JPH07196754A - Rubber-like conjugate-diene polymer composition, its production, aromatic vinyl copolymer resin modified with rubber using the composition and production of the resin - Google Patents

Abstract

PURPOSE:To obtain a rubber-like conjugate-diene polymer composition excellent in drying characteristics, molding performance, cold flow characteristics and hot flow characteristics and to provide a producing method thereof, and to obtain an aromatic vinyl copolymer resin modified with the rubber using the composition and to provide a producing method of the resin. CONSTITUTION:This copolymer resin is produced as follows. In the first process, the total amount of an aromatic vinyl monomer (A) to be used and a part of a conjugate diene monomer (B) to be used are added to an aromatic solvent at a weight ratio of 9:1 to 2:8 and polymerized in the presence of 2-60mol.% of the total amount of an organic alkali-metal catalyst (C) to be used, to form a copolymer of a polymer A with the component B having an active terminal. Subsequently in the second process, all of the remaining components and B and C are added to the reaction mixture and the mixture is allowed to polymerize in an organic solvent to obtain a block copolymer of A and B having an active terminal and a conjugate-diene polymer having an active terminal. In the third process, a coupling agent is added to the reaction mixture of polymerization containing these active polymers and 60-99wt.% of the total active polymers are made to react with each other.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a crumb having an appropriate particle size when coagulated by a steam stripping method, improved dehydration and drying properties, and excellent cold flow resistance and hot flow resistance. When dissolved in styrene monomer, the solution viscosity is extremely low, and when used as a component for imparting impact resistance, such as styrene-based resin, it gives an impact-resistant resin with an improved balance of impact resistance and gloss. The present invention relates to a method for producing a conjugated diene-based rubbery polymer composition, a conjugated diene-based rubbery polymer composition obtained by this method, a rubber-modified aromatic vinyl-based copolymer resin using the same, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Styrenic resins are used for various purposes because they are excellent in moldability and physical properties and are inexpensive, and in particular, they are modified with a rubber-like polymer such as polybutadiene. Rubber-modified styrenic resins such as HIPS and ABS resins have excellent properties such as impact resistance and have been widely used in the field of home appliances and the like.

Polybutadiene rubber and styrene-butadiene copolymer rubber have been conventionally used as toughening agents in the production of rubber-modified styrene resins such as HIPS and ABS resins, but polybutadiene rubber is generally superior. Gives impact resistance. Polybutadiene rubber has cis-1, obtained by solution polymerization using a lithium-based catalyst,
There are low cis polybutadiene rubber having a 4 content of about 25 to 45%, high cis polybutadiene rubber having a cis-1,4 content of 90% or more obtained by solution polymerization with a Ziegler-based catalyst, and the like. It is widely used as a useful toughening agent for rubber-modified styrene resins.

However, in recent years, the applications of rubber-modified styrene resins such as HIPS and ABS resins have been diversified, and there is a growing demand for rubber-modified styrene resins having particularly improved impact resistance and gloss. In order to improve the impact resistance, it is sufficient to increase the filling amount of polybutadiene rubber as a toughening agent. However, when the amount of polybutadiene rubber is increased, the impact resistance is improved, but in the rubber-modified styrene resin production process. Not only does the solution viscosity increase, stirring and transportation become difficult, but the surface gloss of the rubber-modified styrenic resin also decreases significantly.

As a method for improving the surface gloss of a rubber-modified styrenic resin, JP-A-51-131590 discloses a method of using polybutadiene rubber having a relatively low solution viscosity. Is not enough. Further, JP-A-58-4934 and JP-A-2-
229818 and the like disclose a method of using a large amount of polybutadiene rubber having an extremely low solution viscosity as a method for improving impact resistance. Although impact resistance is improved by this method, polybutadiene rubber having an extremely low solution viscosity is difficult to coagulate and dry at the time of production.
There are many problems such as easy flow-through and special consideration for packaging and storage method to prevent it.

Various methods have been proposed for using a styrene-butadiene block copolymer to improve the surface gloss and impact resistance of HIPS. As one of them, in Japanese Patent Laid-Open No. 4-198342, activated polystyrene is produced in the first stage polymerization, and in the second stage polymerization, butadiene and a polymerization catalyst are added in the presence of activated polystyrene to continue the polymerization. The use of a rubber composition containing a polystyrene-polybutadiene block copolymer obtained by coupling with silicon tetrachloride after completion of polymerization is disclosed. The disclosed rubber composition is a crumb having an appropriate particle size upon coagulation and is originally easily dehydrated, but there is a problem that dehydration is not sufficient even in the dehydration and drying steps. Further, the styrene-based impact-resistant resin using this rubber composition does not have a sufficient balance between surface gloss and impact resistance, and needs to be improved.

[0007]

In view of such a background, the present inventors have found that crumbs have an appropriate particle size in the coagulation step after polymerization and can be sufficiently dehydrated in the dehydration and drying steps. Develops a method for producing a rubber composition containing a styrene-butadiene block copolymer that enables the production of a styrene-type impact-resistant resin that has an improved balance of surface gloss and impact resistance with improved cold flow properties. As a result of earnestly studying in order to achieve the result, in the above disclosed method, styrene was polymerized in the presence of a specific amount of butadiene during the first-stage polymerization, and the amount of block styrene in the rubber composition containing the obtained block copolymer was determined. By adjusting the amount to a certain amount or less, the above-mentioned problems in production are improved, and by using this rubber component, rubber-modified aromatic vinyl-based copolymerization such as HIPS or ABS resin having a high degree. Found that the resin is obtained, and have completed the present invention based on the findings.

Therefore, an object of the present invention is to allow a polymer composition produced from a polymer solution to be solidified into a crumb having an appropriate particle size by a steam stripping method,
It is an object of the present invention to provide a method for producing a conjugated diene-based rubbery polymer composition having an improved performance with improved dehydration property. Another object of the present invention is to manufacture by such a method,
It is an object of the present invention to provide a conjugated diene-based rubbery polymer composition which is excellent in drying property, moldability and cold flow property and has an extremely low solution viscosity. Further, another object of the present invention is to use this conjugated diene rubbery polymer composition as a rubber component to obtain a rubber-modified aromatic compound such as HIPS or ABS resin having a high balance of impact resistance and gloss. It is to provide a vinyl-based copolymer resin. Furthermore, another object of the present invention is to provide a method for producing a rubber-modified aromatic vinyl-based copolymer resin such as HIPS or ABS resin, which is imparted with such a high balance of impact resistance and gloss. is there.

[0009]

That is, according to the present invention, when an aromatic vinyl monomer and a conjugated diene monomer are polymerized using an organic alkali metal catalyst, the total amount of the aromatic vinyl monomer (A) and the conjugated diene monomer (B The total weight ratio [(A) to (B)] of (3) is in the range of 3:97 to 15:85, and the total amount of the aromatic vinyl monomer (A) used in the first step and the conjugated diene monomer (B) are used. Of (A) to (B) in a weight ratio of 9: 1 to 5: 5, and 2 to 60 mol% of the total amount of the organic alkali metal catalyst used in the organic solvent. It is polymerized below to form a copolymer of an aromatic vinyl polymer having an active terminal and a conjugated diene monomer, and then in the second step, the total amount of the remaining organic alkali metal catalyst and the total amount of the residual conjugated diene monomer are added. Add organic Polymerization in a medium to form a block copolymer of an aromatic vinyl monomer having an active end and a conjugated diene monomer and a conjugated diene polymer having an active end, and a polymerization reaction system containing the active polymer in the third step A coupling agent is added to 60 to 99% by weight of the total amount of the active polymer, and a) the content of the aromatic vinyl monomer is 3 to 15% by weight, and b) the vinyl bond content of the conjugated diene moiety. 10 to 45% by weight, c) the viscosity of a 5% by weight styrene solution is 5 to 30 cps, d) the content of the block aromatic vinyl monomer is 90% or less of the aromatic vinyl monomer content, and e) the content of the coupling polymer component. A method for producing a conjugated diene-based rubbery polymer composition, characterized in that a rubbery polymer composition having an amount of 60 to 99% by weight is obtained.
It is a conjugated diene rubbery polymer composition obtained by this method.

