JP3359724B2 - Grafting precursor and method for producing grafted aromatic polycarbonate resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graft precursor comprising an aromatic polycarbonate resin and a vinyl copolymer having a radically polymerizable organic peroxide group in a molecule, and is produced by using the same. The present invention relates to a method for producing a grafted aromatic polycarbonate resin. The grafted aromatic polycarbonate resin obtained by this manufacturing method is characterized by being excellent in transparency and fluidity, so that an injection-molded product having extremely small optical distortion can be obtained. The present invention provides a composition which is widely applicable to various uses and is also useful as a compatibilizer, an adhesive, a paint, a coating agent, and a modifier in a polymer blend.

[0002]

2. Description of the Related Art Conventionally, as a material of a transparent molded product for optical use,
Acrylic resin is known as a material for transparent molded articles for optical use because of its characteristics such as good transparency and fluidity and low birefringence (Japanese Patent Application Laid-Open No. 56-131654 and others). But,
Acrylic resin has a drawback that heat resistance is as low as about 70 ° C., impact resistance is low, and warpage easily occurs due to moisture. In order to eliminate the above-mentioned disadvantages, the viscosity average molecular weight is 15,000.
ポ リ カ ー ボ ネ ー ト 18,000 polycarbonate resin is used as a molding material for disks, lenses, etc.
0553) has been studied, but it still has disadvantages such as insufficient fluidity, and its use is limited. In order to improve the fluidity of the aromatic polycarbonate resin, there is a method in which a vinyl resin such as polystyrene, polymethyl methacrylate, an AS resin, and a maleic anhydride-styrene copolymer is melt-blended with the aromatic polycarbonate resin. It is difficult to reduce the dispersed particle diameter to 1 μm or less due to compatibility, and the dispersion becomes optically non-uniform. Therefore, a method of performing bulk graft polymerization using a vinyl monomer as a solvent for an aromatic polycarbonate resin (Japanese Patent Laid-Open No. 63-1)
96612) was also studied, but in this method 0.2 μm
While the following particle dispersion is achieved, the amount of the washing solvent used is large, and the post-treatment step is complicated. Attempts have also been made on suspension graft polymerization (Japanese Patent Application Laid-Open No. 62-138514), but the grafting efficiency of the obtained resin composition is smaller than that obtained by the bulk polymerization method, and it is a property required as an optical material. There was a problem that a certain haze (turbidity) was large.

Next, a method for producing a graft precursor using a radical polymerizable organic peroxide is disclosed in
70713, JP-A-63-312305, JP-A-63-
312306, JP-A-1-131220, JP-A-1-1-1
38214 discloses a method of impregnating and polymerizing a polypropylene or polyethylene polymer. Further, the method of using these grafted precursors as a thermoplastic resin composition is disclosed in JP-A-1-92252 and JP-A-1-1111.
3449, JP-A-1-113456, JP-A-1-252
660, and JP-A-1-256564. These resins all have a low Tg of a resin impregnated with a vinyl monomer and a radical polymerizable organic peroxide. For example, polypropylene: -8 ° C, polyethylene: -125 ° C (Ency)
cropdia of Polymer Science
ce and Engineering, second
edition, vol. 7, p185), and because it is a water suspension, an impregnation temperature sufficiently higher than the Tg of the resin to be impregnated can be selected, and the movement of the resin molecules becomes active.
It could be sufficiently impregnated and good uniform polymerization could be expected. However, like aromatic polycarbonate resin,
For a resin having a high Tg exceeding 100 ° C., the impregnation temperature cannot be higher than 100 ° C. in an aqueous suspension, so that a vinyl monomer, a radical polymerization initiator and a radical polymerizable organic compound are added to the aromatic polycarbonate resin. Conventionally, it has never been considered to carry out graft polymerization by impregnation with a peroxide or the like.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to impregnate an aromatic polycarbonate resin with a vinyl monomer, a specific radically polymerizable organic peroxide and a polymerization initiator. An object of the present invention is to provide a grafted aromatic polycarbonate resin which can be industrially produced by polymerizing the radical polymerizable organic peroxide to form a grafting precursor, and further polymerizing the same.

[0005]

The inventors of the present invention have studied the above-mentioned grafting precursor and a method for producing a grafted aromatic polycarbonate using the same. As a result, unexpectedly, a vinyl monomer was added to the aromatic polycarbonate resin. Can be provided with a graft precursor obtained by impregnating a specific radical polymerizable organic peroxide and a polymerization initiator, and polymerizing the vinyl monomer and the radical polymerizable organic peroxide after the impregnation, and It was found that the grafted aromatic polycarbonate used could be produced, and the present invention was completed. Thus, although the Tg of aromatic polycarbonate is much higher than that of polypropylene or polyethylene, the mechanism by which such a precursor could be formed by impregnation has not been fully elucidated. It is presumed that the use of a porous aromatic polycarbonate resin having a small particle size as a raw material is one of the reasons.

That is, the first invention of the present invention comprises a mixture of 35 to 95% by weight of aromatic polycarbonate resin particles and 65 to 5% by weight of a vinyl copolymer containing the following active oxygen, A graft precursor, wherein a copolymer is present in the aromatic polycarbonate resin particles. The vinyl copolymer has the formula

Embedded image (Where X is R ₂ , Y is —C ₆ H ₃ R ₇ R ₁₁ , —COOR
₈ , —CN, —OCOR ₉ , or —CH ₂ COOR ₈
Is a hydrogen atom or —COOR ₈ , R ₂ is a hydrogen atom or a methyl group, R ₇ and R ₁₁ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or halogen, and R ₈ is an alkyl having 1 to ₈ carbon atoms. R ₉ represents a cycloalkyl group having 3 to 12 carbon atoms, and R ₉ represents an alkyl group having 1 to 2 carbon atoms. ), And the formula

Embedded image (Wherein R ₁₀ is an alkyl group having 1 to 12 carbon atoms, 3 carbon atoms)
12 cycloalkyl group, or -C ₆ H ₄ shows the R ₇₎ structural units represented by (A ₁₎ and a (A _2), wherein

Embedded image (Wherein, R ₁ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₃ and R ₄ each represent an alkyl group having 1 to 4 carbon atoms, R ₅ represents an alkyl group having 1 to 12 carbon atoms, phenyl Group,
An alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms, and R ₂ is the same as in the above formula (A ₁ ). m is 1 or 2. ) And / or formula

Embedded image (Wherein, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₂ , R ₃ , R ₄ and R ₅ are the same as those in the above formulas (A ₁ ) and (B ₁ )) And n is 0, 1 or 2.)
In a structural unit represented by (B ₁₎ and a random copolymer consisting (B ₂₎ and the structural unit (B ₁₎ and (B ₂₎ units ratio of configuration (A ₁₎ and (A ₂ ) 0.1 to 10 parts by weight per 100 parts by weight and 0.01 to 0.73 parts by weight of active oxygen.

A second invention of the present invention relates to a method for producing a grafted aromatic polycarbonate resin, comprising the steps of (a)
An aqueous suspension of aromatic polycarbonate resin particles is prepared, and (b) one or more vinyl monomers are added to the suspension to obtain 35 to 95% by weight of the aromatic polycarbonate resin, (C) 0.1 to 100 parts by weight of the vinyl monomer.
One or two radical polymerizable organic peroxides of 10 to 10 parts by weight
Species or more and 0.01 parts by weight per 100 parts by weight of the vinyl monomer.
To about 5 parts by weight of a radical polymerization initiator, and (d) adding the vinyl polymer to the aromatic polycarbonate resin under the condition that decomposition of the radical polymerizable organic peroxide and the radical polymerization initiator does not substantially occur. Impregnating a monomer, (e) after impregnation, polymerizing the vinyl monomer and the radical polymerizable organic peroxide to form a vinyl copolymer,
And (f) melt-kneading the grafted precursor at 100 to 300 ° C. to obtain a grafted precursor in which the vinyl copolymer is present in the aromatic polycarbonate resin particles. The present invention relates to the above method, wherein a grafting reaction is performed between the resin and the vinyl copolymer to produce a grafted aromatic polycarbonate resin.

Hereinafter, the configuration of the present invention will be described. The production method of the aromatic polycarbonate resin is the same as the production method of the conventional aromatic polycarbonate resin, that is, the one produced by a solution method such as an interfacial polymerization method, a pyridine method, a chloroformate method, and the transesterification melting method. And
Viscosity average molecular weight 2,000-100,000, preferably 5,000-50,000, especially 6,000-3
000. When manufactured by the solution method,
As a method of solidifying and recovering the aromatic polycarbonate resin from the aromatic polycarbonate resin solution after the reaction,
A method of adding a poor solvent to an aromatic polycarbonate resin solution for precipitation, a method of distilling the solvent from the aromatic polycarbonate resin solution and concentrating the same, and forming a powder, adding a poor solvent to the aromatic polycarbonate resin solution Various methods such as adding the mixture to warm water under heating, suspending the mixture in warm water, distilling off the solvent and poor solvent, solidifying to form a water slurry liquid, and circulating through a wet pulverizer to grind. There is a method,
In the present invention, it is rational and preferable to use the aqueous slurry of the aromatic polycarbonate resin as it is as the aqueous suspension of the aromatic polycarbonate resin.

Preferred examples of the dihydric phenol compound used in the production of the aromatic polycarbonate resin of the present invention include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether and bis (4-hydroxyphenyl) ether. 4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl)
Ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy -3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane,
2,2-bis (4-hydroxy-3-chlorophenyl)
Examples include propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and bis (4-hydroxyphenyl) diphenylmethane. .

There is no problem in using an aromatic polycarbonate resin having a reactive unsaturated terminal group in the present invention. The method for producing an aromatic polycarbonate resin having an unsaturated terminal group described above is a conventional method except that a monofunctional compound having a double bond as a molecular weight modifier or a terminal stopper is used in combination with a conventional terminal stopper. It is produced by the same production method as the aromatic polycarbonate resin, that is, by a solution method such as an interfacial polymerization method, a pyridine method, and a chloroformate method. Monofunctional compounds having a double bond for introducing an unsaturated terminal group include acrylic acid, methacrylic acid,
Unsaturated carboxylic acids such as vinyl acetic acid, 2-pentenoic acid, 3-pentenoic acid, 5-hexenoic acid, 9-decenoic acid and 9-undecenoic acid; acrylic acid chloride, methacrylic acid chloride, sorbic acid chloride, allyl alcohol chlorophoric acid Acid chlorides or chloroformates, such as mate, isopropenylphenol chloroformate or hydroxystyrene chloroformate; unsaturated, such as isopropenylphenol, hydroxystyrene, hydroxyphenylmaleimide, allyl hydroxybenzoate or methyl allyl hydroxybenzoate And phenols having a group. These compounds may be used in combination with a conventional terminal stopper, and usually 1 to 1 mol of the above-mentioned dihydric phenol compound.
It is used in the range of 25 mol%, preferably 1.5 to 10 mol%.

