JPH061813A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition which is excellent in transparency, mechanical property, and moldability and has extremely reduced birefringence. CONSTITUTION:The title composition comprises (a) a block copolymer of 20-80wt.% polycarbonate with 80-20wt.% vinyl polymer, (b) a polycarbonate, and (c) a vinyl homopolymer. The contents of the components are: 50 wt.%<=(a)<100wt.%; 0wt.%<(b)<=30wt.%; and 0wt.%<(c)<=20wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition mainly composed of a block copolymer in which a polycarbonate component and a vinyl polymer component are chemically bonded. More specifically, it is a resin composition mainly composed of a block copolymer in which a polycarbonate component and a vinyl polymer component are chemically bonded, and it does not contain a homopolymer of a polycarbonate or a vinyl polymer in a specific amount or more. The present invention relates to a resin composition which is characterized by excellent transparency, a significantly reduced birefringence index, and excellent mechanical properties and moldability.

[0002]

2. Description of the Related Art A resin composition comprising a polycarbonate and a vinyl polymer is known. In particular, a resin composition composed of polycarbonate and polystyrene can theoretically have a birefringence of zero (Takashi Inoue, Taku Saito: Functional Material, P21, March 1987 issue). It is expected to be applied to equipment. However, since the compatibility between polycarbonate and polystyrene is poor, transparency is impaired in a composition simply blended, the effect of reducing birefringence is not recognized, and mechanical properties are significantly deteriorated. .

In order to solve such a problem, Japanese Patent Laid-Open No. 61-61
No. 19630 discloses polystyrene of 5 to 40% by weight.
Chemically bonded polycarbonates are disclosed. Japanese Unexamined Patent Publication (Kokai) No. 61-19656 discloses a resin composition containing 5 to 50% by weight of a styrene resin copolymerized with an unsaturated carboxylic acid. Japanese Patent Laid-Open No. 61-1086
Japanese Patent Publication No. 17 discloses a resin composition in which a polycarbonate having a positive polarizability and a polystyrene having a negative polarizability are mixed. Japanese Unexamined Patent Publication (Kokai) No. 62-20524 discloses a polycarbonate in which a styrene-based copolymer is chemically bonded. JP-A-63-27555, JP-A-63-56556, and JP-A-63-
Japanese Patent No. 66255 discloses a resin composition in which a copolymerized polycarbonate and a styrene-based polymer are blended in an amount of 3 to 50% by weight. JP-A-63-122749 discloses a composition in which a copolymer of styrene and maleic anhydride is mixed with polycarbonate.

However, in the resin compositions disclosed in these publications, the transparency was obtained, but the birefringence was not sufficiently reduced, or the mechanical properties were deteriorated. On the other hand, in some cases, attempts to improve mechanical properties caused problems such as poor transparency and moldability. Therefore, a resin composition composed of a polycarbonate and a vinyl polymer typified by polystyrene, which has excellent transparency, has a significantly reduced birefringence index, and has excellent mechanical properties and moldability, can be used for optical devices. Although the application of is expected, the fact is that it has not been proposed yet.

[0005]

SUMMARY OF THE INVENTION In view of such circumstances, an object of the present invention is to provide a resin composition mainly composed of a block copolymer in which a polycarbonate component and a vinyl polymer component are chemically bonded to each other. Another object of the present invention is to provide a resin composition which is excellent in properties, has a significantly reduced birefringence, and has excellent mechanical properties and moldability. Another object of the present invention is to provide a resin composition suitable for optical equipment such as an optical disc, an optical fiber, an optical card protective film or a lens.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the inventors of the present invention have found that mainly a block copolymer in which a polycarbonate component and a vinyl polymer component are chemically bonded to each other. A resin composition comprising:
The inventors have found that a resin composition satisfying specific conditions solves all the problems of the present invention, and arrived at the present invention. That is, the gist of the present invention is (a) polycarbonate component 2
A block copolymer in which 0 to 80% by weight and 80 to 20% by weight of a vinyl-based polymer component are chemically bonded, a homopolymer of (b) polycarbonate and a homopolymer of (c) vinyl-based polymer. Is a resin composition characterized by satisfying the following formulas (1), (2) and (3). 50 wt% ≤ (a) <100 wt% (1) 0 wt% <(b) ≤ 30 wt% (2) 0 wt% <(c) ≤ 20 wt% (3)

The polycarbonate component used in the present invention is a component composed of an aromatic polycarbonate obtained from bisphenols and carbonic acid. The bisphenols constituting the polycarbonate include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1-
Phenyl-1,1-bis (4-hydroxyphenyl) ethane (bisphenol AP), hydroquinone, resorcinol, 4,4′-dihydroxybiphenyl, 1,1
-Bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5
-Trimethylcyclohexane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ethane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-diethyl-4-hydroxyphenyl) Methane, 1,1-bis (3,5-dimethyl-
4-hydroxyphenyl) ethane, 1,1-bis (3,3
5-diethyl-4-hydroxyphenyl) ethane, 1,
1-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-)
Hydroxyphenyl) propane, 1,1-bis (3,5
-Diethyl-4-hydroxyphenyl) propane, 2,
2-bis (3,5-diethyl-4-hydroxyphenyl) propane, 1,1-bis (3,5-dimethyl-4-)
Hydroxyphenyl) butane, 2,2-bis (3,5-
Dimethyl-4-hydroxyphenyl) butane, 1,1-
Bis (3,5-diethyl-4-hydroxyphenyl) butane, 2,2-bis (3,5-diethyl-4-hydroxyphenyl) butane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ) Cyclohexane, 1,1-
Bis (3,5-diethyl-4-hydroxyphenyl) cyclohexane, bis (3,5-dimethyl-4-hydroxyphenyl) phenylmethane, bis (3,5-diethyl-4-hydroxyphenyl) phenylmethane, 1,1 −
Bis (3,5-dimethyl-4-hydroxyphenyl)-
1-phenylethane, 1,1-bis (3,5-diethyl-4-hydroxyphenyl) -1-phenylethane, bis (3,5-dimethyl-4-hydroxy) diphenylmethane, bis (3,5-diethyl-) 4-hydroxy) diphenylmethane, bis (4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-diethyl-4-hydroxyphenyl) ether, bis (4-hydroxy) Phenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-diethyl-4-hydroxyphenyl) sulfide, bis (4
-Hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,3
5-diethyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (3,5-
Examples thereof include dimethyl-4-hydroxyphenyl) ketone and bis (3,5-diethyl-4-hydroxyphenyl) ketone. These may be used alone or in combination. Of these, bisphenol A is most preferably used.

The polycarbonate component used in the present invention includes those modified with a functional group in order to facilitate chemical bonding with a vinyl polymer. As such a functional group, an unsaturated bond that can be chemically bonded to the vinyl polymer is preferably used. As a method of introducing such an unsaturated bond into the polycarbonate, a method of polymerizing the polycarbonate by replacing a part of the bisphenols with a specific bisphenol having an unsaturated bond, or an interfacial polymerization method is further used as a terminal stopper of the polycarbonate. Examples thereof include a method using a compound having a saturated bond. Specific examples of the specific bisphenol having an unsaturated bond include, for example, 2,2-bis (3-vinyl-4-hydroxyphenyl) propane, bis (3-vinyl-4-hydroxyphenyl) methane, 3,3- Examples include bis (4-hydroxyphenyl) propene and 3,3-bis (4-hydroxyphenyl) butene. As the terminal terminator having an unsaturated bond, acrylic acid chloride, methacrylic acid chloride, sorbic acid chloride, allyl alcohol chloroformate, acid chlorides and chloroformates such as isopropenylphenol chloroformate and hydroxystyrene chloroformate, Mention may be made of phenols having unsaturated groups such as isopropenylphenol, hydroxystyrene, hydroxymaleimide, allyl ester of hydroxybenzoic acid and methylallyl benzoate and amines having unsaturated groups such as allylamine. There is also a method in which the polycarbonate component and the vinyl polymer are chemically bonded radically, either thermally or by using a radical generator, without introducing these unsaturated bonds into the polycarbonate.

Polycarbonate can be produced by a melt polymerization method or an interfacial polymerization method. In the melt polymerization method, for example, a polycarbonate is obtained by reacting diphenyl carbonate and bisphenol at a high temperature under reduced pressure. On the other hand, in the interfacial polymerization method, bisphenols are dissolved in an alkaline aqueous solution, and phosgene is blown into this while mixing and stirring with an organic solvent that is incompatible with water to obtain a polycarbonate. Compared with the melt polymerization method, the interfacial polymerization method can give a polycarbonate with less coloring.

