stabilizer, an antistatic agent, and a colorant. In addition, the addition amount of these additives is not particularly limited.

As described above, the synthetic resin composition according to the present invention is obtained by copolymerizing the synthetic resin with a monomer component containing the vinylcycloalkane represented by the general formula (1) and the unsaturated dicarboxylic acid derivative. And a copolymer comprising:

According to the above configuration, since the synthetic resin composition contains a copolymer, it is excellent in transparency, heat resistance, fluidity and weather resistance. The above synthetic resin composition can be suitably used, for example, as an optical material for an optical lens, an optical disk substrate, various optical components, and the like. The synthetic resin composition can be easily molded by a known molding method such as extrusion molding, injection molding, and compression molding.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, "parts" means "parts by weight".
Is shown.

Example 1 A 1 L flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer, and a stirrer was used as a reaction vessel. In this reaction vessel, 12.5 parts of vinylcyclohexane as a vinylcycloalkane, 12.5 parts of N-cyclohexylmaleimide as an unsaturated dicarboxylic acid derivative (maleimide monomer), 75 parts of toluene as a solvent, and polymerization Kayacaron BIC-75 as an initiator (trade name; manufactured by Kayaku Akzo Co., Ltd.)
After charging 0.33 parts, the system was replaced with nitrogen gas. Therefore, the monomer component is composed of vinylcyclohexane and N-cyclohexylmaleimide.

Then, the content was heated to 110 ° C. while stirring the above contents under a nitrogen gas stream, and a polymerization reaction was carried out for 8 hours while maintaining the temperature. After the completion of the reaction, the reaction solution is cooled, and the reaction solution is poured into a large excess of methyl alcohol, whereby the copolymer (vinylcyclohexane-N-
(Cyclohexylmaleimide copolymer). Thereafter, the copolymer was filtered out and dried.

The obtained copolymer was 14.3 parts, and as a result of an elemental analysis, it contained 79% by weight of a structural unit composed of N-cyclohexylmaleimide. FIG. 1 shows a chart of the infrared absorption spectrum of the copolymer. FIG. 2 shows a ¹ H-NMR chart of the copolymer. And
As a result of measuring GPC (gel permeation chromatography), the weight average molecular weight (Mw) of the copolymer was determined.
Was 5,000 in terms of polystyrene. As a result of thermal analysis, the glass transition temperature of the copolymer was 19
1 ° C.

Next, 50 parts of the above-mentioned copolymer and 50 parts of polystyrene (manufactured by Sumitomo Chemical Co., Ltd .; trade name: ESBRITE) as a synthetic resin (thermoplastic resin) were mixed with a predetermined amount of a solvent. Dissolved in methyl ethyl ketone. The mixture was then precipitated by pouring the solution into a large excess of methyl alcohol. Thereafter, the mixture was filtered out and dried. Thus, a synthetic resin composition according to the present invention was obtained.

As a result of a thermal analysis, the glass transition temperature of the obtained synthetic resin composition was 120 ° C. Further, the glass transition temperature of the copolymer (191 ° C.) and the glass transition temperature of polystyrene (100 ° C.) were not observed. From this, it was found that in the synthetic resin composition, the polystyrene and the copolymer were compatible and both were uniformly mixed.

Further, a film made of the synthetic resin composition was prepared by dissolving the synthetic resin composition in chloroform so as to have a predetermined concentration, and casting (coating) the obtained chloroform solution on a glass plate. The obtained film was colorless and transparent, and was excellent in transparency, heat resistance, weather resistance and fluidity.

Example 2 In Example 1, the amount of the copolymer dissolved in methyl ethyl ketone was changed from 50 parts to 20 parts.
Parts and change the amount of polystyrene from 50 parts to 8 parts.
A synthetic resin composition according to the present invention was obtained by performing the same reaction and operation as in Example 1 except that the amount was changed to 0 parts.

As a result of a thermal analysis, the glass transition temperature of the obtained synthetic resin composition was 110 ° C. Further, the glass transition temperature of the copolymer and the glass transition temperature of polystyrene were not observed. From this, it was found that in the synthetic resin composition, the polystyrene and the copolymer were compatible and both were uniformly mixed.

Further, a film made of the synthetic resin composition was prepared by performing the same operation as in Example 1. The obtained film was colorless and transparent, and was excellent in transparency, heat resistance, weather resistance and fluidity.

Example 3 In Example 1, the amount of the copolymer dissolved in methyl ethyl ketone was changed from 50 parts to 20 parts.
Parts and polymethyl methacrylate as synthetic resin (thermoplastic resin) (manufactured by Mitsubishi Rayon Co., Ltd .; trade name: Acrypet) instead of 50 parts of polystyrene
A synthetic resin composition according to the present invention was obtained by performing the same reaction and operation as in Example 1 except that 80 parts were used.

As a result of a thermal analysis, the glass transition temperature of the obtained synthetic resin composition was 120 ° C. Further, the glass transition temperature of the copolymer and the glass transition temperature (110 ° C.) of polymethyl methacrylate were not observed. From this, it was found that in the synthetic resin composition, polymethyl methacrylate and the copolymer were compatible and both were uniformly mixed.

Further, a film made of a synthetic resin composition was prepared by performing the same operation as in Example 1. The obtained film was colorless and transparent, and was excellent in transparency, heat resistance, weather resistance and fluidity.

[0041]

As described above, the synthetic resin composition of the present invention comprises a synthetic resin and a compound represented by the general formula (1)

[0042]

Embedded image

(Wherein R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a cycloalkyl group having 3 or more carbon atoms which may have a substituent); And a copolymer obtained by copolymerizing a monomer component containing an unsaturated dicarboxylic acid derivative.

As a result, there is an effect that a synthetic resin composition having excellent transparency, heat resistance, fluidity and weather resistance can be provided. The above synthetic resin composition can be suitably used, for example, as an optical material for an optical lens, an optical disk substrate, various optical components, and the like.

[Brief description of the drawings]

FIG. 1 is a chart of an infrared absorption spectrum of a copolymer obtained in one example of the present invention.

FIG. 2 is a ¹ H-NMR chart of the copolymer.

Claims (1)

[Claims] 1. A synthetic resin having the general formula (1): (In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂
Represents a cycloalkyl group having 3 or more carbon atoms which may have a substituent) and a copolymer obtained by copolymerizing a monomer component containing a vinylcycloalkane and an unsaturated dicarboxylic acid derivative. A synthetic resin composition comprising: