JPH10158348A - Impact resistant styrene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an impact resistant styrene-based resin composition extremely superior balance between an impact strength and gloss used in a wide range of household electric appliance, etc., by performing a radical polymerization of an aromatic vinyl monomer using a specific gummy polymer. SOLUTION: This composition is obtained by performing a bulk, bulk suspension or solution polymerization of (A) 75-98 pts.wt. aromatic vinyl monomer or mixture of the aromatic vinyl monomer with a monomer consisting essentially of a monomer copolymerizable therewith, and (B) 2-25 pts.wt. gummy polymer. The component B includes a low molecular polymer added thereto, prepared by reacting a mixture of (i) a conjugated dienic compound and (ii) a polyvinyl aromatic compound with (iii) an organic lithium compound in 0.1-2.0 molar ratio of component (ii)/component (iii) in a hydrocarbon solvent, and having 2-40wt.% content of total component (ii), 500-10,000 weight average molecular weight and 1.2-3.5 molecular weight distribution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an impact-resistant styrenic resin composition having an excellent balance between gloss and impact strength, and a method for producing the same.

[0002]

2. Description of the Related Art Impact-resistant styrenic resins are used in home appliances,
With various applications such as OA equipment, housing and other parts of household electrical equipment, axle parts, office equipment parts, daily miscellaneous goods and toys, better various properties are required, There is a strong demand for an impact-resistant styrenic resin having an excellent balance between properties and impact resistance. Impact-resistant styrenic resin is produced by dissolving polybutadiene rubber and styrene-butadiene copolymer rubber in styrene monomer as a rubbery polymer, and agitating, mass polymerization or mass-suspension polymerization. Is common.
In particular, polybutadiene rubber is widely used for imparting excellent impact resistance.

[0003] In general, the impact resistance can be improved by increasing the content of the rubbery polymer. However, a styrene-based resin containing an increased amount of the rubbery polymer has an improved impact strength, but has a higher gloss. Decrease. On the other hand, the gloss can be improved by reducing the content of the rubber-like polymer or by making the particles of the rubber-like polymer dispersed in the resin finer, but the impact resistance is significantly reduced.

Heretofore, as a method for improving the impact-resistant styrene resin, there are specified a solution viscosity of a conjugated diene-based polymer (Japanese Patent Publication No. 58-4934), Specification of relations
JP-A-44188), and specification of the relationship between the solution viscosity of a conjugated diene polymer and the tensile elastic modulus and swelling degree of a crosslinked organic peroxide (JP-A-60-25001). However, in these methods, the balance between impact resistance and gloss is improved as compared with the case where conventional polybutadiene is used, but it is not always satisfactory.

On the other hand, Japanese Patent Application Laid-Open No. 61-143415,
JP-A-63-165413, JP-A-2-1321
No. 12, JP-A-2-208312 and the like propose a method for improving impact resistance and appearance characteristics by using a styrene-butadiene block copolymer having a specific structure. However, when these methods are examined in detail, it has been found that there is no practically satisfactory balance between impact resistance and appearance characteristics.

[0006] As another impact-resistant styrene resin, a rubber-modified styrene-acrylonitrile copolymer generally called an ABS resin is known. Conventionally, ABS
The resin was produced by an emulsion polymerization method in which styrene and acrylonitrile were graft-polymerized to a rubber latex adjusted to a desired particle size and a desired degree of crosslinking, and were advantageous in terms of gloss and impact resistance. However, the emulsion polymerization method can provide an ABS resin excellent in gloss, impact strength, and rigidity, requires complicated processes, consumes a large amount of energy, is not economical, and requires wastewater treatment. There was a problem.

Recently, a mass AB obtained by dissolving a rubbery polymer in a mixture of styrene and acrylonitrile and performing bulk polymerization or bulk-suspension polymerization or solution polymerization with stirring.
The S resin has attracted attention because it has little impurities such as an emulsifier in the resin and is hardly discolored or colored, and is economically advantageous because there is no need for wastewater treatment or the like. However, since the mass ABS resin has a large dispersed rubber particle diameter and the grafting of styrene and acrylonitrile on the rubbery polymer is not sufficient, the gloss and impact strength are lower than those of the ABS resin obtained by the emulsion polymerization method. It had disadvantages such as inferiority.

As a method for remedying such a defect, a method using a rubbery polymer having a low solution viscosity (JP-A-63-1)
No. 99717, JP-A-63-207803), a method using a specific styrene-butadiene block copolymer (JP-A-2-185509), and the like. However, these methods have not been able to provide a satisfactory mass ABS resin in terms of balance between gloss and impact strength.

[0009]

As described above, since impact resistance and gloss are contradictory properties, it is difficult to improve the conflicting balance between excellent impact resistance and excellent gloss to a satisfactory degree. However, an object of the present invention is to solve the above-described problems and to obtain an impact-resistant styrene-based resin composition having an excellent balance between physical properties of impact resistance and gloss. .

[0010]

In the present invention, as a result of detailed studies on obtaining an impact-resistant styrenic resin having an excellent balance between physical properties of impact resistance and gloss, no prior art toughening agent has been studied. By using a conjugated diene-based polymer having a specific structure, it has become clear that the above object is achieved, and the present invention has been completed.

That is, the present invention relates to a rubbery polymer 2 comprising 75 to 98 parts by weight of a mixture of an aromatic vinyl monomer or a monomer mainly composed of a monomer copolymerizable with an aromatic vinyl monomer. To 25 parts by weight of a styrene-based resin composition obtained by radical polymerization of a bulk polymerization method, a bulk suspension polymerization method, or a solution polymerization method, wherein the rubbery polymer is a hydrocarbon solvent, A mixture of a conjugated diene compound and a polyvinyl aromatic compound was reacted with an organolithium compound in a molar ratio of polyvinyl aromatic compound / organic lithium compound in the range of 0.1 to 2.0 to prepare a mixture. The aromatic compound content is 2 to 40% by weight. (2) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 500.
(3) a conjugated diene-based polymer provided with a low-molecular polymer having a molecular weight distribution (Mw / Mn) of 1.2 to 3.5,

(A) Weight average molecular weight (M) in terms of polystyrene measured by gel permeation chromatography
(B) a molecular weight distribution (Mw / Mn) of 1.1 to 3.0 (C) a total aromatic vinyl compound content of 50% by weight or less (D) an aromatic vinyl having a block The compound content is less than 10% by weight of the total aromatic vinyl compound content. (E) A conjugated diene-based polymer having a ratio of a molecular weight part twice or more of a peak molecular weight (Mwp) of 20% by weight or less. And an impact-resistant styrenic resin composition.