The aromatic polycarbonate resin of the present invention comprises:
The above components are produced as essential components, but the amount of the branching agent is 0.01 to
A branched polycarbonate resin can be used in combination with 3 mol%, particularly in the range of 0.1 to 1.0 mol%. Examples of such branching agents include phloroglysin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl)
Heptene-3,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,1,3,5
-Tri (2-hydroxyphenyl) benzene, 1,
1,1-tri (4-hydroxyphenyl) ethane,
2,6-bis (2-hydroxy-5-methylbenzyl)
-4-methylphenol, α, α ′, α ″ -tri (4
Polyhydroxy compounds exemplified by -hydroxyphenyl) -1,3,5-triisopropylbenzene, and 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin bisphenol , 5,7-bromoisatin bisphenol, 5-bromoisatin bisphenol and the like.

The shape of the aromatic polycarbonate resin of the present invention is preferably a powder or pellet having a particle size of about 0.1 to 5 mm. If the particle size is excessively large, not only is it difficult to disperse in a suspension, but also there is a disadvantage that the impregnation time of a vinyl monomer or the like becomes long. Further, it is more preferable that the material be porous.

The vinyl monomer in the present invention is stable in water, and is preferably insoluble in water and has low affinity with water. For example, a vinyl aromatic monomer, a maleimide, a methacrylate or acrylate monomer, glycidyl methacrylate, acrylonitrile, methacrylonitrile, and one or more selected from the group consisting of vinyl ester monomers are used. Can be As the vinyl aromatic monomer, styrene; o-methylstyrene, p-methylstyrene, α-methylstyrene, o-butylstyrene, p-butylstyrene, 2,4
Alkyl-substituted styrenes such as dimethylstyrene; halogenated styrenes such as chlorostyrene and bromostyrene. Examples of the maleimides include N-alicyclic maleimides such as N-cyclohexylmaleimide; N-aliphatic maleimides such as N-methylmaleimide, Nn-butylmaleimide, N-hexylmaleimide, N-tert-butylmaleimide; -Phenylmaleimide, N- (P-methylphenyl) maleimide, N
-N-aromatic maleimides such as -benzylmaleimide. Examples of the methacrylate or acrylate monomer include alkyl methacrylate or alkyl acrylate exemplified by methyl methacrylate, ethyl methacrylate, butyl acrylate, n-hexyl acrylate, and cyclohexyl methacrylate. As vinyl ester monomers, diethyl fumarate, diisopropyl fumarate,
Fumaric acid esters such as di-n-butyl fumarate and di-2-ethylhexyl fumarate; further, dimethyl maleate, diethyl maleate, diisopropyl maleate;
Maleic esters such as di-n-butyl maleate and di-2-ethylhexyl maleate; and diethyl itaconate, di-n-butyl itaconate, di-2 itaconate
-Itaconic esters such as ethylhexyl.

At least 50% by weight of the vinyl monomer is a vinyl aromatic monomer, preferably styrene or substituted styrene. Also, 50% by weight or less of the vinyl monomer is maleimides and / or vinyl esters, and preferably N-cyclohexylmaleimide or diisopropyl fumarate. The amount of the vinyl monomer used is 65 to 5% by weight of the grafting precursor, preferably 5 to 5% by weight.
0 to 10% by weight.

In the present invention, a molecular weight modifier for a vinyl monomer can be used. Suitable molecular weight regulators include organic sulfur compounds. Examples of the organic sulfur compound include aliphatic or aromatic compounds having 1 to 30 carbon atoms, specifically, n-octyl mercaptan, n-dodecyl mercaptan and the like. Aliphatic mercaptans; aromatic mercaptans, thioglycolic acid and its esters,
Examples include ethylenethioglycolic acid and its esters, ethylenethioglycol, and the like. The amount of the molecular weight modifier used is 0.000 parts per 100 parts by weight of the vinyl monomer.
It is 1 to 5 parts by weight, preferably 0.01 to 1 part by weight.

The radical polymerization initiator has a decomposition temperature of 40 to 90 ° C., preferably 50 to 90 ° C., for obtaining a half life of 10 hours.
80 ° C. Here, the 10-hour half-life temperature is a temperature at which 0.1 mol of a radical polymerization initiator is added to 1 liter of benzene, and the decomposition rate after 50 hours is 50%. Examples of the radical polymerization initiator include diisopropyl peroxydicarbonate, di-n-propylperoxydicarbonate, dimyristyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, di (methoxyisopropyl) peroxydicarbonate, di (2 -Ethylhexyl) peroxy dicarbonate, t-hexyl peroxy neodecanoate, di (3-methyl-3-methoxybutyl) peroxy dicarbonate, t-butyl peroxy neodecanoate, t-hexyl peroxy neohexanoate, t −
Butylperoxyneohexanoate, 2,4-dichlorobenzoyl peroxide, t-hexylperoxypivalate, t-butylperoxypivalate, 3,5
5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cumyl peroxyoctoate, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, m-toluoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyi And 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane. The amount of the radical polymerization initiator used is 0.01 to 5% by weight, preferably 0.05 to 3% by weight, based on the vinyl monomer.

