JP2002003547A - Acenaphthylene derivative-containing copolymer, and molding material, sheet or film and optical part obtained by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is excellent in heat resistance and optical characteristics as well as a low hygroscopic property and low permittivity. SOLUTION: This acenaphthylene-containing copolymer is a graft copolymer having the weight average molecular weight of 3×104 or less and consisting of a polymer (A) comprising at least one kind of acenaphthylene derivative shown by formula (I) and a polymer (B) having a glass transition temperature below that of the polymer (A), and is characterized that the polymer (B) consists of styrene or a styrene derivative and a monomer copolymerizable with the same. (In the formula, R1, R2, R3, R4, R5 or R6, which may be the same or different, shows a hydrogen atom; univalent hydrocarbon group containing a nitrogen atom, oxygen atom or silicon atom; 1-6 alkyl group; univalent aromatic hydrocarbon group; halogen atom; acyl group; alkoxy group; nitrile group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having low moisture absorption, low dielectric constant, excellent heat resistance, and excellent optical properties.

[0002]

2. Description of the Related Art Many monomers having an unsaturated bond having a reactive activity can be produced in a multimer by selecting a catalyst capable of cleaving the unsaturated bond to cause a chain reaction and selecting appropriate reaction conditions. it can. In general, the types of monomers having an unsaturated bond are extremely diverse, and the variety of resins obtained is remarkable. However, there are relatively few types of monomers from which a high molecular weight compound having a molecular weight of 10,000 or more, generally called a high molecular compound, can be obtained. For example, ethylene, substituted ethylene, propylene, substituted propylene, styrene, alkylstyrene, alkoxystyrene, norbornene,
Various acrylic esters, butadiene, cyclopentadiene, dicyclopentadiene, isoprene, maleic anhydride, maleimide, fumaric acid esters, allyl compounds and the like can be mentioned as typical monomers. A wide variety of resins have been synthesized from these monomers or various combinations.

[0003] The applications of these resins are mainly limited to the field of relatively inexpensive consumer appliances, and there is almost no application to high-tech fields such as semiconductor-related materials. The reason is that heat resistance, low hygroscopicity, and dielectric constant cannot be achieved at the same time.

For example, in the field of semiconductor-related materials, it has been desired to reduce the dielectric constant in addition to the conventional heat resistance and low moisture absorption due to the recent increase in the degree of integration. In order to achieve a low dielectric constant, it is in principle essential to reduce the amount of polar groups in the resin. At present, polyimide is often used as a resin for semiconductors. However, at present, it is difficult to reduce the dielectric constant because the resin skeleton contains many carbonyl groups. As a countermeasure, research using a monomer containing fluorine has been actively conducted, but it cannot be said that a sufficiently low dielectric constant has been achieved. There are also problems such as an increase in resin price and complicated synthesis.

[0005] As another method, synthesis of a polymer comprising a hydrocarbon containing no polar group has been attempted. For example, a group of polymers called cyclic polyolefins can be mentioned. Specifically, a polymer obtained by hydrogenating polynorbornene or a polymer comprising polydicyclopentene and a derivative thereof can be given. Although it is possible to realize an extremely low dielectric constant of these polymers, there are problems in that heat resistance is low and water permeability is extremely high although water absorption is extremely low. In particular, high water permeability is a characteristic common to polyolefins, and it is considered to be extremely difficult to solve this.

Other methods include syndiotactic polystyrene synthesized using a Ziegler-Natta or Kaminsky catalyst. This polymer has a structure in which the steric position of the benzene ring with respect to the main chain is alternately located in the opposite direction, achieving extremely high heat resistance, and at the same time, extremely low water absorption and water permeation. Very low levels of properties as well as dielectric constant can be achieved. However, this polymer has a disadvantage that adhesion to a substrate is extremely poor because of its extremely high crystallinity, and there is a problem that the processing method is extremely limited because it is not dissolved in any solvent. That is, a polymer that can solve the above-mentioned problems has not yet been developed.