The present invention also relates to an aromatic vinyl monomer,
Alternatively, with respect to 100 parts by weight of a matrix resin composed of a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer, or a copolymer of an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable therewith. A rubber-modified aromatic vinyl-based copolymer resin in which 3 to 30 parts by weight of a rubber component are dispersed in a particulate form, and the above-mentioned matrix resin has an aromatic vinyl monomer content of 60.
˜100% by weight, the vinyl cyanide monomer content is 0 to 40% by weight, and the weight average molecular weight is 60,000 to 180,000 and the molecular weight distribution is 3.
The content of the aromatic vinyl monomer is 3 to 15% by weight, b) the vinyl bond content of the conjugated diene portion is 10 to 45% by weight, and c) 25.
The viscosity of a 5 wt% styrene solution at 5 ° C is 5 to 50 cps,
d) A rubbery material containing a coupling block copolymer having a block aromatic vinyl monomer content of 90% or less of the aromatic vinyl monomer content and e) a coupling polymer component content of 60 to 99% by weight. It is a polymer composition, and the average particle diameter (Dw) of its dispersed particles is from 0.2 to
It is a rubber-modified aromatic vinyl-based copolymer resin characterized by having a thickness of 2 μm.

Further, the present invention provides a monomer mixture 10 having an aromatic vinyl monomer content of 60 to 100% by weight and a vinyl cyanide monomer content of 0 to 40% by weight.
Based on 0 parts by weight, a) the content of the aromatic vinyl monomer as a rubber component is 3 to 15% by weight, b) the vinyl bond content of the conjugated diene portion is 10 to 45% by weight, and c) 5% by weight at 25 ° C. % Styrene solution has a viscosity of 5 to 50 cps, d) the content of the block aromatic vinyl monomer is 90% or less of the content of the aromatic vinyl monomer, and e) the content of the coupling polymer component is in the range of 60 to 99% by weight. A rubber-like polymer composition containing a coupling block copolymer (3 to 30 parts by weight) and a solvent (2 to 100 parts by weight) are mixed to prepare a raw material liquid, and a polymerization initiator and a chain transfer agent are added to the raw material liquid. Then, the polymerization conversion of the above-mentioned monomer mixture is 40 to 9
A method for producing a rubber-modified aromatic vinyl-based copolymer resin, which comprises subjecting a bulk polymerization or a solution polymerization to 0% to remove a volatile component from the obtained polymerization reaction mixture.

The present invention will be described in detail below. First, the conjugated diene rubbery polymer composition of the present invention and the method for producing the same will be described below. As the aromatic vinyl monomer used in the present invention, styrene, o-methylstyrene, p-methylstyrene, α-methylstyrene, vinyltoluene, divinylbenzene, vinylnaphthalene,
Examples thereof include vinyl anthracene, but styrene is particularly preferable. Examples of the conjugated diene monomer used in the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene and the like, but especially 1,3-butadiene and isoprene. Is preferred.

Aromatic vinyl monomer used in the present invention
And the conjugated diene monomer are used (aromatic vinyl monomer: conjugated diene monomer) in a weight ratio of 3:97 to 15:
It is 85, preferably 4:96 to 10:90.
If the weight ratio of the aromatic vinyl monomer is less than 3, it will be difficult to coagulate the obtained rubber-like polymer composition, and the copolymer
The flowability deteriorates and the moldability decreases. On the other hand, when it is higher than 15, the particle size distribution of the dispersed rubber in the resin obtained by using this rubbery polymer composition tends to be wide, and the impact resistance is lowered, which is not preferable.

The organic alkali metal catalyst used in the present invention is typically an organic monoalkali metal catalyst represented by the general formula RM (wherein R is methyl, ethyl, propyl, butyl, amyl, hexyl, etc.). Or an aryl group such as phenyl, xylyl and naphthyl, and M is an alkali metal such as lithium, potassium, rubidium and cesium). Specific examples of the alkali metal catalyst include methyllithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium naphthalene, and lithium anthracene. sec-Butyllithium is commonly used. The organic alkali metal catalyst is usually used per 100 g of a mixture of an aromatic vinyl monomer and a conjugated diene monomer,
It is used in the range of 0.1 to 10 mmol, preferably 0.2 to 7 mmol.

The coupling agent used in the present invention is not particularly limited as long as it can react with an alkali metal at the end of the polymer to form a chain or branched polymer, and the coupling agents known from the prior art are known. Agents are used. For example, silane compounds such as trichloromethylsilane, dimethyldichlorosilane, silicon tetrachloride and tetramethoxysilane; carbonic acid diesters such as diethyl carbonate; divinyl aromatic compounds such as divinylbenzene; halogen compounds such as carbon tetrachloride; tetrachlorotin. Examples thereof include tin compounds. These may be used alone or in combination of two or more.

The polymerization reaction is usually carried out in a hydrocarbon solvent or a solvent which does not destroy the organic alkali metal catalyst such as tetrahydrofuran, tetrahydropyran or dioxane. Hydrocarbon solvents are usually aliphatic hydrocarbons, aromatic hydrocarbons,
It is selected from alicyclic hydrocarbons. Particularly, carbon number 2 to 12
Propane, butane, i-butane, n-pentane, i-
Pentane, n-hexane, cyclohexane, propene,
1-butene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-
Hexene, benzene, toluene, xylene, ethylbenzene and the like are preferable. Two or more kinds of these solvents may be mixed and used.

Further, in the polymerization system, ether compounds such as tetrahydrofuran, diethyl ether, dioxane and diethylene glycol dimethyl ether are used for controlling the microstructure (1,2-bond content) of the conjugated diene unit. A polar compound such as an amine compound such as tetramethylethylenediamine, trimethylamine, triethylamine or pyridine; a phosphine compound such as triphenylphosphine; The amount of these polar compounds used is usually 0 to 30 mol with respect to 1 mol of the organic alkali metal catalyst.

The method for producing the rubber-like polymer composition of the present invention is characterized by carrying out the following three steps in order. First, in the first step, an aromatic vinyl monomer necessary for producing the rubber-like polymer composition of the present invention.
The weight ratio of the total amount of (A) to a part of the conjugated diene monomer (B) (A to B) is in the range of 9: 1 to 2: 8, preferably 9:
An aromatic vinyl polymer having an active terminal, which is charged in a polymerization reactor at a ratio of 1 to 4: 6 and polymerized in an organic solvent in the presence of 2 to 60 mol% of the total amount of the necessary organic alkali metal catalyst. And a conjugated diene polymer-living copolymer is formed. In the first step, the feature of the present invention is to generate a block copolymer having a polymer block chain mainly containing an aromatic vinyl monomer and a polymer block chain mainly containing a conjugated diene monomer. The boundaries between the two block chains do not have to be clearly distinguished.

When the weight ratio (A / B) of the aromatic vinyl monomer (A) to the conjugated diene monomer (B) exceeds 9, the resulting rubbery polymer composition has cold flow properties and steam stripping. The resulting rubbery polymer composition coagulates into a crumb having an appropriate particle size, but the dispersed rubber particle size in the impact resistant resin obtained by using the rubbery polymer composition of the present invention is improved. The distribution is widened and the impact strength is reduced. When the weight ratio (A / B) of the aromatic vinyl monomer (A) to the conjugated diene monomer (B) is lower than 1, the obtained rubber-like polymer composition is solidified by steam stripping from the polymer solution. And becomes crumbs in the form of fine particles, which makes it difficult to apply the dehydration process and the dehydration is insufficient, which is not preferable. Further, the cold flow resistance of the obtained rubber-like polymer composition is also deteriorated.

The amount of the organic alkali metal catalyst is from 2 to 60 of the total amount necessary for producing the rubbery polymer composition of the present invention.
Must be mol%. If it is less than 2 mol%, the dispersed rubber particle size distribution in the impact-resistant resin obtained by using the rubber-like polymer composition of the present invention tends to be large, which is not preferable. On the other hand, when it exceeds 60 mol%, the cold flow of the obtained rubber-like polymer composition is deteriorated and the handling property of the composition is remarkably lowered. Preferably 3 to 50 mol%
Is.

In the next second step, the remaining total amount of the organic alkali metal catalyst is added to the polymerization reaction system in which the living copolymer of the aromatic vinyl polymer having active ends and the conjugated diene polymer produced in the first step is present. Was added, and the remaining total amount of the conjugated diene monomer was charged and polymerized in an organic solvent, and a block copolymer of a copolymer of an aromatic vinyl having an active end and a conjugated diene and a conjugated diene polymer and A mixture of conjugated diene polymers with active ends is formed.

In the final third step, a coupling agent is added to the polymerization reaction system in which the block copolymer having an active end and the conjugated diene polymer having an active end obtained in the second step are added to obtain an active polymer. Coupling coalescence. The amount of the coupling agent used is preferably in the range of 0.1 to 0.5 mol per mol of the organic alkali metal catalyst used for the polymerization, and the content of the polymer component produced by the coupling is the rubber-like polymer composition. It is preferably 60% by weight or more, and more preferably 70 to 99% by weight. If it is less than 60% by weight, the impact resistance of the impact resistant resin using the rubbery polymer composition of the present invention is lowered and the cold flow property of the composition is also deteriorated.