The radically polymerizable organic peroxide used in the present invention has a decomposition temperature of from 90 ° C. to 110 ° C. to obtain a half-life of 10 hours for the radical polymerizable organic peroxide, which is represented by the general formulas (I) and (II). It is a compound represented.

[0018]

Embedded image (Wherein, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are alkyl groups having 1 to ₄ carbon atoms, and R ₅ is a carbon atom having 1 to 2 carbon atoms. 12 alkyl groups, phenyl groups, alkyl-substituted phenyl groups or 3 carbon atoms
And represents 12 to 12 cycloalkyl groups. m is 1 or 2. )

[0019]

Embedded image (Wherein, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are an alkyl group having 1 to ₄ carbon atoms, and R ₅ is a 1 to 4 carbon atom. 12 alkyl groups, phenyl groups, alkyl-substituted phenyl groups or 3 carbon atoms
And represents 12 to 12 cycloalkyl groups. n is 0 or 1 or 2
Is)

Specifically, as the compound represented by (I), t-butylperoxyacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate, 1,1 , 3,3-tetramethylbutyl peroxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-amylperoxy Methacryloyloxyethyl carbonate, t-hexylperoxy methacryloyloxyethyl carbonate,
1,1,3,3-tetramethylbutyl peroxymethacryloyloxyethyl carbonate, cumylperoxymethacryloyloxyethyl carbonate, p-isopropylcumylperoxymethacryloyloxyethyl carbonate, t-butylperoxyacryloyloxyethoxyethyl carbonate, t-amyl peroxyacryloyloxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate,
1,1,3,3-tetramethylbutyl peroxyacryloyloxyethoxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate, t-butylperoxymethacryloyloxyethoxyethyl carbonate, t-amylperoxymethacryloyl Roxyethoxyethyl carbonate, t
-Hexyl peroxymethacryloyloxyethoxyethyl carbonate, 1,1,3,3-tetramethylbutylperoxymethacryloyloxyethoxyethyl carbonate, cumylperoxymethacryloyloxyethoxyethyl carbonate, p-isopropylcumylperoxymethacryloyloxyethoxyethyl Carbonate, t-
Butyl peroxyacryloyloxyisopropyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate, 1,1,3,3-
Tetramethylbutyl peroxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropylcarbonate, p-isopropylcumylperoxyacryloyloxyisopropylcarbonate, t-butylperoxymethacryloyloxyisopropylcarbonate, t-amylperoxymethacryloyloxyisopropylcarbonate , T-hexyl peroxymethacryloyloxyisopropyl carbonate,
1,1,3,3-tetramethylbutyl peroxymethacryloyloxyisopropyl carbonate, cumylperoxymethacryloyloxyisopropyl carbonate,
Examples thereof include p-isopropylcumylperoxymethacryloyloxyisopropylcarbonate.

Examples of the substance represented by (II) include t-butyl peroxyallyl carbonate, t-amyl peroxyallyl carbonate, t-hexyl peroxyallyl carbonate, 1,1,3,3, -tetramethylbutyl peroxyallyl carbonate. , P-menthane peroxyallyl carbonate, cumyl peroxyallyl carbonate, t-butyl peroxymethallyl carbonate,
t-amyl peroxy methallyl carbonate, t-hexyl peroxy methallyl carbonate, 1,1,3,3
-Tetramethylbutyl peroxymethallyl carbonate, p-menthaneperoxymethallyl carbonate, cumyl peroxymethallyl carbonate, t-butylperoxyallyloxyethyl carbonate, t-amylperoxyallyloxyethyl carbonate, t-hexylperoxyallyloxyethyl carbonate , T-butyl peroxy metalaryloxyethyl carbonate, t-amyl peroxy metalaryloxy ethyl carbonate, t-hexyl peroxy metalaryloxy ethyl carbonate, t-
Butyl peroxy allyloxy isopropyl carbonate, t-amyl peroxy allyloxy isopropyl carbonate, t- hexyl peroxy allyloxy isopropyl carbonate, t- butyl peroxy metalaryloxy isopropyl carbonate, t- amyl peroxy metalyloxy isopropyl carbonate, t-hexyl peroxy metalyloxy isopropyl And carbonate. Among them, t-butyl peroxyacryloyloxyethyl carbonate, t-butyl peroxymethacryloyloxyethyl carbonate, t-butyl
Butyl peroxyallyl carbonate and t-butyl peroxymethallyl carbonate.

The amount of the radical polymerizable organic peroxide to be used is 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl monomer. If the amount is less than 0.1 part by weight, it is difficult to exhibit sufficient grafting performance, and if it exceeds 10 parts by weight, the grafting performance is increased, but the formation of gel is also increased.

The vinyl copolymer of the present invention can be obtained by copolymerizing the above-described vinyl monomer and a radically polymerizable organic peroxide. The number average polymerization degree of the vinyl copolymer is 10 to 5,000, preferably 50 to 1,
000. When the number average degree of polymerization is 10 or less, the mechanical properties of the grafted aromatic polycarbonate resin decrease, and when it exceeds 5,000, the moldability of the grafted aromatic polycarbonate resin deteriorates, which is not preferable.