On the other hand, polymers used for optical lenses and optical waveguide materials for optical applications include acrylic resins and polyolefin resins. Acrylic resins are characterized by excellent transparency and processability and extremely low birefringence. However, there are disadvantages such as high hygroscopicity, relatively low heat resistance, and low toughness. In contrast, polyolefin-based resins have excellent heat resistance and extremely low hygroscopicity, but transparency and low birefringence are inferior to those of acrylic resins. That is, both acrylic resin and polyolefin resin have advantages and disadvantages, and there is a strong demand for the development of a resin that complements the disadvantages of acrylic resin and polyolefin resin.

Therefore, many studies have been made to improve the acrylic resin, that is, to solve the drawbacks of high hygroscopicity and low heat resistance. For example, a method of improving hygroscopicity and heat resistance by using a monomer having a bulky substituent (Japanese Patent Application No. 8-199901,
Japanese Patent No. 2678029). Although the present invention has certain effects, it does not reach the low moisture absorption rate of the polyolefin resin. A further drawback is that the presence of bulky substituents on the side chains results in a marked decrease in toughness and strength, and in particular, susceptibility to breakage during molding. For the purpose of improving this, there is a method that attempts to impart toughness by copolymerizing a monomer that imparts flexibility, but a decrease in heat resistance cannot be avoided, and a bulky substituent has been introduced. The effect diminishes.

Polyolefin resins are extremely advantageous as optical resins because of their low hygroscopicity and high heat resistance. However, with the advancement of optical equipment in recent years, high birefringence is a major disadvantage. Attempts to reduce the birefringence of polyolefin resins have recently been particularly active.

For example, JP-A-8-110402 can be mentioned. The present invention attempts to offset the birefringence inherent in a polyolefin-based resin by mixing a resin or a low-molecular compound having a birefringence of the opposite sign to the birefringence of the polyolefin resin, thereby reducing the birefringence of the resin mixture to zero. Is what you do. In this method, it is necessary that the resin to be mixed and the polyolefin resin are completely compatible. However, in the above invention, the compatibility between the polyolefin-based resin and the claimed resin is insufficient, and a sufficient effect is not exhibited. At present, no resin or additive having a birefringence sign opposite to that of the polyolefin resin and capable of being completely compatible with each other has been found.

Therefore, a method of adding a compatibilizing agent as a third component has been carried out as a polymer alloying technique for the purpose of making the compatibilization as complete as possible, and specifically, this is described in US Pat. No. 4,373,065. ing. In order to mix them with high uniformity, they must be in a molten state or a solution state.However, using any physical method, obtain a practical polymer material with high uniformity and no overall birefringence Is extremely difficult. Further, attempts have been made to achieve complete compatibility by using the third component, but no material has yet been found that can achieve this purpose.

[0012]

SUMMARY OF THE INVENTION The present invention solves the above problems and provides a resin composition which has low moisture absorption and low dielectric constant, and is excellent in heat resistance, optical properties and workability.

[0013]

SUMMARY OF THE INVENTION The present invention is as follows. (1) A polymer (A) composed of at least one kind of acenaphthylene derivative represented by the following general formula (I), and a polymer (B) having a glass transition point equal to or lower than the glass transition point of the polymer (A). A graft copolymer having a weight average molecular weight of 3 × 10 ⁴ or more, and a polymer (B)
Is an acenaphthylene derivative-containing copolymer comprising styrene or a styrene derivative and a monomer copolymerizable therewith.

[0014]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ may be the same or different, and represent a hydrogen atom; a monovalent containing a nitrogen atom, an oxygen atom or a silicon atom. Hydrocarbon group; carbon number 1
Alkyl groups of 6 to 6; monovalent aromatic hydrocarbon groups; halogen atoms; acyl groups; alkoxy groups; (2) The polymer (B) is styrene, a nuclear-substituted alkylstyrene, a nuclear-substituted aromatic styrene, an α-substituted alkylstyrene, a β-substituted alkylstyrene, a nuclear-substituted alkoxystyrene, an alkyl vinyl ether, an aromatic vinyl ether, isobutene (1) The acenaphthylene derivative-containing copolymer according to (1), comprising at least one selected from the group consisting of diisobutylene, aromatic (meth) acrylate and alkyl (meth) acrylate. (3) The polymer (B) has a weight average molecular weight of 1 × 10
The acenaphthylene derivative-containing copolymer according to (1) or (2), which is not more than ⁴ . (4) The polymer (B) according to any one of (1) to (3), wherein a weight fraction of the total weight of the polymer (A) and the polymer (B) is 50% or less. Such an acenaphthylene derivative-containing copolymer. (5) The acenaphthylene derivative-containing copolymer according to any one of (1) to (4), wherein the polymer (A) is a random copolymer. (6) A molded material obtained by molding the acenaphthylene derivative-containing copolymer according to any one of (1) to (5). (7) A sheet obtained from the acenaphthylene derivative-containing copolymer according to any one of the above (1) to (5). (8) A film obtained from the acenaphthylene derivative-containing copolymer according to any one of the above (1) to (5). (9) An optical component using the molding material, sheet or film according to (6) to (8).