Hereinafter, the present invention will be described in detail. The production of the living anionic polymer used for producing the conjugated diene polymer of the present invention is carried out by reacting a mixture of a conjugated diene monomer and a monomer containing a polyvinyl aromatic compound with an organolithium compound. Is done. The first method for producing a living anionic polymer of the present invention comprises the steps of: preparing a mixture of a monomer containing a conjugated diene monomer and a polyvinyl aromatic compound in a hydrocarbon solvent containing a polar compound; Is produced by completing the reaction in the presence of

In the second production method, 1 to 99% by weight, preferably 1% by weight of the total amount of the conjugated diene monomer in a hydrocarbon solvent is used.
A reaction of a mixture of 0 to 80% by weight of a monomer containing a polyvinyl aromatic compound is started in the presence of an organolithium compound, and then the remaining conjugated diene-based monomer is continuously added to the reaction system. After the supply of all the conjugated diene-based polymers has been completed, the reaction is completed. The addition time of the remaining conjugated diene-based monomer can be arbitrarily selected. Alternatively, it is manufactured by supplying the remaining conjugated diene-based monomer in one to several steps and sequentially supplying the same, and after completing the supply of all the conjugated diene-based monomers, completing the reaction.

In the third production method, the total amount of the conjugated diene-based monomer in a hydrocarbon solvent containing a polar compound is 1 to
A mixture of 99% by weight, preferably 10-80% by weight of a monomer containing a polyvinyl aromatic compound is polymerized by the presence of an organolithium compound, and then the remaining conjugated diene-based monomer is added to the reaction system. And the polymerization is completed after the supply of all the conjugated diene-based polymers is completed. The addition time of the remaining conjugated diene-based monomer can be arbitrarily selected. Alternatively, it is manufactured by supplying the remaining conjugated diene-based monomer in one to several steps and sequentially supplying the same, and after completing the supply of all the conjugated diene-based monomers, completing the polymerization.

Examples of the hydrocarbon solvent used for preparing the living anionic polymer include aliphatic hydrocarbons such as butane, pentane and hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, benzene, toluene, xylene, and the like.
Aromatic hydrocarbons such as ethylbenzene and diethylbenzene are used, and one kind or two or more kinds may be arbitrarily combined. Preferred examples include hexane and cyclohexane. Further, as the polar compound to be added to the hydrocarbon solvent used for preparing the living anionic polymer, a tertiary monoamine, a tertiary diamine, a cyclic or chain ether or the like is used.

Examples of tertiary monoamines include trimethylamine, triethylamine, methyldiethylamine,
1,1-dimethoxyamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytriethylamine,
Compounds such as N, N-dimethylformamide diisopropyl acetal, N, N-dimethylformamide, dicyclohexyl acetal and the like can be mentioned.

Examples of tertiary diamines include N, N,
N ', N'-tetramethyldiaminomethane, N, N,
N ′, N′-tetramethylethylenediamine, N, N,
N ′, N′-tetramethylpropanediamine, N, N,
N ', N'-tetramethyldiaminobutane, N, N,
N ', N'-tetramethyldiaminopentane, N, N,
Compounds such as N ′, N′-tetramethylhexanediamine, diperidinopentane, diperidinoethane and the like can be mentioned. Examples of the chain ether include compounds such as dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.

Examples of cyclic ethers include tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-
Bis (2-oxolanyl) propane, 1,1-bis (2
-Oxolanyl) ethane, 2,2-bis (2-oxolanyl) butane, 2,2-bis (5-methyl-2-oxolanyl) propane, and compounds such as 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane. . Among these polar compounds, tertiary diamines such as N, N, N ', N'-tetramethylethylenediamine,
And tetrahydrofuran which is a chain ether is preferred. In using the polar compound, one kind or two or more kinds may be arbitrarily combined.

The amount of the polar compound used is in the range of 30 to 50,000 ppm, preferably 200 to 20,000 ppm, based on the hydrocarbon solvent used in producing the living anionic polymer. . When the amount used is less than 30 ppm, the molecular weight distribution of the obtained living anionic polymer is widened, and when the obtained polymer is used as a modifier for impact-resistant styrenic resin, the balance between gloss and impact strength is reduced. Inferior and not preferred. On the other hand, if the usage is 5
If it exceeds 000 ppm, it is difficult to separate the polar compound from the polymerization solvent in the solvent recovery step when producing a conjugated diene polymer, which is not preferable.

The conjugated diene monomers used for preparing the living anionic polymer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-butadiene.
Pentadiene, 3-methyl-1,3-pentadiene,
1,3-heptadiene, 1,3-hexadiene and the like, and one kind or two or more kinds are used in optional combination.
Preferred monomers include 1,3-butadiene and isoprene. The amount of the conjugated diene monomer is not particularly limited, but may be 3 to 1 mol of the organic lithium compound.
The range of from mol to 100 mol is preferred.

The production of the living anionic polymer having a specific structure used in the present invention may be carried out by using a conjugated diene monomer as an essential component. It is also possible to use a mixture with the monomer as a conjugated diene-based monomer. For example, an anionic polymerization initiator can be prepared using a mixture of an aromatic vinyl-based monomer. Examples of the aromatic vinyl monomer include styrene, p-methylstyrene, α-methylstyrene, 3,5-dimethylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and the like.
One type or a combination of two or more types may be used.

