JP2002003682A - Resin composition low in both hydroscopic property and birefringence and molding materials sheet or film and optical parts obtained from the resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition low in hygroscopic property, birefringence and dielectric constant, and excellent in fluidity. SOLUTION: The resin composition contains polymers (A), (B) and/or (C). The polymer (A) contains at least one acenaphthylene or its derivative represented by general formula (I) (wherein R1, R2, R3, R4, R5 and R6 may be the same or different, and are each H, univalent hydrocarbon containing nitrogen, oxygen or silicon atom, 1-6C alkyl group, univalent aromatic hydrocarbon group, a halogen atom, acryl group, alkoxyl group or nitrile group). The polymer (B) consists of polystyrene or its derivative, and the polymer (C) is composed of a monomer copolymerizable with styrene or its derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having low moisture absorption, low birefringence, low dielectric constant and excellent fluidity.
The present invention relates to a molded material, a sheet, a film, and an optical component obtained by molding the resin composition.

[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]

DISCLOSURE OF THE INVENTION The present invention provides a low moisture absorption,
An object of the present invention is to provide a resin composition having low birefringence, low dielectric constant, and excellent fluidity, a molding material, a sheet or a film, and an optical component obtained by molding the resin composition.

[0013]

The present invention provides a resin composition containing the following polymers (A), (B) and / or (C), a molding material obtained by molding the same, a sheet, a film, The present invention relates to optical components. (A) a polymer containing one or more of acenaphthylene or an acenaphthylene derivative represented by the following general formula (I) (B) a polymer composed of polystyrene or a polystyrene derivative (C) a monomer copolymerizable with styrene or a styrene derivative Polymer consisting of body

[0014]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and include a hydrogen atom; containing a nitrogen atom, an oxygen atom or a silicon atom. A monovalent hydrocarbon group; an alkyl group having 1 to 6 carbon atoms; a monovalent aromatic hydrocarbon group; a halogen atom; an acyl group; an alkoxy group; a nitrile group.) In the present invention, the polymer (A) , (B) and / or (C) have a saturated water absorption of 0.4% or less, and a birefringence at 200% stretching of −2 × 10 ⁻⁶ to 2 ×.
It is preferably in the range of 10 ^-6 .

In the present invention, the weight average molecular weight of the polymer (A) is preferably less than 80,000. The weight average molecular weight of the polymer (B) and / or the polymer (C) is preferably 50,000 or more.

In the present invention, the above polymer (A) is added to the total amount of the polymers (A), (B) and / or (C) by 3%.
It is preferably from 0 to 90% by weight.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, the low moisture absorption, low birefringence resin composition of the present invention and a molding, sheet or film obtained by molding the same will be described in detail.

In the present invention, the polymer (A) is not particularly limited as long as it is a polymer containing one or more of acenaphthylene or an acenaphthylene derivative represented by the above general formula (I). Is also good.

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆
May be the same or different, and represent 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 A group; a halogen atom; an acyl group; an alkoxy group; a nitrile group.

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

The alkyl group having 1 to 6 carbon atoms includes, for example, methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 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 monomer used for the polymer (A), the above acenaphthylene or acenaphthylene derivative 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 a polymer comprising polystyrene or a polystyrene derivative. In the present invention, examples of the monomer used for producing the polymer (B) composed of polystyrene or a polystyrene derivative include styrene, nucleus-substituted alkylstyrene, nucleus-substituted aromatic styrene, α-substituted alkylstyrene, and β-substituted alkyl. Styrene, nucleus-substituted alkoxystyrene 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 nuclear-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 alkylstyrene include α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-n-butylstyrene, α-isobutylstyrene, α-t-butylstyrene, and α-n-butylstyrene. 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 nucleus-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.

The polymer (C) is a polymer comprising a monomer copolymerizable with styrene or a styrene derivative. Examples of the monomer copolymerizable with styrene or a styrene derivative used in the polymer (C) include styrene, a nucleus-substituted alkylstyrene, a nucleus-substituted aromatic styrene, an α-substituted alkylstyrene, a β-substituted alkylstyrene, Nucleus-substituted alkoxystyrene, alkyl vinyl ether, aromatic vinyl ether, isobutene, diisobutylene, C1
C8 (meth) acrylic ester and the like can be mentioned. These may be used alone or in combination of two or more.

The nucleus-substituted alkylstyrene, nucleus-substituted aromatic styrene, α-substituted alkylstyrene, β-substituted alkylstyrene and nucleus-substituted alkoxystyrene are the same as those used in the polymer (B). .