[0015]

Next, the acenaphthylene derivative-containing copolymer which is the graft copolymer of the present invention will be described in detail.

The acenaphthylene derivative-containing copolymer of the present invention comprises a polymer (A) comprising at least one of the acenaphthylene derivatives represented by the general formula (I) and a glass transition point of the polymer (A) or lower. It is a graft copolymer comprising a polymer (B) having a glass transition point.

In the above general formula (I) representing the acenaphthylene derivative used in the polymer (A), R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ and R ₆ may be the same or different,
A hydrogen atom; a monovalent hydrocarbon group containing a nitrogen atom, an oxygen atom or a silicon atom; an alkyl group having 1 to 6 carbon atoms; a monovalent aromatic hydrocarbon group; a halogen atom; an acyl group; an alkoxy group; Represents a group.

The monovalent hydrocarbon group containing a nitrogen atom, an oxygen atom or a silicon atom includes, for example, dimethylaminoethyl group, diethylaminoethyl group, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group,
Examples include a hexoxy group, a dimethylsilyl group, and a diethylsilyl group.

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, a 2-methylbutyl group and a 3-methylbutyl group. Methylbutyl group, t-pentyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethyl Butyl group, 2,4-dimethylbutyl group,
Examples include a 3,3-dimethylbutyl group, a 3,4-dimethylbutyl group, a 4,4-dimethylbutyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, and a cyclohexyl group.

Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a naphthyl group and a benzyl group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group and an isobutyryl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and a hexoxy group.

The above description is merely an example, and the present invention is not limited to these.

As the polymer (A) used for the acenaphthylene derivative-containing copolymer, the above acenaphthylene derivatives can be used alone or in combination of two or more.

As the acenaphthylene derivative having the above substituent, specifically, methyl acenaphthylene is preferably used.

The polymer (B) is not particularly limited as long as it has a glass transition point equal to or lower than the glass transition point of the polymer (A). Styrene, nuclear substituted alkyl styrene, nuclear substituted aromatic styrene, α-substituted alkyl styrene, β-substituted alkyl styrene, nuclear substituted alkoxy styrene, alkyl vinyl ether, aromatic vinyl ether, isobutene, diisobutylene, aromatic (meth) acrylate and alkyl (Meta)
Acrylate and the like can be mentioned.

Examples of the nuclear-substituted alkylstyrene include:
o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-propylstyrene, m-propylstyrene, p-
Propyl styrene, on-butyl styrene, mn-butyl styrene, pn-butyl styrene, o-isobutyl styrene,
m-isobutylstyrene, p-isobutylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, on-pentylstyrene, mn-pentylstyrene, p-
n-pentylstyrene, o-2-methylbutylstyrene, m-2-
Methyl butyl styrene, p-2-methyl butyl styrene, o-
3-methylbutylstyrene, m-3-methylbutylstyrene,
p-3-methylbutylstyrene, ot-pentylstyrene, m-
t-pentylstyrene, pt-pentylstyrene, on-hexylstyrene, mn-hexylstyrene, pn-hexylstyrene, o-2-methylpentylstyrene, m-2-methylpentylstyrene, p-2-methylpentylstyrene, o 3-methylpentylstyrene, m-3-methylpentylstyrene, p-
3-methylpentylstyrene, o-1-methylpentylstyrene, m-1-methylpentylstyrene, p-1-methylpentylstyrene, o-2,2-dimethylbutylstyrene, m-2,2-dimethylbutylstyrene, p-2,2-dimethylbutylstyrene,
o-2,3-dimethylbutylstyrene, m-2,3-dimethylbutylstyrene, p-2,3-dimethylbutylstyrene, o-2,4-dimethylbutylstyrene, m-2,4-dimethylbutylstyrene,
p-2,4-dimethylbutylstyrene, o-3,3-dimethylbutylstyrene, m-3,3-dimethylbutylstyrene, p-3,3-dimethylbutylstyrene, o-3,4-dimethylbutylstyrene,
m-3,4-dimethylbutylstyrene, p-3,4-dimethylbutylstyrene, o-4,4-dimethylbutylstyrene, m-4,4-dimethylbutylstyrene, p-4,4-dimethylbutylstyrene,
o-2-ethylbutylstyrene, m-2-ethylbutylstyrene, p-2-ethylbutylstyrene, o-1-ethylbutylstyrene, m-1-ethylbutylstyrene, p-1-ethylbutylstyrene, o- Cyclohexylstyrene, m-cyclohexylstyrene, p-cyclohexylstyrene and the like can be used. What is shown here is an example and is not limited to these. These may be used alone or in combination of two or more.