As the organic lithium compound used for preparing the living anionic polymer, n-butyllithium, s
ec-butyllithium, tert-butyllithium, n
Although it is a monoorganic lithium compound such as -propyllithium, iso-propyllithium, or benzyllithium, a monoorganic lithium compound such as n-butyllithium or sec-butyllithium is preferably used.

The monomer containing a polyvinyl aromatic compound used for preparing the living anionic polymer is a polyvinyl aromatic compound alone or a mixture of a polyvinyl aromatic compound and an aromatic vinyl monomer. Examples of polyvinyl aromatic compounds include o, m and p-divinylbenzene, o, m and p-diisopropenylbenzene,
1,2,4-trivinylbenzene, 1,2-vinyl-
3,4-dimethylbenzene, 1,3-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4′-trivinylbiphenyl, 1,2-divinyl-3, 4-dimethylbenzene,
1,5,6-trivinyl-3,7-diethylnaphthalene and the like, which can be used alone or in combination of two or more. In particular, divinylbenzene and diisopropenylbenzene are preferable, and divinylbenzene and diisopropenylbenzene include o-, m-, and p-isomers.
Mixtures of these isomers, divinylbenzene and diisopropenylbenzene, are also practically satisfactory. Examples of the aromatic vinyl monomer include styrene, p-methylstyrene, α-methylstyrene, 3,5-dimethylstyrene,
Ethyl vinyl benzene, vinyl xylene, vinyl naphthalene and the like may be used alone or in combination of two or more.

The content of the aromatic vinyl monomer in the monomer containing the polyvinyl aromatic compound is 100/0 by weight ratio of polyvinyl aromatic compound / aromatic vinyl monomer.
-10/90, preferably 100 / 0-50 /
The range is 50. The amount of the polyvinyl aromatic compound used for adjusting the living anionic polymer is in the range of 0.1 to 2.0 mol based on the organolithium compound. Preferably, 0.15 to 1.5, more preferably 0.2
~ 1.0. A conjugated diene-based polymer obtained by using a living anionic polymer having a polyvinyl aromatic compound / monoorganic lithium compound molar ratio adjusted to less than 0.1 is used as a toughening agent for impact-resistant styrene-based resins. If it does, the balance between gloss and impact strength is inferior, which is not preferable. On the other hand, when it exceeds 2.0, only those having a wide molecular weight distribution of the living anionic polymer can be obtained, and the obtained conjugated diene copolymer is used as a toughening agent for impact-resistant styrene resin. In such a case, giant particles are easily generated, and the gloss is unfavorably reduced.

The total content of the polyvinyl aromatic compound in the living anionic polymer is in the range of 2 to 40% by weight. When the amount is less than 2% by weight, when the obtained polymer is used as a toughening agent for an impact-resistant styrenic resin, the balance between gloss and impact strength is poor, which is not preferable. If it exceeds 40% by weight, only a living anion polymer having a wide molecular weight distribution can be obtained, and gel formation may occur in some cases, which is not preferable. Further, when the obtained polymer is used as a modifier for impact-resistant styrenic resin, giant particles are likely to be generated, and gloss is unfavorably reduced. The temperature at the time of producing a living anionic polymer is 10 ° C to 1 ° C.
It is in the range of 40 ° C, preferably in the range of 35 ° C to 110 ° C. The reaction time generally depends on the reaction temperature during preparation, but ranges from 5 minutes to 24 hours.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of the living anionic polymer prepared by the method of the present invention.
Ranges from 500 to 20,000, preferably 50
0 to 10,000, more preferably 1,000 to 10,000.
It is in the range of 10,000. Weight average molecular weight of 20,0
When a polymer obtained by using a living anionic polymer exceeding 00 is used as a toughening agent for an impact-resistant styrenic resin, the balance between gloss and impact strength is poor, which is not preferable. If it is less than 500, the molecular weight distribution of the living anionic polymer is undesirably wide.

The molecular weight distribution (Mw / Mn) is from 1.2 to
It is in the range of 3.5, preferably 1.2 to 2.5. The molecular weight distribution (Mw / Mn) exceeds 3.5. When a polymer obtained by using a living anionic polymer is used as a toughening agent for an impact-resistant styrenic resin, giant particles are easily formed. The gloss is undesirably reduced. The conjugated diene-based polymer used for producing the impact-resistant styrene-based resin composition of the present invention comprises at least one conjugated diene-based monomer or at least one conjugated diene-based monomer and at least one aromatic It can be produced by subjecting a vinyl monomer to solution polymerization in the presence of the above-mentioned living anionic polymer.

Examples of the conjugated diene monomer include 1,3
-Butadiene, isoprene, 2,3-dimethyl-1,3
-Butadiene, 1,3-pentadiene, 3-methyl-
1,3-pentadiene, 1,3-heptadiene, 1,3
-Hexadiene and the like, used alone or in combination of two or more. Preferred monomers include 1,3-butadiene and isoprene. Examples of the aromatic vinyl monomer include styrene, p-methylstyrene, α-methylstyrene, 3,5-dimethylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and the like. Used. Particularly, styrene is preferred.

The hydrocarbon solvent used in the solution polymerization includes:
Aliphatic hydrocarbons such as butane, pentane and hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene are used. Preferred examples include hexane and cyclohexane. As a method for producing a conjugated diene-based polymer, a method of preparing the living anion polymer of the present invention, subsequently adding a conjugated diene-based monomer and continuing the polymerization reaction,
Further, it can be produced by, for example, a method in which the living anionic polymer of the present invention is added to a hydrocarbon solvent in which a conjugated diene-based monomer is present and the polymerization reaction is continued.