In the present invention, a vinyl monomer, a radically polymerizable organic peroxide, and a radical polymerization initiator are added to an aromatic polycarbonate resin in an aqueous medium, and the radical polymerization is substantially carried out with the radically polymerizable organic peroxide. It is necessary to impregnate under conditions where decomposition of the initiator does not occur. When the radical polymerization initiator is decomposed during the impregnation, the molecular weight of the grafting precursor becomes non-uniform. In addition, when the radical polymerizable organic peroxide is decomposed during the impregnation, the composition of the graft precursor becomes non-uniform, which is not preferable. Vinyl monomer, radically polymerizable organic peroxide, and radical polymerization initiator in an aromatic polycarbonate resin in an aqueous medium,
The following method can be mentioned as a method for impregnating the radical polymerizable organic peroxide and the radical polymerization initiator under conditions that do not substantially cause decomposition. For example, an aromatic polycarbonate resin, a vinyl monomer, a radically polymerizable organic peroxide and a radical polymerization initiator are suspended in an aqueous medium and heated to a temperature at which decomposition of the radical polymerization initiator does not substantially occur. The aromatic polycarbonate resin is impregnated with the monomer, the radical polymerizable organic peroxide and the radical polymerization initiator. In order not to substantially decompose the radical polymerization initiator during the impregnation, the temperature at the time of the impregnation in this case is preferably 5 ° C. or more lower than the 10-hour half-life temperature of the radical polymerization initiator. As another method, an aromatic polycarbonate resin, a vinyl monomer, and a radical polymerizable organic peroxide are suspended in an aqueous medium and heated at a temperature at which decomposition of the radical polymerizable organic peroxide does not substantially occur. Then, a vinyl monomer and a radical polymerizable organic peroxide are impregnated into the aromatic polycarbonate resin. In this case, the temperature at the time of impregnation is preferably lower by at least 5 ° C. than the 10-hour half-life temperature of the radically polymerizable organic peroxide. Then, after lowering to a temperature at which decomposition of the radical polymerization initiator does not substantially occur,
Add a radical polymerization initiator. In any case, it is necessary to prevent decomposition of the radical polymerization initiator and the radically polymerizable organic peroxide during the impregnation in order to make the molecular weight and composition of the grafting precursor uniform. Aqueous media include suspending agents such as polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, polyacrylic acid, sodium polyacrylate and other water-soluble polymers; calcium phosphate, sodium phosphate, potassium phosphate, magnesium oxide and other poorly water-soluble inorganics. Substances can be used as appropriate. The concentration of the reaction components such as the aromatic polycarbonate resin in the aqueous suspension is arbitrary, but usually, the reaction components 5-1 to 100 parts by weight of water are used.
00 parts by weight.

Next, the temperature of the aqueous suspension is gradually raised to a temperature at which the decomposition of the radical polymerization initiator starts, and the polymerization reaction proceeds to form a graft precursor. In the polymerization reaction, the temperature and the time at which the radical polymerization initiator is decomposed by 50% or more and the conversion of the vinyl monomer becomes 50% or more are maintained. The residual amount of the radical polymerization initiator is usually 1 to 50% by weight, preferably 20% by weight or less based on the initial charge amount. After the polymerization reaction, solid-liquid separation is performed, and a grafting precursor is recovered. The obtained graft precursor is washed with water, hot water or the like, if necessary, and dried.

Here, the vinyl resin constituting the grafting precursor must contain 0.01 to 0.73% by weight as the amount of active oxygen. Active oxygen content is 0.
If the amount is less than 01% by weight, the grafting ability of the grafting precursor is extremely reduced, which is not preferable. On the other hand, when the content exceeds 0.73% by weight, the gel-forming ability at the time of grafting increases, which is similarly unfavorable. In this case, the amount of active oxygen can be measured by an iodometry method.

Next, the grafting precursor is added in an amount of 100 to 3
The mixture is melt-kneaded at a temperature of 50 ° C., and the aromatic polycarbonate resin and the vinyl copolymer are grafted to produce a grafted aromatic polycarbonate resin. Melt kneading can be either batch or continuous. The melt-kneading may be carried out at the above temperature, and specific devices include, for example, a Banbury mixer, an extruder, an injection molding machine and the like. It is also possible to recover some unreacted monomers by distillation under reduced pressure during melt kneading. A vinyl monomer which is unstable in water or has high affinity for water, for example, maleic anhydride, acrylic acid, methacrylic acid or the like can be melt-kneaded with the grafting precursor. In this case, it is preferable that these components are mixed in advance, kept for a predetermined time, aged, and uniformly dispersed.

Melting and kneading using the grafted aromatic polycarbonate resin as a compatibilizer to add a normal aromatic polycarbonate resin or a vinyl resin such as polystyrene, polymethyl methacrylate, or AS resin to form a polymer alloy. Is also possible. In this case, 0 to 200 parts by weight of the polycarbonate and 0 to 100 parts by weight of the vinyl resin are kneaded with 100 parts by weight of the grafted aromatic polycarbonate resin. The aromatic polycarbonate resin and vinyl resin used for polymer alloying are not particularly limited, but a styrene resin is particularly preferable as the vinyl resin.