Examples of the nucleus-substituted aromatic styrene include, for example, o-
Phenylstyrene, m-phenylstyrene, p-phenylstyrene and the like can be used. What is shown here is an example and is not limited to these.

Examples of the α-substituted alkyl styrene include α-methyl styrene, α-ethyl styrene, α-propyl styrene, α-n-butyl styrene, α-isobutyl styrene, α-t-butyl styrene, α-n- Pentylstyrene, α-2-methylbutylstyrene, α-3-methylbutylstyrene, α-t-butylstyrene, α-t-pentylstyrene, α-n-hexylstyrene, α-2-methylpentylstyrene, α- 3-methylpentylstyrene, α-1-methylpentylstyrene, α-2,2-dimethylbutylstyrene,
α-2,3-dimethylbutylstyrene, α-2,4-dimethylbutylstyrene, α-3,3-dimethylbutylstyrene, α-3,4-
Dimethylbutylstyrene, α-4,4-dimethylbutylstyrene, α-2-ethylbutylstyrene, α-1-ethylbutylstyrene, α-cyclohexylstyrene, and the like can be used. What is shown here is an example and is not limited to these. These may be used alone or in combination of two or more.

Examples of the β-substituted alkylstyrene include β-methylstyrene, β-ethylstyrene, β-propylstyrene, β-n-butylstyrene, β-isobutylstyrene, β-t-butylstyrene, β-n-butylstyrene. Pentylstyrene, β-2-methylbutylstyrene, β-3-methylbutylstyrene, β-t-pentylstyrene, β-n-hexylstyrene, β-2-methylpentylstyrene, β-3-methylpentylstyrene, β 1-methylpentylstyrene, β-2,2-dimethylbutylstyrene, β-2,3-dimethylbutylstyrene, β-2,4-dimethylbutylstyrene, β-3,3-dimethylbutylstyrene, β-3 , 4-dimethylbutylstyrene, β-
4,4-dimethylbutylstyrene, β-2-ethylbutylstyrene, β-1-ethylbutylstyrene, β-cyclohexylstyrene and the like can be used. What is shown here is an example and is not limited to these. These may be used alone or in combination of two or more.