As a method for producing an aromatic vinyl-conjugated diene copolymer, a living anion polymer of the present invention is prepared, and then a conjugated diene monomer is added. , A method of adding an aromatic vinyl monomer and continuing the polymerization reaction, a method of preparing the living anionic polymer of the present invention, and subsequently adding a conjugated diene monomer and an aromatic vinyl monomer and continuing the polymerization reaction, etc. Can be manufactured by Further, the living anionic polymer of the present invention is added to a hydrocarbon solvent in which a conjugated diene monomer is present, and after the polymerization of the monomer is completed, an aromatic vinyl monomer is added to continue the polymerization reaction. It can be produced by, for example, a method in which the living anion polymer of the present invention is added to a hydrocarbon solvent containing a conjugated diene monomer and an aromatic vinyl monomer, and the polymerization reaction is continued.

The polymer used in the present invention is, for example, a compound represented by the general formula (1) c- (B) n (2) c- (AB) n (3) c- (BA) n And B are a conjugated diene polymer or a random copolymer of a conjugated diene and an aromatic vinyl compound, and may have a taper block in which the ratio of the aromatic vinyl compound gradually increases. Represents a main polymer block, c represents a residue of a living anionic polymer, n is an integer of 1 to 10, and may be a mixture of each.) is there.

The conjugated diene-based polymer used in the present invention is a low-molecular-weight polymer having a specific structure, that is, the residual double bond of the polyvinyl aromatic compound in the low-molecular-weight polymer is added to the conjugated diene-based polymer. It was made. As a result, it has been found that it has been found that, when used in an impact-resistant styrene-based resin composition, it is possible to greatly improve the balance between impact strength and gloss of the resin.

Next, the conjugated diene copolymer of the present invention has a weight average molecular weight (Mw) of 10 to 6 in terms of polystyrene measured by gel permeation chromatography.
Limited to the range of 50,000. Preferably, it is in the range of 100,000 to 550,000. More preferably, it is in the range of 20 to 500,000. The weight average molecular weight of the conjugated diene polymer used is 1
When it is smaller than 10,000, when used as a toughening agent for an impact-resistant styrenic resin, the impact strength of the obtained resin is inferior. When a conjugated diene-based polymer having a weight average molecular weight of more than 650,000 is used as a toughening agent for an impact-resistant styrene-based resin, it is not preferable because large particles are easily generated and gloss is reduced. Furthermore, during the production of the impact-resistant styrenic resin composition,
It takes a lot of time to dissolve in the styrene-based monomer and transfer this solution, which causes a serious problem in the production process.

The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably in the range of 1.1 to 3.0. When Mw / Mn exceeds 3.0, when used as a toughening agent for an impact-resistant styrenic resin, the distribution of rubber particle diameters is widened, giant particles are easily formed, and gloss is undesirably reduced. The ratio of the molecular weight portion at least twice the molecular weight (Mwp) at the peak of the molecular weight distribution curve of the conjugated diene polymer of the present invention is 20% by weight or less. Preferably, it is at most 15% by weight, more preferably at most 10% by weight. If it exceeds 20% by weight, when used as a toughening agent for impact-resistant styrenic resins, giant particles are likely to be formed and gloss is undesirably reduced.

The total aromatic vinyl compound content of the conjugated diene polymer of the present invention is 50% by weight or less. If it exceeds 50% by weight, when used as a toughening agent for an impact-resistant styrenic resin, the glossiness of the resin is good, but the impact strength is poor, which is not preferred. The content of the aromatic vinyl compound serving as a block in the conjugated diene polymer of the present invention is less than 10% by weight based on the total aromatic vinyl compound content.

The microstructure of the conjugated diene polymer of the present invention slightly affects the impact resistance of the obtained resin. For example, when butadiene is used as the conjugated diene monomer, the 1,2-vinyl content is 10 to 80.
% And the cis-1,4-content are preferably in the range of 10 to 85%, and especially the 1,2-vinyl content is 12 to 40%.
% Is preferred. If a conjugated diene-based polymer having a 1,2-vinyl content outside this range is used, the resulting impact-resistant styrene-based resin will have poor impact strength.

The method for adjusting the 1,2-vinyl content is not particularly limited, and any conventional method can be used. For example, when polymerizing a conjugated diene polymer, dimethyl ether, diethyl ether, Tetrahydrofuran (THF), bis (2-oxolanyl) ethane, 2,2-bis (oxolanyl) propane, 1,1-
Polymerization is achieved by adding ethers such as bis (oxolanyl) ethane; amines such as dimethylamine; and thioethers such as dimethyl sulfide and diethyl sulfide.

Furthermore, hexamethylphosphoramide (HM
PA) (Japanese Patent Publication No. 43-5904), a method of adding tetramethylethylenediamine (TMEDA) (Japanese Patent Publication No. 42-17199), and a method of adding diethylene glycol dimethyl ether. Further, the 1,2-vinyl bond may be polymerized so as to be uniform in the molecular chain, or may be polymerized so as to gradually decrease along the molecular chain (Japanese Patent Publication No. 47-875). Gazettes), or may be polymerized so as to bond in a block manner (US Pat. No. 3,301,840).

In order to polymerize the 1,2-vinyl bond uniformly in the molecular chain, the polymerization initiation temperature is usually from 30 to 90.
° C., a method of performing polymerization at a constant temperature as much as possible, and a method of performing polymerization at an elevated temperature in order to perform polymerization such that the 1,2-vinyl bond gradually decreases along the molecular chain, That is, a method in which the polymerization start temperature is usually 30 to 80 ° C and the polymerization end temperature is 85 to 120 ° C, a method in which the 1,2-vinyl content regulator is gradually added during the polymerization, and the like are employed.

The impact-resistant styrene resin composition of the present invention is a styrene resin composition containing 2 to 25 parts by weight of the above-mentioned conjugated diene polymer. The effect of improving the impact strength aimed at by the present invention is insufficient, and it is difficult to achieve the object of the present invention. On the other hand, when the amount is more than 25 parts by weight, the impact strength is improved, but the properties inherent in the polystyrene resin, for example, the tensile strength, rigidity, and further the appearance properties such as gloss are unfavorably deteriorated. Further, the viscosity of the graft polymerization solution becomes extremely high, and it becomes difficult to produce the impact-resistant styrene resin composition of the present invention.