[0029]

【Example】

Example 1 3.4 kg of sodium hydroxide was dissolved in 4.2 L of water.
While maintaining at 0 ° C., 6.6 kg of 2,2-bis (4-hydroxyphenyl) propane (= BPA) and 8 g of hydrosulfite were dissolved. Methylene chloride 2
While adding 8 L and stirring, 260 g of p-tert-butylphenol was added, and then 3.3 kg of phosgene was added to 60 g.
I blew in minutes. After the phosgene blowing was completed, the reaction solution was vigorously stirred to emulsify the reaction solution. After emulsification, 8 g of triethylamine was added, and stirring was continued for about 1 hour to carry out polymerization. The polymerization liquid was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid. The water was washed repeatedly until the pH of the washing became neutral, and 35 L of isopropanol was added to precipitate the polymer. I let it. The precipitate was filtered and then dried under vacuum to obtain a white powdery aromatic polycarbonate resin. As a result of measuring the viscosity of this aromatic polycarbonate resin, the viscosity average molecular weight (Mv) was 16,000. This resin is P
Called C1. 500 g of the powder of the aromatic polycarbonate resin PC1 was placed in a stainless steel autoclave having an inner volume of 5 L, and pure water was 2500 mL. As a suspending agent, polyvinyl alcohol (PVA-224 manufactured by Kuraray Co., Ltd., saponification degree = 88 mol%, 4% concentration) Viscosity (20 ° C.) = 44 cp
s) was added. As a vinyl monomer, 500 g of a styrene monomer was added. Also, 12.5 g of t-butyl peroxymethacryloyloxyethyl carbonate (peromer: manufactured by NOF Corporation, 10 hour half-life temperature of 105 ° C.) as a radical polymerizable organic peroxide, and benzoyl peroxide (radical polymerization initiator) as a radical polymerization initiator 2.5 g of a 10-hour half-life temperature of 74 ° C.) were added. The temperature of the autoclave was maintained at 60 to 65 ° C., and the mixture was stirred for 2 hours to impregnate the aromatic polycarbonate resin powder with styrene, a radically polymerizable organic peroxide, and a radical polymerization initiator.
The temperature was further raised to 80 ° C. and stirring was continued for 7 hours. At this point, the decomposition rate of the radical polymerization initiator reached 78%. The conversion of the styrene monomer was 90%. The amount of active oxygen measured by the iodometry method is
The content was 0.12% by weight per vinyl resin portion. After the polymer powder was separated from the suspension and washed with hot water, the water was thoroughly shaken off. The water content at this time was 8% by weight. The wet powder was supplied to a vented twin-screw extruder having a shaft diameter of 30 mm and L / D = 32, and extruded at a resin temperature of 220 ° C. The obtained pellet was transparent. This pellet is called PC-PS1. Further, the pellet was freeze-ground and a non-grafted styrene monomer was extracted with n-heptane using a Soxhlet extractor, but substantially no monomer was extracted. Further, when extracted with toluene and examined for the amount of styrene homopolymer produced, 0.32 g per 100 g of polymer was obtained.
Of polymer were extracted. Analysis of this by IR confirmed that it was polystyrene. The birefringence of a lens (thickness: 3 mm) obtained by injection-molding the obtained pellet was 10 nm or less, and a lens having very little optical distortion was obtained. The lens had a total light transmittance of 90% and a haze of 0.8%.

Example 2 A grafting reaction was carried out in the same manner as in Example 1 except that 2.5 g of t-butyl peroxymethacryloyloxyethyl carbonate was used as a radical polymerizable organic peroxide.
The amount of active oxygen of the obtained grafted precursor measured by an iodometry method was 0.023% by weight per vinyl resin portion. Further, when the obtained pellet was molded, a pellet having very little optical distortion was obtained. Specifically, the birefringence of the molded lens (thickness: 3 mm) was 10 nm or less, the total light transmittance was 89%, and the haze was 1.0%.

Example 3 A graft reaction was carried out in the same manner as in Example 1 except for the charged ingredients for the graft reaction. The raw materials were charged by placing 500 g of aromatic polycarbonate resin powder in a 5 L stainless steel autoclave, 2,500 mL of pure water, and PVA-22.
1.25 g of 4 was added. 350 g of a styrene monomer was added as a vinyl monomer. Also, 17.5 g of t-butyl peroxymethacryloyloxyethyl carbonate as a radical polymerizable organic peroxide, 2.5 g of benzoyl peroxide as a radical polymerization initiator, and 0.34 g of n-dodecyl mercaptan as a molecular weight regulator were added. The amount of active oxygen of the obtained grafted precursor measured by an iodometry method was 0.25 per vinyl resin part.
% By weight. Further, when the obtained pellet was molded, a pellet having very little optical distortion was obtained. Specifically, the molded lens (thickness: 3 mm) had a birefringence of 10 nm or less, a total light transmittance of 89%, and a haze of 1.1%.