Examples of the nuclear-substituted alkoxystyrene include o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-propoxystyrene, and m-propoxystyrene. , P-propoxystyrene, on-butoxystyrene, mn-butoxystyrene, pn-butoxystyrene, o-isobutoxystyrene, m-isobutoxystyrene, p-isobutoxystyrene, ot-butoxystyrene,
mt-butoxystyrene, pt-butoxystyrene, on-pentoxystyrene, mn-pentoxystyrene, pn-pentoxystyrene, o-2-methylbutoxystyrene, m-2-methylbutoxystyrene, p-2-methylbutoxy styrene,
o-3-methylbutoxystyrene, m-3-methylbutoxystyrene, p-3-methylbutoxystyrene, ot-pentoxystyrene, mt-pentoxystyrene, pt-pentoxystyrene, on-hexoxystyrene, mn- Hexoxystyrene, pn-hexoxystyrene, o-2-methylpentoxystyrene, m-2-methylpentoxystyrene, p-2-methylpentoxystyrene, o-3-methylpentoxystyrene, m-
3-methylpentoxystyrene, p-3-methylpentoxystyrene, o-1-methylpentoxystyrene, m-1-methylpentoxystyrene, p-1-methylpentoxystyrene, o-
2,2-dimethylbutoxystyrene, m-2,2-dimethylbutoxystyrene, p-2,2-dimethylbutoxystyrene, o-2,3-
Dimethylbutoxystyrene, m-2,3-dimethylbutoxystyrene, p-2,3-dimethylbutoxystyrene, o-2,4-dimethylbutoxystyrene, m-2,4-dimethylbutoxystyrene, p-2,4- Dimethylbutoxystyrene, o-3,3-dimethylbutoxystyrene, m-3,3-dimethylbutoxystyrene,
p-3,3-dimethylbutoxystyrene, o-3,4-dimethylbutoxystyrene, m-3,4-dimethylbutoxystyrene, p-3,
4-dimethylbutoxystyrene, o-4,4-dimethylbutoxystyrene, m-4,4-dimethylbutoxystyrene, p-4,4-dimethylbutoxystyrene, o-2-ethylbutoxystyrene, m-2-ethylbutoxy Styrene, p-2-ethylbutoxystyrene, o-1-ethylbutoxystyrene, m-1-ethylbutoxystyrene, p-1-ethylbutoxystyrene, o-cyclohexoxystyrene, m-cyclohexoxystyrene,
p-cyclohexoxystyrene, o-phenoxystyrene,
m-phenoxystyrene, p-phenoxystyrene and the like can be used. What is shown here is an example and is not limited to these. These may be used alone or in combination of two or more.

Examples of the alkyl vinyl ether include methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, t-pentyl, n-hexyl and 2-methylpentyl ,
3-methylpentyl, 4-methylpentyl, 1-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 2,4-dimethylbutyl, 3,3-dimethylbutyl, 3,4-dimethylbutyl, Alkyl vinyl ethers having an alkyl such as 4,4-dimethylbutyl, 2-ethylbutyl, 1-ethylbutyl, cyclohexyl and the like can be mentioned. What is shown here is an example, and the present invention is not limited to these. These may be used alone or in combination of two or more.

Examples of the aromatic vinyl ether include phenyl vinyl ether. What is shown here is an example, and the present invention is not limited to these.

As the aromatic (meth) acrylate, for example, phenyl (meth) acrylate, benzyl (meth) acrylate and the like can be used. What is shown here is an example, and the present invention is not limited to these.

As the alkyl (meth) acrylate,
Ethyl, propyl, n-butyl, isobutyl, t-butyl,
n-pentyl, 2-methylbutyl, 3-methylbutyl, t-pentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-methylpentyl, 2,2-dimethylbutyl, 2,3 -Dimethylbutyl, 2,4-dimethylbutyl,
Examples thereof include alkyl (meth) acrylates having an alkyl such as 3,3-dimethylbutyl, 3,4-dimethylbutyl, 4,4-dimethylbutyl, 2-ethylbutyl, 1-ethylbutyl, and cyclohexyl. What is shown here is an example, and the present invention is not limited to these.

The acenaphthylene derivative-containing copolymer which is a graft copolymer comprising the polymer (A) and the polymer (B) has a weight average molecular weight of 3 × 10 ⁴ or more.
If the weight average molecular weight is less than 3 × 10 ⁴ , sufficient strength may not be secured. More preferably, it is 5 × 10 ⁴ or more.

The polymer (B) preferably has a weight average molecular weight of 1 × 10 ⁴ or less. More preferably, it is 8 × 10 ³ or less. Thereby, the birefringence can be reduced.

In order to make the weight average molecular weight of the acenaphthylene derivative-containing copolymer or polymer (B) of the present invention within the above range, the type and amount of the catalyst used in the synthesis and the use of a polymerization inhibitor can be selected. Or by using a chain transfer agent or adjusting the polymerization temperature.

The weight average molecular weight of the polymer in the present invention can be determined by GPC measurement in a tetrahydrofuran solution.