The aromatic vinyl monomer content in the rubbery polymer composition of the present invention obtained by the above method is 3 to 15% by weight, preferably 4 to 10% by weight. If it is less than 3% by weight, the cold flow resistance is poor, and if it exceeds 15% by weight, the impact resistance of the impact resistant resin produced by using the rubber-like polymer composition of the present invention becomes low.

The block aromatic vinyl monomer content is 90% or less of the aromatic vinyl monomer content, preferably 20 to 80%, more preferably 40 to 78% by weight. When it exceeds 90%, the cold-flow property of the rubber-like polymer composition of the present invention is improved, but the dehydration property is deteriorated, and the dispersed rubber particles in the impact-resistant resin obtained by using the composition. The diameter distribution is likely to be widened, impact resistance is lowered, and the balance with gloss is deteriorated. On the other hand, if it is less than 20%, the cold flow property of the composition is deteriorated and the moldability is also deteriorated. The amount of block aromatic vinyl used here is a method of oxidatively decomposing a block polymer with an organic peroxide using OsO ₄ as a catalyst [LM Kolthoff, et al., Polymers
ci., Voll, 429 (1948)].

Further, the rubber-like polymer composition of the present invention has a viscosity of a 5% by weight styrene solution at 25 ° C. of 5 to 50 cp.
s. If this viscosity is lower than 5 cps, the impact resistance of the impact resistant resin containing this as a rubber component is poor, and on the contrary, 5
When it is higher than 0 cps, the gloss becomes poor. The rubber-like polymer composition has a styrene content of 3 to 15% by weight. If the aromatic vinyl monomer content of the rubber component is less than 3% by weight, the cold flow becomes worse. Further, if it exceeds 15% by weight, the impact resistance becomes poor.

The structure of the coupling block copolymer in the above-mentioned rubbery polymer composition of the present invention can be represented by the general formula [(Z- X) _n ] _m Y (where X is a block polymer mainly containing a conjugated diene monomer, Z is a random polymer of a block polymer portion mainly containing a conjugated diene monomer and a conjugated diene monomer / aromatic vinyl monomer) Part or a random polymer part of the conjugated diene monomer / aromatic vinyl monomer and a block polymer part mainly containing the aromatic vinyl monomer, and the content of the aromatic vinyl monomer in the polymer block is 90% or less of the amount of bound styrene. ,
Preferably, it is a copolymer of 20 to 80%, Y represents a residue of the polyfunctional coupling agent, m is an integer of 2 or more and represents the number of functional groups of the polyfunctional coupling agent, and n is n. It is a block copolymer having a linear or branched structure represented by an integer of 1 or more). In addition to this, as the block copolymer, for example, when coupling with a tetrafunctional coupling agent is taken as an example, the active aromatic vinyl monomer conjugated diene monomer block copolymer and the active Since there is a conjugated diene monomer polymer, (X-Z) _1-3 Y (conjugated diene monomer polymer)
A mixture of various coupling block copolymers represented by _3-1 is produced. Therefore, the rubber-like polymer composition of the present invention is a coupling conjugated diene monomer copolymer obtained by coupling various coupling block copolymers and active conjugated diene monomer polymers according to the functionality of the coupling agent used. Composed of a coalesced mixture.

Next, the rubber-modified aromatic vinyl copolymer resin of the present invention will be described. The matrix resin is an aromatic vinyl monomer, or a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer, or a copolymer of an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable therewith. is there. However, the content of the aromatic vinyl monomer is 60 to 100% by weight, the content of the vinyl cyanide monomer is 0 to 40% by weight, and the content of the other vinyl monomers is 39% by weight or less. is there. Those having a vinyl cyanide monomer content of more than 40% by weight have poor fluidity.

As the aromatic vinyl monomer, those mentioned above can be used. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile, α-chloroacrylonitrile, and the like, and other vinyl-based monomers that can be copolymerized with these include acrylic acid esters such as butyl acrylate. Examples thereof include methacrylic acid esters such as methyl methacrylate, maleic anhydride, phenylmaleimide, ethylene, propylene, butadiene and vinyl chloride.

The weight average molecular weight of the matrix resin is 60,000 to 180,000, preferably 95,000.
It is 150,000. If the weight average molecular weight of this matrix resin is less than 60,000, the impact resistance is poor, and if it exceeds 180,000, the fluidity is poor. Furthermore,
The molecular weight distribution (Mw / Mn) of the matrix resin is 3.1.
The following is preferably 2.7 or less. If this molecular weight distribution exceeds 3.1, the impact resistance becomes extremely poor. The weight average molecular weight of the matrix resin in the present invention is the polystyrene equivalent weight average molecular weight determined by gel permeation chromatography (GPC method), and the molecular weight distribution of the matrix resin is determined by the weight average molecular weight. Is a value obtained by calculating the number average molecular weight in the same manner as above and calculating the weight average molecular weight / number average molecular weight.