The average particle diameter of the conjugated diene polymer particles dispersed in the impact-resistant styrene resin composition obtained in the present invention is preferably adjusted to a range of 0.2 to 2.5 μm. Preferably, it is in the range of 0.1 to 1.5 μm. When the average particle size is less than 0.05 μm, the impact resistance of the resin composition is poor, and when it exceeds 2.5 μm, the gloss of the resin composition is poor, which is not preferable.

The rubber particle diameter of the polymer is adjusted by dissolving the conjugated diene polymer in a mixture mainly composed of an aromatic vinyl monomer or a copolymerizable monomer, and performing bulk polymerization, bulk suspension polymerization, When graft polymerization is performed by solution polymerization, conditions under which shear stress is applied to the rubber solution, for example, the rubber particle diameter can be adjusted by changing the rotation speed of the stirrer,
By using the conjugated diene polymer of the present invention, further small rubber particles can be obtained. The method for obtaining the impact-resistant styrenic resin composition of the present invention is not particularly limited as long as the constitutional requirements of the present invention are satisfied, and a known method can be used.

Usually, the conjugated diene polymer of the present invention is dissolved in a mixture of an aromatic vinyl monomer or a monomer mainly composed of a monomer copolymerizable with the aromatic vinyl monomer, Graft polymerization is performed by bulk polymerization, bulk suspension polymerization, or solution polymerization while stirring so as to apply shearing stress to the rubber solution, and copolymerized with an aromatic vinyl monomer or aromatic vinyl monomer. A preferred method is to obtain an impact-resistant styrene-based resin composition in which the conjugated diene-based polymer is dispersed in the form of particles in a matrix composed of a copolymer mainly composed of possible monomers.

The aromatic vinyl monomer used in the present invention includes α-alkyl-substituted styrenes such as styrene, vinylnaphthalene, α-methylstyrene, α-ethylstyrene, α-methyl-p-methylstyrene, m-methylstyrene, Nucleic alkyl-substituted styrenes such as p-methylstyrene, 2,4-dimethylsterene, ethylvinylbenzene, p-tert-butylbutylstyrene, and halogenated styrenes such as monochlorostyrene, dichlorostyrene, tribromostyrene, and tetrabromostyrene. , P-hydroxystyrene, o-methoxystyrene, etc., and are used as one kind or as a mixture of two or more kinds. Of these, styrene, α-methylstyrene and p-methylstyrene are preferred.

The copolymerizable monomer other than the aromatic vinyl monomer is selected from unsaturated nitrile monomers, (meth) acrylates, and other copolymerizable monomers. is there. Examples of unsaturated nitrile monomers include acrylonitrile, methacrylonitrile, and the like,
Acrylonitrile is preferred.

Examples of (meth) acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate,
Dodecyl acrylate, cyclohexyl acrylate,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate,
Octyl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate and the like can be mentioned, and methyl methacrylate is preferable. Other copolymerizable monomers include acrylic acid, methacrylic acid, vinyl acetate, maleic anhydride, N-methylmaleimide, N-phenylmaleimide and the like.

In obtaining the resin composition of the present invention,
The polymerization may be carried out by adding an inert solvent to a mixture mainly composed of the aromatic vinyl monomer or a monomer copolymerizable with the aromatic vinyl monomer. As the inert solvent, one or more polar solvents such as methyl ethyl ketone and cyclohexanone may be used in addition to ethylbenzene and toluene. The amount of the inert solvent is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the vinyl monomer mixture in which the conjugated diene polymer is dissolved. In the present invention, when radical polymerization of a mixture mainly composed of an aromatic vinyl monomer or a monomer copolymerizable with an aromatic vinyl monomer in which a conjugated diene polymer is dissolved, an organic peroxide is used. The polymerization can also be carried out in the presence.

As the organic peroxide, 1,1-bis (t
Peroxy ketals such as -butylperoxy) cyclohexane and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane; di-t-butyl peroxide, 2,5-dimethyl-2, 5-di (t-
Dialkyl peroxides such as butylperoxy) hexane and dicumyl peroxide; diacyl peroxides such as benzoyl peroxide, m-toluoyl peroxide and lauroyl peroxide; dimyristyl peroxydicarbonate and diisopropylperoxydi Peroxydicarbonates such as carbonate;
t-butyl peroxyisopropyl carbonate, t-
Peroxyesters such as butylperoxyacetate, di-t-butyldiperoxyisophthalate and t-butylperoxybenzoate; ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide; p-menthahydroperoxide; Hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azo compounds such as azobisisobutyronitrile and azobiscyclohexanecarbonitrile are used. These can be used alone or in combination of two or more.

The amount of the organic peroxide used is preferably in the range of 10 to 1,000 ppm in the vinyl monomer mixture.
A chain transfer agent is used. As a chain transfer agent, for example,
Mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, α-methylstyrene dimer, 1-phenylbutene-2-fluorene, dipentene and chloroform, terpenes, halogen compounds and the like can be used.

In the present invention, known stabilizers such as antioxidants and ultraviolet inhibitors may be added. Examples of the antioxidant include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
2,6-di-tert-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2′-methylenebis (4-ethyl-6-t
-Butylphenol), 4,4'-thiobis (6-t-
Butyl-3-methylphenol), 2,4-bis [(octylthio) methyl] -o-cresol, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], tris (di Nonylphenyl) phosphite, tris (2,4
(T-butylphenyl) phosphite, and the like, in an amount of 0.1 to 100 parts by weight of the resin composition.
The amount is from 0.01 to 5 parts by weight, preferably from 0.1 to 2 parts by weight.