The polymer (B) has a glass transition point equal to or lower than the glass transition point of the polymer (A).
In order for the polymer (B) to have a glass transition point equal to or lower than the glass transition point of the polymer (A), for example, when producing the polymer (B), a polymer having a low glass transition point may be used. It is possible by selecting and polymerizing a monomer.

Specifically, the preferred glass transition point of the polymer (A) is 110 ° C., more preferably 120 ° C.,
The preferred glass transition point of the polymer (B) is 110 ° C. or less,
The temperature is more preferably 90 ° C or lower.

The glass transition point can be measured as follows.

Evaluation is made by measuring the glass transition point by DSC (differential scanning calorimetry). The DSC measurement is carried out at a rate of temperature rise of 10 ° C./min.

In order to obtain the acenaphthylene derivative-containing copolymer of the present invention, there is no particular limitation as long as the obtained polymer is a graft copolymer. It is obtained by adding a monomer constituting the polymer (B) before the active molecular terminal is deactivated and further polymerizing it before the active molecular terminal is deactivated. Alternatively, conversely, polymerization is carried out using a monomer constituting the polymer (B) by an ordinary method, and a monomer constituting the polymer (A) is added before the terminal of the active molecule is deactivated. Obtained by polymerization.

Specifically, for example, a monomer which can be copolymerized with styrene or a styrene derivative, which has been prepared in advance by radical polymerization or the like, is dissolved in toluene, THF, NMP or the like, and further represented by the general formula (I). After dissolving acenaphthylene or acenaphthylene derivative, tin chloride as a catalyst,
A method of performing cationic polymerization by adding a Lewis acid such as aluminum chloride, and 2,6-bis (t-butyl) pyridine as a co-catalyst, or the like.

Further, after synthesizing a polymer having a functional group such as an acid anhydride, an epoxy group, or a hydroxyl group, a functional group (amino group, hydroxyl group,
A graft polymer can also be obtained by synthesizing a polymer having an epoxy group or the like at the molecular terminal, mixing these two polymers, and reacting them under appropriate reaction conditions.

The polymer (A) is preferably a random copolymer using two or more acenaphthylene derivatives. With this configuration, the acenaphthylene derivative-containing copolymer of the present invention can have reduced crystallinity, thereby increasing transparency.

As a polymerization method for obtaining the polymer (A) and the polymer (B), a usual method is used. For example, the polymer is produced by cationic polymerization, anionic polymerization, radical polymerization, living radical polymerization or the like. be able to. The above polymerization method can be selected depending on the catalyst used.

The catalyst used for the cationic polymerization is not particularly limited, and a known catalyst can be used. For example, Lewis acids such as aluminum chloride, iron chloride, tin chloride, zinc chloride, strontium chloride, and scandium chloride; protic acids such as sulfuric acid, paratoluenesulfonic acid, hydrochloric acid, and nitric acid; and alkyl aluminum chloride can be used. What is shown here is an example, and the present invention is not limited to these. These may be used alone or in combination of two or more.

The catalyst used for the anionic polymerization is not particularly limited, and a known catalyst can be used. For example, butyl lithium or the like can be used. What is shown here is an example, and the present invention is not limited to these.

The catalyst used for the radical polymerization is not particularly limited, and a known catalyst can be used. For example, peroxides such as benzoyl peroxide, lauryl peroxide, and methyl ethyl ketone peroxide can be used. What is shown here is an example, and the present invention is not limited to these. These may be used alone or in combination of two or more.

The catalyst used for the living radical polymerization is not particularly limited, and a known catalyst can be used. For example, a combination system of benzoyl peroxide and a nitroxide compound, a combination system of Ru complex / alkoxyaluminum, and the like can be given. What is shown here is an example, and the present invention is not limited to these. These may be used alone or in combination of two or more.

The polymerization method includes ordinary solution polymerization, suspension polymerization,
It can be synthesized by a method such as bulk polymerization. Particularly, a solution polymerization method is most preferable.

The solvent used is not particularly limited, and a known solvent can be used. For example, chloromethane, dichloromethane, trichloromethane, tetrachloromethane,
Chloroethane, dichloroethane, trichloroethane, tetrachloroethane, chloroethylene, dichloroethylene, nitrobenzene, dinitrobenzene, trinitrobenzene, methylbenzene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, alkylbenzenes such as triethylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. And esters such as MMA, ethyl acetate and butyl acetate. What is shown here is an example,
It is not limited to these. These alone or 2
More than one species can be used.