The molecular weight of the polycarbonate used in the present invention is not particularly limited, but the number average molecular weight of the homopolymer of the polycarbonate of the component (b) is 3,000 to 10.
It is preferably in the range of 10,000. When the number average molecular weight is less than 3,000, the mechanical performance of the resin composition is deteriorated, which is not preferable. On the contrary, this is 100,0
When it exceeds 00, the moldability is rapidly lowered, which is not preferable. The molecular weight of the present invention is measured by gel permeation chromatography calibrated with monodisperse polystyrene. The molecular weight of the polycarbonate component in the block copolymer in which the polycarbonate component constituting the resin composition of the present invention and the vinyl polymer component are chemically bonded is not particularly limited.

The vinyl polymer component used in the present invention is obtained by polymerizing a vinyl monomer mainly containing styrene. Such vinyl-based monomers include, for example, o-, m-, p-methylstyrene, other than styrene,
alkyl styrenes such as o-, m-, p-ethylstyrene, p-tert-butylstyrene, o-, m-,
p-chlorostyrene, dichlorostyrene, o-, m-,
Halogenated styrenes such as p-bromostyrene and dibromostyrene, α-methylstyrene, o-, m-, p-
Hydroxystyrene and the like, and mixtures thereof. Further, this vinyl-based polymer may be copolymerized with 50 mol% or less of another vinyl-based monomer in order to improve physical properties. Examples of other vinyl-based monomers include methacrylic acid esters, acrylic acid esters, vinyl acetate, butadiene, acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride and the like. The monomer constituting the vinyl-based polymer preferably used in the present invention is styrene, and the most preferable vinyl-based polymer contains at least 70 mol% of styrene.

As the method for producing the vinyl polymer, a general radical polymerization method can be used, but the method is not limited to this, and an anionic polymerization method or a cationic polymerization method can also be appropriately used. The molecular weight of the vinyl polymer used in the present invention is not particularly limited, but the number average molecular weight of the homopolymer of the vinyl polymer of component (c) is 1,
Those of 000 to 200,000 are preferable. When the number average molecular weight is less than 1,000, physical properties of the resin composition, particularly mechanical properties are deteriorated, which is not preferable. Conversely, 200,000
If it exceeds, not only the moldability of the resin composition is lowered, but also its transparency is lowered and the birefringence is increased, which is not preferable. Further, there is no particular limitation on the molecular weight of the vinyl-based polymer component in the block copolymer in which the polycarbonate component and the vinyl-based polymer component constituting the resin composition of the present invention are chemically bonded. The molecular weight was measured by gel permeation chromatography as in the case of polycarbonate.

Such vinyl-based polymer components include those modified with a functional group in order to facilitate chemical bonding with the aromatic polycarbonate component. Typical examples of such a functional group include a carboxyl group, a hydroxyl group, an amino group, an epoxy group, and an oxazoline group. Examples of the method of introducing such a functional group into the vinyl polymer include a method of copolymerizing a monomer having these functional groups, a method of using a radical initiator or a chain transfer agent having these functional groups, or a vinyl polymer. After that, there is a method of chemically denaturing it.

A method of introducing a carboxyl group into a vinyl polymer is, for example, 4,4'-azobis-4-.
It is convenient to use an initiator having a carboxyl group such as cyanovaleric acid because a vinyl polymer having a carboxyl group at the terminal can be easily obtained. Further, for example, anionic polymerization of styrene is carried out using sodium naphthalene as an initiator, and the obtained polymer is treated with carbon dioxide to obtain a vinyl polymer having a carboxyl group at the terminal. Further, by copolymerizing acrylic acid, methacrylic acid, maleic anhydride, etc., a vinyl polymer having a carboxyl group in its main chain can be obtained.

As a method for introducing a hydroxyl group into a vinyl polymer, for example, a hydrogen peroxide-ferrous iron ion type redox initiator is used in a radical polymerization method to easily obtain a vinyl polymer having a hydroxyl group at a terminal. This is convenient because it can be done. Further 2,2
There is also a method of introducing a hydroxyl group into a vinyl polymer by radical polymerization using an initiator having a hydroxyl group such as -azobis (2-cyano-n-propanol). Further, for example, anionic polymerization of styrene is carried out using sodium naphthalene as an initiator, and the obtained polymer is treated with ethylene oxide to obtain a vinyl polymer having a hydroxyl group at the terminal. A vinyl polymer having a hydroxyl group in its main chain can also be obtained by copolymerizing vinyl acetate and then saponifying it.