As the ultraviolet stabilizer, for example, 2- (5
-Methyl-2-hydroxyphenyl) pentotriazole, triazoles such as 21 (3,5-di-tert-butyl-2-droxyphenyl) pentotriazole, and pis (2,2,6,6-tetramethyl) Hindered amines such as -4-piperidyl) sebacate, and pt-
Butylphenyl salicylate, 2,2′-dihydroxy-4-methoxybenzophenone and the like. Particularly preferred are triazole-based and hindered amine-based single or combined systems. The addition amount of these ultraviolet stabilizers is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, per 100 parts by weight of the resin composition. Also,
If necessary, it is also possible to add an internal lubricant such as liquid paraffin, mineral oil, organic polysiloxane and the like which are usually used. For example, 0.005 to 10 parts by weight of polydimethylsiloxane, which is an organic polysiloxane, may be added to 100 parts by weight of the resin composition.

The gel content (toluene-insoluble content) in the impact-resistant styrenic resin composition obtained as described above is preferably in the range of 5 to 75% by weight, more preferably 10 to 75% by weight. ５０50% by weight. If the gel content is too small, the impact resistance of the resin composition will be poor. The swelling index of the gel in the resin composition in toluene is preferably in the range of 7 to 15, and more preferably 7 to 12. If the swelling index is too small, the impact resistance is inferior. The control of the swelling index can be adjusted by the final reaction rate and the devolatilization temperature of the unreacted monomer when the vinyl monomer is graft-polymerized by bulk polymerization, bulk suspension polymerization or solution polymerization.

The molecular weight of the matrix resin portion is preferably 70,000 to 400,000, more preferably 100,000 to 300,000 in terms of polystyrene equivalent weight average molecular weight measured by gel permeation chromatography. If it is less than 70,000, the impact resistance is reduced, and if it exceeds 400,000, the fluidity is poor and processing is not preferred. Further, when processing the resin composition obtained by the present invention, a flame retardant and a flame retardant auxiliary can be blended as necessary to give a flame retardant formulation. There are various types of flame retardants, but all known flame retardants are included, and halogen-based flame retardants, phosphorus-based flame retardants, and the like are effective. For example, decabromodiphenyl oxide, tetrabromopisphenol A, oligomers of tetrabromopisphenol A, tris- (2,3-dibromopropyl-1) isocyanurate, ammonium phosphate, red phosphorus, tricresyl phosphate and the like can be mentioned. Can be Examples of the flame retardant auxiliary include antimony trioxide,
Examples include antimony pentoxide, sodium antimonate, antimony trichloride, antimony pentachloride, zinc borate, barium metaborate, and zirconium oxide. Flame retardants are
Preferably, 5 to 40 parts by weight are used per 100 parts by weight of the resin, and the flame retardant aid is preferably 2 to 40 parts by weight per 100 parts by weight of the resin.
20 parts by weight are used.

If necessary, various additives such as a lubricant, a releasing agent, a filler, an antistatic agent, and a coloring agent can be added. Still other thermoplastic resins, such as general-purpose polystyrene, AS resin, ABS resin, AES resin, MBS
Resin, styrene butadiene methacrylic resin, polyphenylene ether, polycarbonate, styrene-butadiene copolymer, methyl methacrylate / styrene copolymer resin, maleic anhydride / styrene copolymer resin, polyamide resin, polyester resin, etc. Good.
By adding these resins, heat resistance, rigidity, impact resistance, appearance, paintability, and the like are imparted, and the resin is blended according to its use.

The impact-resistant styrenic resin composition of the present invention is molded by a processing method such as injection molding or extrusion molding, and can be made into a variety of practically useful products. It is used in a wide variety of applications, such as electrical appliances, cabinets and housings of OA equipment, interior and exterior parts of automobiles, parts of houses and furniture, broadcasting and communication antenna parts, and the like.

[0057]

EXAMPLES Some examples will be shown below to show specific embodiments of the present invention. However, these examples are intended to explain the technical contents of the present invention more specifically, and limit the present invention. Not something. Various measurements were made according to the following methods. [Weight average molecular weight of living anionic polymer] GPC
(Polystyrene equivalent molecular weight) measured and calculated by (gel permeation chromatography). (GPC measurement conditions) Measuring model LC Module 1 solvent manufactured by Waters Solvent Chloroform column Shodex K-801 1 K-802 1 K-803 1 (3 in total) Column temperature 35 ° C Delivery flow rate 1.0 ml / Min Sample concentration 0.1% by weight Sample injection amount 0.1ml Detector Showex RI Shodex RI SE-61

[Weight average molecular weight and peak molecular weight of polymer] These are the molecular weights in terms of polystyrene measured and calculated by GPC (gel permeation chromatography). (GPC measurement conditions) Measurement model LC Module 1 solvent manufactured by Waters THF (tetrahydrofuran) column PL gel manufactured by Polymer Laboratories × 3 Column temperature 35 ° C. Liquid sending flow 0.7 ml / min Sample concentration 0.1 wt% Sample injection amount 0 .1 ml detector Showex Denko Shodex RI SE-61

[Microstructure] The polybutadiene rubber was measured by a Morello method [Chim Ind 41 , 758 (1959)] using an infrared spectrophotometer (FT-IR1650 manufactured by PerkinElmer). The styrene-butadiene copolymer was measured by the Hampton method [Analytical Chemistry, 21 , 923 (1949)]. [Bound styrene content] UV spectrophotometer (Hitachi UV20
0) was measured by a standard method. [Block styrene content] A method of oxidatively decomposing a block copolymer with t-butyl hydroperoxide using osmium tetroxide as a catalyst [IM Kolthoff, et.al., J. Po.
ym. Sci. 1,429 (1946)], was measured using an ultraviolet spectrophotometer (Hitachi UV200), and expressed as a percentage by weight based on the block copolymer before decomposition.