Example 4 In Example 1, instead of 260 g of p-tert-butylphenol, 25 g of p-isopropenylphenol and p
An aromatic polycarbonate resin was obtained in exactly the same manner except that 225 g of -tert-butylphenol was used.
The viscosity average molecular weight (M
v) was 17,000. This resin is called PC2. Thereafter, a grafting reaction was carried out according to Example 1, and the obtained resin was purified. The amount of active oxygen measured by an iodometry method of the grafting precursor obtained in the middle was 0.055% by weight per vinyl resin portion. Also,
When the finally obtained pellet was molded, it was transparent and had very little optical distortion. Specifically, the molded lens (thickness: 3 mm) had a birefringence of 10 nm or less, a total light transmittance of 88%, and a haze of 1.4%.

Example 5 500 g of an aromatic polycarbonate resin PC1 was placed in a 5 L stainless steel autoclave, and pure water 250 g was added.
0 mL, 1.25 g of PVA-224, 500 g of styrene monomer, and t- as a radical polymerizable organic peroxide.
12.5 g of butyl peroxymethacryloyloxyethyl carbonate were added. Thereafter, the temperature of the autoclave was kept at 90 ° C., and the mixture was stirred for 1 hour to impregnate the polycarbonate with styrene and a radically polymerizable organic peroxide. Next, the temperature of the autoclave was lowered to 65 ° C., and 2.5 g of benzoyl peroxide (10-hour half-life temperature 74 ° C.) was added as a radical polymerization initiator. The temperature of the autoclave was maintained at 60 to 65 ° C, and the mixture was stirred for 1 hour to impregnate the aromatic polycarbonate resin powder with the radical polymerization initiator. The temperature was further raised to 80 ° C. and stirring was continued for 7 hours.
Thereafter, the polymer powder was separated from the suspension according to Example 1, washed with hot water, and then the water was shaken off. The amount of active oxygen of the obtained grafted precursor measured by an iodometry method was 0.13% by weight per vinyl resin portion. Furthermore, this wet powder (grafting precursor)
Was supplied to a vent-type twin-screw extruder, and extruded at a resin temperature of 220 ° C. The obtained pellet was transparent. Lens obtained by injection molding of the obtained pellet (thickness 3 mm)
Has a birefringence of 10 nm or less and has a very small optical distortion. The lens had a total light transmittance of 90% and a haze of 0.7%.

Example 6 A graft reaction was carried out in exactly the same manner as in Example 5 except that styrene monomer (500 g) was replaced with styrene monomer (458 g) and cyclohexylmaleimide (42 g). The amount of active oxygen of the obtained grafted precursor measured by an iodometry method was 0.12% by weight per vinyl resin portion. Furthermore, this wet powder (grafting precursor)
Was supplied to a vent-type twin-screw extruder, and extruded at a resin temperature of 220 ° C. The obtained pellet was transparent. Lens obtained by injection molding of the obtained pellet (thickness 3 mm)
Has a birefringence of 10 nm or less and has a very small optical distortion. The total light transmittance of the lens is 90%,
Haze was 0.8%.

Example 7 In Example 5, the suspending agent was changed to sodium polyacrylate 7.5.
g, and the graft reaction was carried out in exactly the same manner except that 500 g of the styrene monomer was replaced with 458 g of the styrene monomer and 42 g of cyclohexylmaleimide. The amount of active oxygen of the obtained grafted precursor measured by an iodometry method was 0.12% by weight per vinyl resin portion. Further, the wet powder (grafting precursor) was supplied to a vent-type twin-screw extruder, and extruded at a resin temperature of 220 ° C. The obtained pellet was transparent. The birefringence of a lens (thickness: 3 mm) obtained by injection-molding the obtained pellet was 10 nm or less, and a lens having very little optical distortion was obtained. The total light transmittance of the lens was 90%, and the haze was 0.8%.

Example 8 500 g of the styrene-grafted polycarbonate resin PC-PS1 obtained in Example 1 and 500 g of the polycarbonate produced in Example 1 were melt-kneaded at 250 ° C. to obtain pellets. When the pellets were injection molded, the molded product was transparent and had little optical distortion. Specifically, the birefringence of the molded lens (thickness: 3 mm) was 10 nm or less, the total light transmittance was 90%, and the haze was 0.8%.

Example 9 500 g of the styrene-grafted polycarbonate resin PC-PS1 obtained in Example 1 was mixed with a commercially available styrene-maleic anhydride copolymer resin (Dilark # 332, MTC
150 g (made by ARCO) were melt-kneaded at 250 ° C. to obtain pellets. When the pellets were injection molded, the molded product was transparent and had little optical distortion. Specifically, the birefringence of the molded lens (thickness: 3 mm) was 10 nm or less, the total light transmittance was 88%, and the haze was 1.5%.

Comparative Example 1 The same operation was performed as in Example 1 except that t-butylperoxymethacryloyloxyethyl carbonate (radical polymerizable organic peroxide) was not added, but the obtained pellets were cloudy. The molded lens had a total light transmittance of 80% and a haze of 40%, and the birefringence could not be measured.

Comparative Example 2 500 g of the polycarbonate produced in Example 1 and a commercially available styrene-maleic anhydride copolymer resin (Dilark #
332) 500 g was melt-kneaded at 250 ° C. to obtain pellets. When the pellets were injection-molded, the molded lenses had large optical distortion. Specifically, the birefringence of a molded lens (3 mm thick) is partially different and is 50 nm.
１００100 nm.