As a method of introducing an amino group into a vinyl polymer, there is a method of introducing an amino group into a vinyl polymer by using a chain transfer agent such as ethanethionyl ammonium chloride in radical polymerization.
As a method of introducing an epoxy group into a vinyl polymer, there is a method of copolymerizing a vinyl monomer containing an epoxy group such as glycidyl methacrylate. As a method of introducing an oxazoline group into a vinyl polymer, there is a method of copolymerizing a vinyl monomer containing an oxazoline group such as vinyloxazoline.

As a method for producing a block copolymer in which a polycarbonate component and a vinyl polymer component are chemically bonded, for example, the following method may be mentioned. A. A method for reacting a vinyl monomer with a polycarbonate modified with a functional group capable of reacting with a vinyl monomer. B. A method of reacting a polycarbonate-forming component with a vinyl polymer modified with a functional group capable of reacting with the polycarbonate-forming component. C. Preferably, a method of reacting a polycarbonate, at least one of which is modified with a functional group, and a vinyl polymer.

A. As an example of a method of reacting a vinyl monomer with a polycarbonate modified with a functional group capable of reacting with a vinyl monomer, one obtained by polymerizing using isopropenylphenol chloroformate as a terminal stopper is There is a method of obtaining a block copolymer in which a polycarbonate component and a vinyl polymer component are chemically bound by radically polymerizing a polycarbonate having an unsaturated bond at the polymer terminal and a vinyl monomer.

B. As an example of a method of reacting a vinyl polymer modified with a functional group capable of reacting with the polycarbonate-forming component, and the polycarbonate-forming component,
An acid chloride group-containing polystyrene obtained by polymerizing a vinyl monomer using an initiator having a carboxyl group such as 4,4′-azobis-4-cyanovaleric acid and then treating the vinyl monomer with thionyl chloride, There is a method of obtaining a block copolymer in which a polycarbonate component and a vinyl-based polymer component are chemically bonded by interfacially polymerizing a polycarbonate-forming component (for example, bisphenol A and phosgene).

C. Preferably, at least one of the modified polycarbonate with a functional group and the vinyl-based polymer, as an example of a method of reacting, by melting and mixing the polycarbonate and a vinyl-based polymer containing a carboxyl group, decarboxylation There is also a method in which an acid exchange reaction is carried out in association therewith to obtain a block copolymer in which a polycarbonate component and a vinyl polymer component are chemically bonded.

As described above, various resin compositions or copolymers of a polycarbonate and a vinyl polymer (for example polystyrene), which are transparent and have a low birefringence and excellent mechanical properties, have been proposed. . However, although transparency was obtained with these resin compositions or copolymers, the birefringence was not sufficiently reduced or the mechanical properties were deteriorated. On the other hand, in some cases, problems such as poor transparency and moldability have occurred when attempting to improve mechanical properties.

The present inventors have diligently investigated such problems of the prior art in a resin composition mainly composed of a block copolymer in which a polycarbonate component and a vinyl polymer component are chemically bonded, and as a result, It was found from the production method that the resin composition necessarily contained a certain amount of a homopolymer of polycarbonate or vinyl-based polymer, and the resin composition thus obtained did not exhibit satisfactory performance. Therefore, as a result of various investigations, in the resin composition of the present invention, by not containing more than a specific amount of a homopolymer of a polycarbonate or a vinyl-based polymer that is a component that constitutes the transparency, birefringence, The present invention has been completed based on the finding that satisfactory performance can be obtained in each of mechanical properties and moldability.

That is, in the resin composition of the present invention, the block copolymer (a) in which 20 to 80% by weight of the polycarbonate component and 80 to 20% by weight of the vinyl polymer component are chemically bonded accounts for 50% by weight or more. , Polycarbonate present as a homopolymer (b) is 0% by weight <(b)
≦ 30% by weight, and the vinyl-based polymer (c) which is also present as a homopolymer is 0% by weight <(c) ≦ 20.
% By weight. With such a composition, satisfactory performances can be obtained in the properties of transparency, birefringence, mechanical properties and moldability. For (b) and (c), (b) +
(C) is preferably 1 to 50% by weight. (B)
When the homopolymer of the component polycarbonate is present in an amount of more than 30% by weight, the birefringence of the resin composition increases rapidly, and in a remarkable case, the transparency is impaired and the moldability also deteriorates. When the amount of the homopolymer of the vinyl-based polymer as the component (c) exceeds 20% by weight, the birefringence of the resin composition increases, and in the same case, the transparency is impaired and the mechanical properties are rapidly increased. Fall to.