The alkyl of the alkyl vinyl ether is not particularly limited, and any alkyl may be used. For example,
Methyl, 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, 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.

The C1-C8 (meth) acrylic esters include methyl (meth) acrylate and ethyl (meth) acrylate.
Acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate,
Examples thereof include n-octyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. 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.

In the present invention, the above (A), (B),
The method for producing the polymer (C) is not particularly limited, and the polymer can be produced by a usual method. For example, it can be produced by cationic polymerization, anionic polymerization, radical polymerization, living radical polymerization and the like. 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 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 to be 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 average molecular weight of the polymer (A) is preferably less than 80,000,
More preferably, it is less than 000. When the weight average molecular weight of the polymer (A) is less than 80,000, the fluidity of the resin and the transparency of the resin tend to decrease.

The weight average molecular weight of the polymer (A) can be adjusted to the above range by selecting the type and amount of the catalyst used in the polymerization, using a polymerization inhibitor, using a chain transfer agent,
It can be prepared by adjusting the polymerization temperature.

The weight average molecular weight of the polymer (B) and / or the polymer (C) is preferably at least 50,000, more preferably at least 100,000. When the weight average molecular weight of the polymer (B) and / or the polymer (C) is less than 50,000, the strength of the molding material tends to decrease.

The weight average molecular weight of the polymer (B) and / or the polymer (C) is adjusted to the above range by selecting the type and amount of the catalyst used in the polymerization, using a polymerization inhibitor,
It can be prepared by selecting the type and amount of the catalyst to be used, using a polymerization inhibitor, using a chain transfer agent, adjusting the polymerization temperature, and the like.

The weight average molecular weight can be determined by GPC measurement in a tetrahydrofuran solution.

The polymer (A) obtained by the above method,
(B) and (C) can be isolated by a usual method and used for a resin composition.

The method of mixing the polymers (A), (B) and / or (C) in the present invention is not particularly limited, and a predetermined amount of each polymer is weighed in a solid state, and these are melt-kneaded. Or by dissolving each polymer in a solvent such as toluene, THF, or NMP, and then removing the solvent.

In the present invention, the polymer (A) is added to the total amount of the polymers (A), (B) and / or (C) by 3
It is preferably from 0 to 90% by weight, more preferably from 60 to 85% by weight. When the amount of the polymer (A) is less than 30% by weight or more than 90% by weight based on the total amount of the polymers (A), (B) and / or (C), the absolute value of the birefringence tends to increase. is there.

The ratio to the total amount of the polymer (B) is preferably 10 to 40% by weight, and the ratio to the total amount of the polymer (C) is preferably 0 to 30% by weight.

The resin composition of the present invention obtained as described above has a saturated water absorption of 0.4% or less and a birefringence at the time of stretching of 200% of from −2 × 10 ⁻⁶ to 2 × 10 ^−. It is preferably in the range of ⁶ . More preferred saturated water absorption is 0.2%
The birefringence after 200% stretching is more preferably -1 × 10 ^-6 to 1 × 10 ^-6 .

If the saturated water absorption exceeds 0.4%, the change in the refractive index at the time of water absorption is undesirably large. Also, 200%
If the birefringence during stretching is out of the range of −2 × 10 ⁻⁶ to 2 × 10 ⁻⁶ , it is not preferable because linearly polarized light may greatly change to elliptically polarized light.

In order to keep the saturated water absorption within the above range, the ratio of the polymer (A) to the whole resin composition is from 30 to 90.
The weight% may be used.

In order to set the birefringence at the time of stretching by 200% within the above range, the ratio of the polymer (A) to the entire resin composition may be set to 30 to 90% by weight.

The saturated water absorption (%) in the present invention is 70%.
It can be calculated by immersing the test piece in warm water at ° C. and measuring the water absorption when the water absorption reaches saturation. “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.

The birefringence of the molded material obtained by stretching it by 200% at a temperature 5 ° C. lower than its glass transition temperature is, for example, the ellipsometer AEP-10.
It can be measured using Model 0 (manufactured by Shimadzu Corporation). The measurement conditions are as follows: temperature: 25 ° C., laser beam wavelength: 632.8 nm. The measurement of the glass transition temperature of the molding material can be obtained as follows. The measurement of the glass transition temperature is DS
It can be measured by C (differential scanning calorimetry). The DSC measurement is carried out at a rate of temperature rise of 10 ° C./min.