[0040]

According to the present invention, a grafted aromatic compound which is useful as a molding material for an optical disk, an optical lens, etc., a compatibilizer, an adhesive, a paint, etc. in a polymer blend because the grafting is sufficiently performed. A polycarbonate resin can be obtained. For example, when styrene is used as a vinyl monomer, it is particularly suitable as a polycarbonate resin molding material for optics, and when styrene, acrylonitrile or methacrylonitrile is used, a compatibilizer or a surface coating of an aromatic polycarbonate resin is used. Useful as primer for

[0041]

[Table 1]

[0042]

[Table 2]

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tatsuo Iwai 6-1-1, Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory (72) Inventor Motoyuki Sugiura 102 Masafukuda, Minowa-cho, Anjo-shi, Aichi Prefecture Address (56) References JP-A-62-138514 (JP, A) JP-A-63-312305 (JP, A) JP-A-63-270713 (JP, A) JP-A-55-133405 (JP, A) JP-A-2-6514 (JP, A) JP-A-5-65320 (JP, A) JP-A-59-25817 (JP, A) JP-A-55-31882 (JP, A) JP-B-48-25075 (JP, B1) JP 476751 (JP, B1) (58) Fields surveyed (Int. Cl. ⁷ , DB name) C08F 283/02-283/05

Claims (7)

(57) [Claims] 1. Aromatic polycarbonate resin particles 35 to 9
Vinyl copolymer 6 containing 5% by weight and the following active oxygen 6
A graft precursor comprising a mixture of 5 to 5% by weight, and wherein the vinyl copolymer is present in the aromatic polycarbonate resin particles. The vinyl copolymer has the formula: (Where X is R ₂ , Y is —C ₆ H ₃ R ₇ R ₁₁ , —COOR
₈ , —CN, —OCOR ₉ , or —CH ₂ COOR ₈
Is a hydrogen atom or —COOR ₈ , R ₂ is a hydrogen atom or a methyl group, R ₇ and R ₁₁ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or halogen, and R ₈ is an alkyl having 1 to ₈ carbon atoms. R ₉ represents a cycloalkyl group having 3 to 12 carbon atoms, and R ₉ represents an alkyl group having 1 to 2 carbon atoms. ) And the formula (Wherein R ₁₀ is an alkyl group having 1 to 12 carbon atoms, 3 carbon atoms)
12 cycloalkyl group, or -C ₆ H ₄ shows the R ₇₎ structural units represented by (A ₁₎ and a (A _2), the formula ## STR3 ## (Wherein, R ₁ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₃ and R ₄ each represent an alkyl group having 1 to 4 carbon atoms, R ₅ represents an alkyl group having 1 to 12 carbon atoms, phenyl Group,
An alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms, and R ₂ is the same as in the above formula (A ₁ ). m is 1 or 2. ) And / or the formula (Wherein, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₂ , R ₃ , R ₄ and R ₅ are the same as those in the above formulas (A ₁ ) and (B ₁ )) And n is 0, 1 or 2.)
In a structural unit represented by (B ₁₎ and a random copolymer consisting (B ₂₎ and the structural unit (B ₁₎ and (B ₂₎ units ratio of configuration (A ₁₎ and (A ₂ ) 0.1 to 10 parts by weight per 100 parts by weight and 0.01 to 0.73 parts by weight of active oxygen. _2. 50% by weight of the structural units (A ₁ ) and (A ₂ )
The graft precursor according to claim 1, wherein the above is a vinyl aromatic unit. 3. 50% by weight of the structural units (A ₁ ) and (A ₂ )
The graft precursor according to claim 1, wherein the following are maleimides and / or vinyl ester units. 4. A method for producing a grafted aromatic polycarbonate resin, comprising: (a) preparing an aqueous suspension of aromatic polycarbonate resin particles; and (b) adding one or two vinyl monomers to the suspension. By adding the above, 35 to 95% by weight of the aromatic polycarbonate resin and 65 to 5% by weight of the vinyl monomer, (c) 0.1% per 100 parts by weight of the vinyl monomer was further added to the suspension. (D) adding 10 to 10 parts by weight of one or more radically polymerizable organic peroxides and 0.01 to 5 parts by weight of a radical polymerization initiator per 100 parts by weight of the vinyl monomer; (E) impregnating the aromatic polycarbonate resin with the vinyl monomer under a condition that decomposition of the polymerizable organic peroxide and the radical polymerization initiator does not substantially occur; And the radical polymerizable organic peroxide A vinyl-based copolymer is produced by polymerizing the vinyl-based copolymer and a graft-forming precursor in which the vinyl-based copolymer is present in the aromatic polycarbonate resin particles. Is melt-kneaded at 100 to 300 ° C. to cause a grafting reaction between the aromatic polycarbonate resin and the vinyl copolymer to produce a grafted aromatic polycarbonate resin. . 5. The method for producing a grafted aromatic polycarbonate resin according to claim 4, wherein 50% by weight or more of the vinyl monomer is a vinyl aromatic monomer. 6. The method for producing a grafted aromatic polycarbonate resin according to claim 4, wherein 50% by weight or less of the vinyl monomer is a maleimide and / or a vinyl ester monomer. 7. The process for producing a grafted aromatic polycarbonate resin according to claim 4, wherein the impregnation temperature is at least 5 ° C. lower than the 10-hour half-life temperature of the radically polymerizable organic peroxide or radical polymerization initiator.