In the resin composition of the present invention, the polycarbonate component constituting the block copolymer (a) in which the polycarbonate component and the vinyl polymer are chemically bonded is 20 to 80% by weight. Is 80 to 20% by weight. Less than 20% by weight of the polycarbonate component in the block copolymer, and 80
The birefringence of the resin composition increases in the range of more than wt%.

In the resin composition of the present invention, a block copolymer (a) in which a polycarbonate component and a vinyl polymer are chemically bonded, a homopolymer of polycarbonate (b) and a homopolymer of vinyl polymer (ha) )
The composition ratio of and can be confirmed by extraction with a specific solvent. As shown in Reference Examples 5 and 6, a homopolymer of polycarbonate that is not chemically bonded to a vinyl-based polymer is substantially completely extracted with hexafluoroisopropanol. Also, vinyl polymers that are not chemically bonded to the polycarbonate are substantially completely extracted with cyclohexane. The block copolymer in which the polycarbonate component and the vinyl polymer are chemically bonded is not substantially extracted by either hexafluoroisopropanol or cyclohexane.
Therefore, the composition ratio of each component in the resin composition of the present invention can be confirmed by fractionally extracting using the above solvent. In other words, in the present invention, the block copolymer in which the polycarbonate component (a) and the vinyl polymer are chemically bonded is defined as a component that is not extracted by hexafluoroisopropanol or cyclohexane. Further, the homopolymer of polycarbonate as the component (b) is defined as a component extracted with hexafluoroisopropanol. Further, the homopolymer of the vinyl polymer as the component (c) is defined as a component extracted with cyclohexane.

In the present invention, the conditions for the fractional extraction with the above solvent for confirming the composition ratio of the resin composition are as follows. That is, the homopolymer of polycarbonate that is not chemically bonded to the vinyl polymer is extracted with hexafluoroisopropanol, and the extraction conditions are a Soxhlet extractor and boiling point for 16 hours. A homopolymer of vinyl polymer that is not chemically bonded to polycarbonate is extracted with cyclohexane.
The extraction condition is a Soxhlet extractor, and the boiling point is 16
Do on time.

The resin composition of the present invention further comprises a heat stabilizer, an antioxidant, and
It is also possible to add weathering agents, flame retardants, plasticizers, release agents, colorants, reinforcing agents and the like. As such heat stabilizers and antioxidants, phosphorus compounds, hindered phenols,
There are hindered amines, sulfur compounds, copper compounds or mixtures thereof. Of these, phosphorus compounds and hindered phenols are particularly preferable.

If desired, other polymers may be added to the resin composition of the present invention. Examples of such a polymer include polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural rubber, chlorinated butyl rubber, chlorinated polyethylene, styrene-butadiene block. Elastomers such as copolymers, butadiene-styrene radial teleblock copolymers,
Styrene-maleic anhydride copolymer, styrene-phenylmaleimide copolymer, polyethylene, polypropylene, butadiene-acrylonitrile copolymer, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyvinylidene fluoride, polysulfone, polyphenylene sulfide, Examples thereof include polyether sulfone, phenoxy resin, polyphenylene ether, polymethyl methacrylate, polyether ketone, polyamide, polyarylate, and polytetrafluoroethylene.

The resin composition of the present invention can be made into a desired molded article by a usual molding method. For example, hot melt molding methods such as injection molding, extrusion molding, blow molding, and sintering molding can be applied. Alternatively, a thin film can be formed from an organic solvent solution by a casting method. The resin composition obtained by the method of the present invention is excellent in transparency, has a greatly reduced birefringence, and is excellent in mechanical properties and moldability. Therefore, various molded products, films, sheets, optical discs, etc. It is also suitably used for optical applications such as optical fibers, optical guard protective films, and lenses.

[0030]

The present invention will be specifically described with reference to the following examples. Reference Example 1 [Vinyl polymer having a carboxyl group at the end (S
Synthesis example of 1)] After sufficiently replacing the reaction tank with nitrogen,
4'-azobis-4-cyanovaleric acid (AC
Using VA) as a polymerization initiator, 100 parts by weight of styrene was radically polymerized at 90 ° C. ACVA was dissolved in 1,4-dioxane and continuously added during the polymerization as well as at the beginning of the polymerization. After reacting for 1 hour, the obtained polymer was dropped into methanol to cause precipitation, which was filtered and dried to obtain a white powder. The molecular weight of the obtained vinyl-based polymer (S1) was measured by Toyo Soda Co., Ltd. GPC measuring device HLC-802A.
Was measured using. The carboxyl group is chloroform /
It was determined by dissolving in a mixed solvent of benzyl alcohol = 1/1 (volume ratio) and titrating this with potassium hydroxide. The molecular weight and the value of the carboxyl group are listed in Table 1.