The resin composition according to the present invention can be processed into a molding, a sheet or a film. In the present invention, when the resin composition is formed into a molding, a sheet or a film, optional components can be added as necessary. They are low dielectric constant, low moisture absorption, semiconductor related materials that can satisfy the characteristics such as high heat resistance, or optical materials, furthermore, paints, photosensitive materials, adhesives, sewage treatment agents, heavy metal collectors,
Ion exchange resin, antistatic agent, antioxidant, antifogging agent, antirust agent, antistaining agent, bactericide, insect repellent, medical material, flocculant, surfactant, lubricant, binder for solid fuel, conductive treatment Application to agents and the like is also possible.

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.

[0066]

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. (3) Heat resistance (Tg) The heat resistance was evaluated by measuring the glass transition temperature by DSC (differential scanning calorimetry). DSC
Was measured at a temperature rising 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-10 manufactured by Shimadzu Corporation.
This was performed using 00G. The test was performed at room temperature at a test speed of 0.5 mm / min, a span of 20 mm, and a specimen width of 10
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 birefringence of a molded article obtained by stretching it by 150% at a temperature 5 ° C. lower than the glass transition temperature was measured. The measurement was performed at 25 ° C. using an ellipsometer AEP-100 manufactured by Shimadzu Corporation. The laser beam wavelength is 632.8
nm. (8) Fluidity (MI) The fluidity of the resin composition was determined by measuring a melt flow rate at 220 ° C. under a load of 5 kgf.

[0068]

Example 1 10.0 g of acenaphthylene and 3 parts of toluene
0.0 g was put into a 100 ml flask,
Then, 0.05 g of lauroyl peroxide was added and reacted for 12 hours with stirring. Thereafter, the reaction mixture was gradually added into 100 g of methanol to obtain 9.8 g of a white precipitate. The white precipitate was dried under reduced pressure to obtain a polymer (A). The weight average molecular weight of this polymer is 35
000.

Next, 20.0 g of styrene and 0.1 g of benzoyl peroxide were put into a 100 ml flask, and dissolved by stirring. Then, 60 g of distilled water and 0.01 g of calcium phosphate were added to the monomer mixture. The mixture was added and reacted at 70 ° C. with stirring for 12 hours. The obtained particulate polymer was isolated, washed with hydrochloric acid, and then dried at 50 ° C. for about 2 hours to obtain a polymer (B). The weight average molecular weight of the obtained polymer was 200000.

6.0 g of the polymer (A) and 4.0 g of the polymer (B)
0 g was dissolved in 20 g of toluene and added to about 300 g of methanol to precipitate a solid. The solid was dried at 40 ° C. for 6 hours to obtain a white precipitate of the target resin composition.
The resin composition is melt-pressed to a thickness of 2 m.
m was prepared and used as a test piece. The above evaluation was performed using this test piece. Table 1 shows the evaluation results.

[0071]

Example 2 Acenaphthylene 8.0 g, styrene 2.0
g and toluene 30.0 g into a 100 ml flask, and at 60 ° C., 0.05 g of lauroyl peroxide.
Was added and reacted with stirring for 12 hours. afterwards,
This reaction mixture was gradually added into 100 g of methanol to obtain 9.8 g of a white precipitate. The white precipitate was dried under reduced pressure to obtain a polymer (A). The weight average molecular weight of this polymer was 34,000.

Next, 20.0 g of styrene and 0.1 g of benzoyl peroxide were charged into a 100 ml flask and dissolved by stirring. Then, 60 g of distilled water and 0.01 g of calcium phosphate were added to the monomer mixture. The mixture was added and reacted at 70 ° C. with stirring for 12 hours. The obtained particulate polymer was isolated, washed with hydrochloric acid, and then dried at 50 ° C. for about 2 hours to obtain a polymer (B). The weight average molecular weight of the obtained polymer was 200000.

Next, 14.0 g of styrene, 5.0 g of 4-methylstyrene, 1.0 g of butyl acrylate, and 0.1 g of benzoyl peroxide were charged into a 100 ml flask, and dissolved by stirring. 60 g and 0.01 g of calcium phosphate were added to the monomer mixture.
The mixture was reacted for 12 hours with stirring. The obtained particulate polymer was isolated, washed with hydrochloric acid, and then dried at 50 ° C. for about 2 hours to obtain a polymer (C). The weight average molecular weight of the obtained polymer was 240,000.

6.0 g of polymer (A) and 1. g of polymer (B)
5 g and 2.5 g of the polymer (C) were dissolved in 20 g of toluene and added to about 300 g of methanol to precipitate a solid. The solid was dried at 40 ° C. for 6 hours to obtain a white precipitate of the target resin composition. This resin composition 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.