[Izod Impact Strength] The obtained composition was compression-molded to prepare a 3.2 mm thick test piece, which was subjected to JI
It was measured according to SK-7110. [Gloss] The gloss (incidence angle: 60 °) of the gate portion and the end gate portion was measured and averaged according to ASTM D638. [Rubber Particle Diameter] An electron micrograph was taken of the obtained resin by an ultra-thin section method, and 800 to 100 rubber particles in the photograph were taken.
It is the result of measuring the particle diameter of 0 particles and averaging the weight. That is, average rubber particle diameter = Σn D ⁴ / Σn D ³ (n is the number of rubber particles having a particle diameter D)

(Adjustment of Living Anionic Polymer) Adjustment of A to C An autoclave with a stirrer and a jacket having an internal volume of 10 L was washed, dried, and purged with nitrogen, and dried under the conditions shown in Table 1 to obtain 1,3. Butadiene, cyclohexane, tetrahydrofuran and divinylbenzene are added, then n
-Butyllithium was added and reacted at 75 ° C. for 1 hour to prepare. The living anionic polymer prepared under the conditions shown in Table 1 was soluble in cyclohexane and had no gel.
The divinylbenzene used for preparing the catalyst was 56% by weight of an isomer mixture (m-divinylbenzene = 40% by weight, p-
A commercially available divinylbenzene containing 16% by weight of divinylbenzene and the balance of 44% by weight of ethylvinylbenzene was used.

Preparation of DF An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed, dried, and purged with nitrogen. Then, under the conditions shown in Table 1, 80 g of dried 1,3-butadiene, cyclohexane, and tetrahydrofuran were added. Divinylbenzene was added, followed by n-butyllithium. Then the remaining 1,
120 g of 3-butadiene was continuously added to the reactor over 1 hour, and then reacted for 30 minutes to prepare.
The reaction temperature was 75 ° C. The living anionic polymer prepared under the conditions shown in Table 1 was soluble in cyclohexane and had no gel. Commercially available divinylbenzene containing 56% by weight of an isomer mixture (m-divinylbenzene = 40% by weight, p-divinylbenzene = 16% by weight) and the balance of ethylvinylbenzene = 44% by weight was used. .

Preparation of GI An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed, dried and purged with nitrogen. Under the conditions shown in Table 1, 80 g of dried 1,3-butadiene, cyclohexane and divinylbenzene were used. And then n-butyllithium. After that, the remaining 1,3-butadiene 120
g was continuously added to the reactor over 1 hour, and then reacted for 30 minutes to adjust. The reaction temperature was 75 ° C. The living anionic polymer prepared under the conditions shown in Table 1 was soluble in cyclohexane and had no gel.
The divinylbenzene used for preparing the catalyst was 56% by weight of an isomer mixture (m-divinylbenzene = 40% by weight, p-
A commercially available divinylbenzene containing 16% by weight of divinylbenzene and the balance of 44% by weight of ethylvinylbenzene was used. For the preparation of H, m-divinylbenzene was used. The molecular weight distribution curve of the living anionic polymer H is shown by the solid line in FIG.

Preparation of J A living anionic polymer was prepared in the same manner as in Example 1 except that N, N, N ′, N′-tetramethylethylenediamine (TMEDA) was used as a polar compound. Preparation of K A living anionic polymer was prepared in the same manner as in Example 1 except that m-diisopropenylbenzene was used as the polyvinyl aromatic compound. Preparation of LP Under the conditions shown in Table 2, A living anionic polymer was prepared in the same manner as in Example 1. The molecular weight distribution curve of the living anionic polymer N is shown by the dotted line in FIG.

[0065]

[Table 1]

[0066]

[Table 2]

(Examples 1 to 11) (I) Production of butadiene polymer An autoclave equipped with a stirrer and a jacket having an inner volume of 10 L was washed, dried and purged with nitrogen, and then subjected to the conditions shown in Tables 3 and 4. Then, 1,3-butadiene and cyclohexane, which were previously purified and dried, were added, tetrahydrofuran was added as a 1,2-vinyl regulator, and the living anionic polymer shown in Table 1 was further added, and polymerization was started at 60 ° C. did. After the completion of the polymerization, methanol was added to completely inactivate the living polymer. To the polymer solution thus obtained, 2,6-di-tert-butyl-4-methylphenol was added as a stabilizer in an amount of 0.5 part by weight per 100 parts by weight of the polymer, and the solvent was removed by steam stripping. Heat roll (1
(10 ° C.) to obtain a butadiene polymer shown in Tables 3 and 4.

(II) Production of Styrene Butadiene Copolymer An autoclave with a stirrer and a jacket having an internal volume of 10 L was washed, dried and purged with nitrogen, and then purified and dried under the conditions shown in Table 3 in advance. 3-butadiene 400
g, styrene and cyclohexane, then tetrahydrofuran as a 1,2-vinyl regulator, and the living anionic polymer shown in Table 1 was added.
Polymerization was started at ℃. The polymerization conversion of the copolymer is about 20
%, The remaining 1,3-butadiene was further fed into the polymerization system at a constant rate for 10 minutes. After polymerization,
Methanol was added to completely inactivate the living polymer. As a stabilizer in the polymer solution thus obtained,
0.5 parts by weight of 2,6-di-tert-butyl-4-methylphenol was added per 100 parts by weight of the polymer, and the solvent was removed by steam stripping. After dehydration, the resultant was dried by a hot roll (110 ° C.).
Rubber sample No. shown in Table 3 1, 5 styrene butadiene copolymers were obtained.

After washing and drying the autoclave with a stirrer and a jacket having an internal volume of 10 L and purging with nitrogen, 1,3 butadiene, styrene and cyclohexane previously purified and dried were added under the conditions shown in Table 3, and then randomized. Tetrahydrofuran is added as an agent,
The living anionic polymer shown in the table was added, and polymerization was started at 60 ° C. After the completion of the polymerization, methanol was added to completely inactivate the living polymer. The polymer solution thus obtained was used as a stabilizer with 2,6-G tert.
-Butyl-4-methylphenol was added in an amount of 0.5 part by weight per 100 parts by weight of the polymer, the solvent was removed by steam stripping, and after dehydration, the product was subsequently dried by a hot roll (110 ° C.). Sample No. Thus, a styrene-butadiene copolymer No. 8 was obtained.