Reference Example 2 [Synthesis Example of Vinyl Polymer (S2) Having Alcohol Hydroxyl Group at Terminal] After sufficiently replacing the reaction tank cooled to −30 ° C. with nitrogen, 200 parts by weight of distilled water and styrene 1 were added.
00 parts by weight and 0.5 parts by weight of sodium dodecylbenzene sulfonate were added to the reaction vessel. While stirring the reaction layer, 1 part by weight of 30% hydrogen peroxide solution and 1% ferrous sulfate aqueous solution were continuously added at a volume ratio of 7: 3. The obtained polymer was dropped into methanol to cause precipitation, which was filtered and dried to obtain a white powder. The molecular weight of the obtained vinyl polymer S2 and the amount of alcoholic hydroxyl groups were measured. The molecular weight was measured as described above. The alcoholic hydroxyl group was obtained by dissolving the obtained vinyl polymer in pyridine, adding acetic anhydride to this to acetylate the alcoholic hydroxyl group, and titrating the excess acetic anhydride with sodium hydroxide. The molecular weight and the value of alcoholic hydroxyl group are shown in Table 1.
Listed in.

Reference Example 3 [Synthesis example of vinyl-based polymer (S3) having no functional group] Using benzoyl peroxide as a polymerization initiator, 100 parts by weight of styrene was radical-polymerized at 90 ° C. in the same manner as in Reference Example. Thus, a vinyl polymer (S3) having no functional group was obtained. The molecular weight was determined in the same manner as in Reference Example 1. The results are also shown in Table 1.

Reference Example 4 [Polycarbonate having an unsaturated group at the end (C1, C
Synthesis Example of 2)] 440 g of sodium hydroxide was dissolved in 5.3 liters of water, and 912 g of bisphenol A and 1.0 g of hydrosulfide were dissolved while maintaining the temperature at 20 ° C. To this, 3.0 liters of methylene chloride was added and phosgene was blown in with stirring, and after 30 minutes, methylene chloride 2 containing 50 g of p-isopropenylphenol 2
500 g was added and phosgene was bubbled in for another 30 minutes.
After blowing phosgene, the mixture was vigorously stirred to emulsify the reaction solution. After emulsification, 60 ml of a 1% methylene chloride solution of triethylamine was added, and stirring was continued for about 1 hour to carry out polymerization. After the polymerization, it was separated into an aqueous layer and an organic layer, and the organic layer was neutralized with acetic acid, and after repeatedly washing with water several times, the solution was dropped into methanol for precipitation, followed by filtration and drying to obtain a white powder. The molecular weight of this polycarbonate (C1) having an unsaturated terminal group was measured by GPC in the same manner as above. The molecular weights are listed in Table 1. The amount of p-isopropenylphenol was 10
An unsaturated group-containing polycarbonate was obtained in the same manner as C1 except that the amount was 0 g (C2). The molecular weight of C2 is listed in Table 1.

[0034]

[Table 1]

Reference Example 5 10 g each of the polycarbonate (C1) polymerized in Reference Example 4 and the polystyrene (S3) polymerized in Reference Example 3
Each was weighed and dissolved in 100 ml of methylene chloride. This solution was placed in a wide-bottom glass container, methylene chloride was vaporized at room temperature, and this was treated at 80 ° C. under reduced pressure for 16 hours to give a film of a resin composition of polycarbonate and polystyrene (thickness: about 0). .5
mm) was obtained. This film was cut into 2 mm square pieces, 5 g of which was taken, and the boiling point (58.6 g) was measured with 250 g of hexafluoroisopropanol using a Soxhlet extractor.
Extraction was carried out for 16 hours. The components dissolved in hexafluoroisopropanol were removed by vaporizing hexafluoroisopropanol with an evaporator, and the solidified components were vacuum dried (80 ° C., 16 hours) and then weighed. Further, a part thereof was dissolved in chloroform and the proton NMR was measured.

Next, the extraction residue of hexafluoroisopropanol was extracted with 125 g of cyclohexane at the boiling point (80.7 ° C.) for 16 hours using the same Soxhlet extractor. The components dissolved in cyclohexane were removed by vaporizing cyclohexane with an evaporator, and the solidified components were vacuum dried (80 ° C., 16 hours) and then weighed. Further, a part thereof was dissolved in chloroform and the proton NMR was measured. The results are listed in Table 2. From Table 2 it is clear that the polycarbonate is virtually completely extracted with hexafluoroisopropanol. It is also clear that polystyrene is virtually completely extracted with cyclohexane. Further, it is clear from the results in Table 2 that polycarbonate is not substantially extracted with cyclohexane, and polystyrene is not substantially extracted with hexafluoroisopropanol.