[0075]

Comparative Example 1 10.0 g of acenaphthylene and toluene 3
0.0 g was put into a 100 ml flask,
Then, 0.05 g of lauroyl peroxide was added and reacted for 12 hours with stirring. Thereafter, the reaction mixture was gradually added into 100 g of methanol to obtain 9.8 g of a white precipitate. The white precipitate was dried under reduced pressure to obtain a polymer (A). The weight average molecular weight of this polymer is 35
000.

Next, 20.0 g of styrene and 0.1 g of benzoyl peroxide were charged into a 100 ml flask, and dissolved by stirring. Then, 60 g of distilled water and calcium phosphate were added to a monomer mixture at a concentration of 0.1 g. 01 g, 70 ° C
The mixture was reacted for 12 hours while stirring. The obtained particulate polymer was isolated, washed with hydrochloric acid, and then washed at 50 ° C. for about 2 hours.
After drying for an hour, a polymer (B) was obtained. The weight average molecular weight of the obtained polymer was 200000.

4.0 g of polymer (A) and 6. g of polymer (B)
0 g was dissolved in 20 g of toluene and added to about 300 g of methanol to precipitate a solid. The solid was dried at 40 ° C. for 6 hours to obtain a white precipitate of the target resin composition.
The resin composition is melt-pressed to a thickness of 2 m.
m was prepared and used as a test piece. The above evaluation was performed using this test piece. Table 1 shows the evaluation results.

[0078]

Comparative Example 2 Acenaphthylene 20.0 g and toluene 6
0.0 g was put into a 200 ml flask,
Then, 0.1 g of lauroyl peroxide was added and reacted for 12 hours with stirring. Thereafter, the reaction mixture was gradually added to 100 g of methanol to form a white precipitate 1
9.8 g were obtained. The white precipitate was dried under reduced pressure to obtain a polymer (A). The weight average molecular weight of this polymer is 35
000.

[0079] 10.0 g of the polymer (A) was added to 20 g of toluene.
And added to about 300 g of methanol to precipitate a solid. The solid was dried at 40 ° C. for 6 hours to obtain a white precipitate of the target resin composition. A melt having a thickness of 2 mm is produced by melt-pressing the resin composition.
A test piece was used. The above evaluation was performed using this test piece.
Table 1 shows the evaluation results.

[0080]

[Table 1]

[0081]

According to the present invention, low hygroscopicity, low birefringence,
A resin composition having low dielectric constant and excellent fluidity can be provided. Further, using a molding material obtained by molding the resin composition, a sheet or a film, low hygroscopicity,
An optical component having low birefringence and low dielectric constant can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) G02B 1/04 G02B 1/04 (72) Inventor Akihiro Yoshida 14 Goi Minamikaigan, Ichihara-shi, Chiba Hitachi Chemical Inside the Goi Works Co., Ltd. (72) Inventor Tetsuro Yamanaka 14 Goi South Coast, Ichihara-shi, Chiba Hitachi Chemical Co., Ltd. Within the Goi Works Co., Ltd. (72) Keiko Ushikubo 14 Goi-Minami Coast, Ichihara-shi, Chiba Hitachi Chemical Co., Ltd. Goi Office F term (reference) 4F071 AA22 AA22X AA30X AA33X AA39 AA69 AA81 AA88 AF10 AF30 AF40 AF45 AH19 BB03 BC01 4J002 BC03X BC04X BC07X BC08X BC09X BC12X BK00W CE00W GP00

Claims (9)

[Claims] 1. A resin composition containing the following polymers (A), (B) and / or (C). (A) a polymer containing one or more acenaphthylene or an acenaphthylene derivative represented by the following general formula (I) (B) a polymer composed of polystyrene or a polystyrene derivative (C) a monomer copolymerizable with styrene or a styrene derivative Polymer consisting of a body (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 saturated water absorption is 0.4% or less,
The resin composition according to claim 1, wherein the birefringence at the time of 0% stretching is in the range of -2 x ^10-6 to 2 x ^10-6 . 3. The weight average molecular weight of the polymer (A) is:
The resin composition according to claim 1, wherein the resin composition is less than 80,000. 4. The resin composition according to claim 1, wherein the weight average molecular weight of the polymer (B) and / or the polymer (C) is 50,000 or more. 5. The polymer (A) is a polymer (A),
The resin composition according to any one of claims 1 to 4, wherein the content is 30 to 90% by weight based on the total amount of (B) and / or (C). 6. A molding obtained by molding the resin composition according to claim 1. Description: 7. A sheet obtained from the resin composition according to any one of claims 1 to 5. 8. A film obtained from the resin composition according to claim 1. 9. An optical component using the molded material, sheet or film according to claim 6.