[0070]

[Table 3]

[0071]

[Table 4]

(III) Production of Impact-Resistant Styrene Resin Composition Next, using the various butadiene polymers shown in Tables 3 and 4 by the bulk polymerization method described below, the impact-resistant styrene resin composition was used. I got Ethylbenzene and styrene were added to the stirrer and the jacketed reactor in the types and ratios shown in Table 5, and then the rubber sample Nos. 2,
As a rubber of 3,6,7,9 to 11 and a stabilizer, n-
Octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate 0.3
Parts by weight and 0.05 parts by weight of t-dodecyl mercaptan were added and dissolved by stirring.

To this, 1 × 10 ^-4 mol of di-tert-butyl peroxide was added per 1 mol of the monomer, and 1
Polymerization was performed at 10 ° C. for 3 hours, 140 ° C. for 5 hours, and 180 ° C. for 2 hours. Furthermore, after heating at 230 ° C. for 30 minutes, unreacted products were removed under reduced pressure, and the obtained polymer was pulverized.
The extruder was used to make pellets. Table 5 shows the physical properties of the obtained impact-resistant styrenic resin composition. As is clear from the results of the examples, it is understood that the impact-resistant styrene resin composition produced using the butadiene polymer of the present invention has an excellent balance between gloss and impact strength.

(IV) Production of ABS Resin Using the same reactor as in Example 1, ethylbenzene, styrene and acrylonitrile were added in the types and ratios shown in Table 5, and then the rubber samples No. 1 and 4,5
0.3 parts by weight of n-octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate and 0.05 parts by weight of t-dodecylmercaptan were added as a rubber and a stabilizer, and stirred. Dissolved. 1 × 10 ^-4 mol of di-tert-butyl peroxide was added to 1 mol of the monomer at 110 ° C.
For 3 hours, at 140 ° C. for 5 hours, and at 180 ° C. for 2 hours. Further, after heating at 230 ° C. for 30 minutes, unreacted products were removed under reduced pressure, and the obtained polymer was pulverized and formed into pellets with an extruder to obtain an ABS resin. Obtained ABS
Table 5 shows the physical properties of the resin composition. It can be seen that the ABS resin produced using the butadiene polymer of the present invention has a small rubber particle diameter and is excellent in balance between gloss and impact strength.

(V) Production of MBS resin Using the same reactor as in Example 1, ethylbenzene, styrene and methyl methacrylate were added in the kinds and ratios as shown in Table 5, and then the rubber sample No. shown in Table 3 was added. . N-octadecyl-3- (3
0.3 parts by weight of ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate and 0.05 parts by weight of t-dodecylmercaptan were added and dissolved by stirring. 1 × 10 ⁻⁴ mol of di-tert-butyl peroxide was added to 1 mol of the monomer, and polymerization was performed at 110 ° C. for 3 hours, 140 ° C. for 5 hours, and 180 ° C. for 2 hours. Further, after heating at 230 ° C. for 30 minutes, unreacted products were removed under reduced pressure, and the obtained polymer was pulverized and formed into pellets with an extruder to obtain an MBS resin.

[0076]

[Table 5]

(Comparative Examples 1 to 6) (I) Production of butadiene polymer A method similar to that of Example 1 was carried out using the living anionic polymers B and E in Table 1 and the living anionic polymer in Table 2. To obtain a butadiene polymer. (II) Production of Impact-Resistant Styrenic Resin Composition The rubber sample No. was prepared in the same manner as in Example 1. 12 ~
Using a rubber of No. 17, an impact-resistant styrenic resin composition was obtained. Table 6 shows the physical properties of the obtained impact-resistant styrene resin composition. When a block copolymer outside the range of the present invention was used, impact strength or gloss was inferior, and an impact-resistant styrene-based resin composition excellent in both was not obtained.

[0078]

[Table 6]

[0079]

The impact-resistant styrenic resin composition of the present invention is different from the conventional impact-resistant styrenic resin composition in that:
Products with remarkably excellent physical properties balance of impact resistance and gloss can be obtained, electronic devices such as TVs and VTRs, home appliances such as air conditioners and refrigerators, general devices such as OA office equipment, stationery,
It can be used in a wide variety of applications such as toys, leisure sports goods, household goods, building materials and housing parts, and food containers.

[Brief description of the drawings]

FIG. 1 is a diagram showing a molecular weight distribution curve of a living anion polymer H and a living anion polymer N.

Claims (1)

[Claims] 1. 75 to 98 parts by weight of a mixture of an aromatic vinyl monomer or a monomer mainly composed of a monomer copolymerizable with an aromatic vinyl monomer, and 2 to 25 parts by weight of a rubbery polymer And an impact-resistant styrene-based resin composition obtained by radical polymerization of a bulk part by a bulk polymerization method, a bulk suspension polymerization method, or a solution polymerization method, wherein the rubbery polymer is a conjugated diene-based resin in a hydrocarbon solvent. The mixture of the compound and the polyvinyl aromatic compound was adjusted by reacting the organolithium compound at a molar ratio of polyvinyl aromatic compound / organic lithium compound in the range of 0.1 to 2.0. (1) All polyvinyl aromatic compounds The content is 2 to 40% by weight. (2) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography is 500.
(3) A rubbery polymer provided with a low molecular weight polymer having a molecular weight distribution (Mw / Mn) of 1.2 to 3.5, wherein the rubbery polymer comprises: (A) a gel The weight average molecular weight (Mw) in terms of polystyrene measured by permeation chromatography is 10
650,000 (B) Molecular weight distribution (Mw / Mn) is 1.1 to 3.0 (C) Total aromatic vinyl compound content is 50% by weight or less (D) Total aromatic vinyl content of block is 50% by weight (E) a rubbery polymer having a ratio of a molecular weight part twice or more the peak molecular weight (Mwp) of not more than 20% by weight of an impact-resistant styrene resin. Composition.