The polymerization temperature is preferably in the range of -100 ° C to 150 ° C. When the polymerization reaction is carried out at a temperature lower than -100 ° C, the reactivity decreases, and it is difficult to obtain a sufficient high molecular weight product. If the temperature exceeds 150 ° C., the reactivity of the growth terminal is too high, and a chain transfer reaction occurs in a remarkably large amount, so that it may be difficult to obtain a high molecular weight product.

In the present invention, the weight fraction of the polymer (B) in the acenaphthylene derivative-containing copolymer is 5%.
It is preferably 0% or less. When the content is within the range of 50% or less, high heat resistance can be obtained. More preferably, it is 5 to 40% by weight.

The acenaphthylene derivative-containing copolymer according to the present invention can be processed into a molding, sheet or film. In the present invention, when the acenaphthylene derivative-containing copolymer is used as a molding material, sheet or film, optional components can be added as necessary. They are semiconductor-related materials or optical components that can satisfy properties such as low dielectric constant, low moisture absorption, and high heat resistance, as well as paints,
Photosensitive materials, adhesives, sewage treatment agents, heavy metal scavengers, ion exchange resins, antistatic agents, antioxidants, antifogging agents, rust inhibitors, antistaining agents, bactericides, insect repellents, medical materials, coagulation It can also be applied to agents, surfactants, lubricants, binders for solid fuel, conductive treatment agents and the like.

The optical parts using the molding material of the present invention include a pickup lens for CD, a pickup lens for DVD, a lens for FAX, a lens for LBP, an oligo mirror, a prism and the like.

[0060]

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

The evaluation method used in the examples is as follows. (1) Weight average molecular weight The molecular weight of the synthesized polymer was determined by GPC measurement in a tetrahydrofuran solution. (2) Saturated water absorption (%) The water absorption of the sample was determined by immersing the sample in 70 ° C. hot water and measuring the water absorption when the water absorption reached saturation.
The “point of time when the water absorption reaches saturation” is a state in which the water absorption does not change even after being left in the 70 ° C. warm water for a longer time. (3) Heat resistance (Tg) The heat resistance was evaluated by measuring the glass transition point by DSC (differential scanning calorimetry). The DSC measurement was performed at a heating rate of 10 ° C./min. (4) Dielectric constant 20 KV, 1 KHz, 25 using a Precision LCR meter 4284A manufactured by Hewlett-Packard Company.
It was measured under the condition of ° C. (5) Bending strength The bending strength of the test piece was AGS-1 manufactured by Shimadzu Corporation.
000G. The test was performed at room temperature at a test speed of 0.5 mm / min, a span of 20 mm, and a test piece width of 1.
The measurement was performed under the condition of 0 mm. (6) Transmittance The transmittance of the prepared sample was measured at 25 ° C. using V-570 manufactured by JASCO Corporation. Measurement wavelength is 400-800n
The transmittance measured in the range of m was defined as the total light transmittance. (7) Birefringence The obtained molding material was heated at a temperature 5 ° C.
The birefringence of the film stretched by 50% was measured. The measuring equipment is
It measured at 25 degreeC using the ellipsometer AEP-100 made by Shimadzu Corporation. The laser beam wavelength is 632.8n
m. (8) Film forming property After dissolving the obtained polymer in toluene and casting it on a Kapton film, about 60 ° C / 2 hours + 100 ° C /
The solvent was removed under the condition of 2 hours to prepare a film of about 50 μm, and the bending property was visually examined.

[0062]

Example 1 8.0 g of styrene and 2.0 of chlorostyrene
g and 30.0 g of dichloroethane were charged into a 100 ml flask, 0.05 g of lauroyl peroxide was added at about 60 ° C., and the mixture was reacted for 12 hours. afterwards,
The reaction was carried out at 100 ° C. for 6 hours to obtain a homogeneous solution. After 10.0 g of acenaphthylene was added to the reaction mixture reacted for a predetermined time, the mixture was stirred until it became uniform,
The temperature was raised to 0 ° C., and 0.05 g of SnCl ₄ was added and reacted for 12 hours. The obtained homogeneous solution was gradually added to 100 g of methanol to obtain 19.8 g of a white precipitate. The white precipitate was dried under reduced pressure to obtain a target polymer. This white precipitate was melt-pressed to produce a molded material having a thickness of 2 mm, which was used as a test piece. The above evaluation was performed using this test piece. Table 1 shows the evaluation results.