[0037]

[Table 2]

Reference Example 6 Pellets of the resin composition of Example 1 were subjected to fractional extraction using hexafluoroisopropanol and cyclohexane in the same manner as in Reference Example. 5.23 g of pellet was used for extraction. In this case, components that were not extracted remained in both hexafluoroisopropanol and cyclohexane. From the NMR measurement results, it was found that this was a component (block copolymer) in which a polycarbonate component and a vinyl polymer component were chemically bonded. N
According to the result of MR analysis, the weight% ratio of the polycarbonate component and the polystyrene component of the block copolymer is as shown in Table 3. Table 3 also shows these results.

[0039]

[Table 3]

Next, a resin composition was actually manufactured and various performances were evaluated. The polycarbonates used were C1 and bisphenol A and carbonic acid having a number average molecular weight of 20,000 (manufactured by Mitsubishi Gas Chemical Co., Inc., Iupilon 3000, which is referred to as C2), and the vinyl-based polymer was S1 listed in the reference example. It is S3. In the examples and comparative examples, performance evaluation was performed by the following method. Extraction amount of hexafluoroisopropanol Using about 5 g of the resin composition, 250 parts by weight of hexafluoroisopropanol was used, and extraction was performed at the boiling point for 16 hours using a Soxhlet extractor. The amount of hexafluoroisopropanol extracted from the resin composition was defined as a value (expressed as a percentage) obtained by dividing the weight of the extracted components by the weight of the entire resin composition.

Cyclohexane extraction amount The residue extracted with hexafluoroisopropanol was 12
Using a Soxhlet extractor with 5 g of cyclohexane,
Extraction was performed at that boiling point for 16 hours. The amount of cyclohexane extracted from the resin composition was defined as a value (expressed in%) obtained by dividing the weight of the extracted components by the weight of the entire resin composition.

Weight Ratio of Polycarbonate Component to Polystyrene Component in Block Copolymer (PC / PS) The residue extracted with hexafluoroisopropanol and cyclohexane from the resin composition was dissolved in chloroform, and the polycarbonate component was determined by NMR measurement. The weight% ratio with the polystyrene component was determined.

Light transmittance After pellets of the resin composition were vacuum dried at 80 ° C. for 16 hours, the cylinder temperature was 260 ° C. (however, 280 in Comparative Example 1).
C., and Comparative Example 2 used a cylinder temperature of 200.degree. ), Injection molding is performed at a mold temperature of 80 ° C, and one side is 5c.
A test piece having a thickness of 3 mm and a thickness of 3 mm was prepared. As a molding machine, a 125/75 MST type molding machine manufactured by Mitsubishi Heavy Industries, Ltd. was used. Using this test piece, the total light transmittance was measured based on ASTM D1003. The measurement was performed using a Nippon Denshoku SZ-Σ80 type colorimeter. Thereafter, the molding complied with this condition.

Birefringence: A pellet of the resin composition was dissolved in methylene chloride to prepare a 20 wt% solution, which was manufactured by Yasuda Seiki Co., Ltd.
film applicator No542-AB-
A 100 μm thick film was made using S. The film was left to stand at room temperature for 12 hours and then dried in a vacuum dryer at 100 ° C. for 12 hours to remove the solvent. This film was stretched 10% to 50% at 215 to 220 ° C. using a hot air circulation type uniaxial stretching device manufactured by Satake Chemical Machinery Co., Ltd., and the birefringence of the film was measured with an optical-pol polarization microscope (wavelength 546 nm) manufactured by Nikon Corporation. did.

Bending Strength and Flexural Modulus Injection molding was carried out in the same manner as in the measurement of light transmittance,
A 1/8 inch bending test piece was prepared. The flexural strength and flexural modulus of the obtained test piece were measured based on ASTM D790.

Izod Impact Test An Izod impact test was conducted using the above test piece. The measurement was performed based on ASTM D256.

Deflection Temperature Under Heat Load (HDT) The deflection temperature under heat load (HDT) was measured using the above test piece. The measurement was performed based on ASTM D648. The load was 18.6 kg / cm ² .