[0063]

Example 2 4.0 g of styrene and 1.0 of chlorostyrene
g and 30.0 g of dichloroethane were charged into a 100 ml flask, and 0.025 g of lauroyl peroxide was added at about 60 ° C., followed by a reaction for 12 hours. Thereafter, the reaction was carried out at 100 ° C. for 6 hours to obtain a uniform solution. After 10.0 g of acenaphthylene was added to the reaction mixture reacted for a predetermined time, the mixture was stirred until it became uniform, the solution was cooled to -40 ° C, and 0.05 g of SnCl ₄ was added.
Allowed to react for hours. The obtained homogeneous solution was gradually added into 100 g of methanol to obtain 14.5 g of a white precipitate. The white precipitate was dried under reduced pressure to obtain a target polymer. This white precipitate was melt-pressed to produce a molded material having a thickness of 2 mm, which was used as a test piece. The above evaluation was performed using this test piece. Table 1 shows the evaluation results.

[0064]

Comparative Example 1 A test piece was obtained in the same manner as in Example 1 except that chloromethylstyrene was not used. The above evaluation was performed using this test piece. Table 1 shows the evaluation results.

[0065]

[Table 1]

[0066]

According to the present invention, it is possible to provide a resin composition having low hygroscopicity and low dielectric constant, and excellent in heat resistance and optical properties.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Akihiro Yoshida 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Industry Co., Ltd. (72) Inventor Tetsuro Yamanaka 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Inside the Goi Works Co., Ltd. AA16 BA01 BA05 BA06 BA16 BA24 BB07 BB08 BB10 DA02 DA03 DA05 DA15 DA17 DA18 DA19 DA20 DB02 DB03 DB05 DB32 GA01 GA08

Claims (9)

[Claims] 1. A polymer (A) comprising at least one acenaphthylene derivative represented by the following general formula (I):
A graft copolymer comprising a polymer (B) having a glass transition point equal to or lower than the glass transition point of the polymer (A), wherein the weight average molecular weight is 3 × 10 ⁴ or more; ) Is an acenaphthylene derivative-containing copolymer comprising styrene or a styrene derivative and a monomer copolymerizable therewith. Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ may be the same or different, and represent a hydrogen atom; a monovalent containing a nitrogen atom, an oxygen atom or a silicon atom. Hydrocarbon group; carbon number 1
Alkyl groups of 6 to 6; monovalent aromatic hydrocarbon groups; halogen atoms; acyl groups; alkoxy groups; ) 2. The polymer (B) comprises styrene, a nucleus-substituted alkylstyrene, a nucleus-substituted aromatic styrene, an α-substituted alkylstyrene, a β-substituted alkylstyrene, a nucleus-substituted alkoxystyrene, an alkyl vinyl ether, an aromatic vinyl ether, 2. The acenaphthylene derivative-containing copolymer according to claim 1, comprising at least one selected from the group consisting of isobutene, diisobutylene, aromatic (meth) acrylate and alkyl (meth) acrylate. 3. The acenaphthylene derivative-containing copolymer according to claim 1, wherein the polymer (B) has a weight average molecular weight of 1 × 10 ⁴ or less. 4. The polymer (B) according to claim 1, wherein the weight fraction of the total weight of the polymer (A) and the polymer (B) is 50% or less. 13. The acenaphthylene derivative-containing copolymer according to claim 1. 5. The acenaphthylene derivative-containing copolymer according to claim 1, wherein the polymer (A) is a random copolymer. 6. A molded material obtained by molding the acenaphthylene derivative-containing copolymer according to any one of claims 1 to 5. 7. A sheet obtained from the acenaphthylene derivative-containing copolymer according to any one of claims 1 to 5. 8. A film obtained from the acenaphthylene derivative-containing copolymer according to any one of claims 1 to 5. 9. An optical component using the molded material, sheet or film according to claim 6.