Melt Viscosity Using a Koka type flow tester, measurements were made at the temperatures shown in Tables 4, 5 and 6 at a shear rate of 1000 sec ⁻¹ .

Examples 1 to 4 The raw materials having the formulations shown in Table 4 were vacuum dried at 80 ° C. for 16 hours, and then 0.01 part by weight of zinc acetate was added to 100 parts by weight of the raw material to prepare a twin screw extruder ( (PCM45, made by Ikegai Steel Co., Ltd.)
Melt kneading at a cylinder temperature of 260 ° C. and extruding,
This was cut into pellets. In each case, good pelletization was possible. During the melt-kneading, the pressure was reduced to 50 mmHg or less using the vent port of the cylinder. The extraction amount of hexafluoroisopropanol and cyclohexane was measured using the pellets of the obtained resin composition. Various test pieces were obtained using the obtained pellets and various performance evaluations were performed. The results are shown together in Table 4.

[0050]

[Table 4]

Comparative Examples 1 to 4 The raw materials having the formulations shown in Table 5 were vacuum dried at 80 ° C. for 16 hours, and then a twin-screw extruder (PCM45, manufactured by Ikegai Iron & Steel Co., Ltd.) was used. Example 2 is 200 ° C., Comparative Example 3
And 4 were melt-kneaded at a cylinder temperature of 260 ° C., extruded, and cut into pellets. In each case, good pelletization was possible. During the melt-kneading, the pressure was reduced to 50 mmHg or less using the vent port of the cylinder. The extraction amount of hexafluoroisopropaol and cyclohexane and the like were measured using the pellets of the obtained resin composition.
Various test pieces were obtained using the obtained pellets and various performance evaluations were performed. The results are shown together in Table 5.

[0052]

[Table 5]

Example 5 C2 produced in Reference Example 4 (500 g), styrene monomer (1000 g) and methyl ethyl ketone (50 g) were placed in a pressure-resistant reaction tank, and after nitrogen substitution, the temperature was raised to 120 ° C. with stirring and n-dodecyl mercaptan was added. Was reacted for 2 hours while adding 300 g of a styrene monomer solution containing 2 g of. After completion of the reaction, the reaction product was dropped into methanol to cause precipitation, which was filtered and dried to obtain a white powder. The obtained white powder resin composition was vacuum dried at 80 ° C. for 16 hours, and then melt-kneaded and extruded at a cylinder temperature of 260 ° C. using a twin-screw extruder (PCM45, manufactured by Ikegai Iron & Steel Co., Ltd.) and cut into pieces. It was made into pellets. It was possible to pelletize satisfactorily. During the melt-kneading, the pressure was reduced to 50 mmHg or less using the vent port of the cylinder. The pellets of the obtained resin composition were used to measure the amount of extraction with cyclohexane and hexafluoroisopropanol. Also, various test pieces were obtained using the obtained pellets, and various performance evaluations listed in Table 6 were performed.
The results are shown together in Table 6.

Comparative Example 5 A resin composition was obtained in the same manner as in Example 5 except that C1 produced in Reference Example 4 was used. Various performance evaluations were performed in the same manner as in Example 5. The results are listed in Table 6.

Comparative Example 6 A resin composition was obtained in the same manner as in Examples 1 to 4 except that the raw materials having the formulations shown in Table 4 were used. Various performances of the obtained resin composition were evaluated in the same manner as in the examples. The results are listed in Table 6.

[0056]

[Table 6]

[0057]

As shown concretely in the examples, the resin composition of the present invention is mainly composed of a block copolymer in which a polycarbonate component and a polystyrene component are chemically bonded, and is a homopolymer of polycarbonate or vinyl polymer. By not containing more than a specified amount, the transparency is excellent, the birefringence is greatly reduced, and excellent mechanical properties and moldability are provided. Further, the resin composition of the present invention is suitable for optical equipment such as an optical disk, an optical fiber, an optical card protective film or a lens due to the above excellent characteristics.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Megumi Ogasa 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Ltd. Central Research Laboratory

Claims (1)

[Claims] 1. (a) Polycarbonate component 20 to 80
It comprises a block copolymer in which 80 wt% to 80 wt% of a vinyl-based polymer component is chemically bonded, a homopolymer of (b) a polycarbonate, and a homopolymer of a (c) vinyl-based polymer. 1), (2)
And a resin composition satisfying the formula (3). 50 wt% ≤ (a) <100 wt% (1) 0 wt% <(b) ≤ 30 wt% (2) 0 wt% <(c) ≤ 20 wt% (3)