The rubber-like polymer composition which is the rubber component of the present invention has a coupling block copolymer which is a linear or branched block copolymer, and particularly includes a branched block copolymer. By using the rubber-like polymer composition as the rubber component of the rubber-modified aromatic vinyl-based copolymer resin, its impact resistance is remarkably higher than that of the conventionally known linear polybutadiene rubber or linear styrene-butadiene rubber. The property is improved. This is probably because the branched rubber has a larger molecular weight than linear polybutadiene rubber and linear styrene-butadiene rubber.
A branched random or block SBR coupled with a trifunctional or higher functional coupling agent has been conventionally known as a branched styrene-butadiene copolymer rubber (SBR), but the reason is often the same under the same reaction conditions. Although not understood, it has been confirmed that the branched rubber of the present invention exhibits superior strength physical properties.

The rubber component is dispersed in the matrix resin in the form of particles, and the average particle diameter (Dw) of the rubber dispersed particles is 0.
It is 2 to 2 μm, preferably 0.3 to 1 μm. If the average particle diameter of the rubber dispersed particles is less than 0.2 μm, the impact resistance is poor, and conversely, if it exceeds 2 μm, the gloss property is poor.
The particle size distribution is preferably 2.0 or less, and if it exceeds 2.0, the impact resistance is significantly reduced.

The rubber-dispersed particles containing the copolymer resin component have a good balance between gloss characteristics and impact resistance, and the graft ratio of the copolymer resin component to the rubber-dispersed particles is 0.4 to 0.4. 2.0 is preferable. If the graft ratio is less than 0.4, both the gloss and impact resistance are inferior, and if it exceeds 2.0, the flowability and impact resistance are particularly poor. A swelling ratio of 5 to 15 is preferable, and a swelling ratio of less than 5 gives poor impact resistance and a swelling ratio of more than 10 gives poor gloss.

Next, a method for producing the rubber-modified aromatic vinyl-based copolymer resin of the present invention by solution polymerization will be described. A monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer is graft-copolymerized with a polymerization initiator and a chain transfer agent in the presence of a rubber component and a solvent. Solvents that can be used are benzene, toluene,
Besides aromatic hydrocarbon compounds such as xylene and ethylbenzene, ketone compounds such as acetone, methyl ethyl ketone and acetophenone, and alcohol compounds such as propyl alcohol and phenol can be used, but the aromatic hydrocarbon compounds are used alone. Alternatively, it is preferable to use the aromatic hydrocarbon compound and the ketone compound or the alcohol compound in combination. The amount of solvent used is monomer mixture 1
It is 2 to 100 parts by weight with respect to 00 parts by weight. When the amount of the solvent used is small, the viscosity of the reaction liquid becomes high, so that it becomes difficult to control the formation of the rubber dispersed particles, and when the amount is too large, the efficiency of the polymerization reaction deteriorates.

As the polymerization initiator, it is preferable to add a radical initiator such as an organic peroxide. Examples of the radical initiator used include benzoylperoxide, lauroylperoxide, and tert-butylperoxide.
Oxy (2-ethylhexanonate), 1,1-bis (tertiarybutylperoxy) -3,3,5-trimethylcyclohexane, di-tertiarybutylperoxyhexahydroterephthalate, azobisisobutyrate One or more of ronitrile, azobis-2-methylbutyronitrile and the like can be used. The amount used is not particularly limited, but 0.005 to 0.5 parts by weight is preferable with respect to 100 parts by weight of the monomer mixture. In addition, chain transfer agents include mercaptans, α-methylstyrene dimer, terpyrine and the like. The polymerization reaction is carried out at a polymerization temperature of 8 with proper stirring by a complete mixing tank, a plug flow type reactor, or a polymerization process combining these.
It is preferable to carry out at 0 to 160 ° C.

In the present invention, the molecular weight of the matrix resin can be controlled by changing the type and amount of chain transfer agent and the position of addition. Further, the particle size of the rubber dispersed particles can be controlled by changing the stirring conditions in addition to the type and amount of the chain transfer agent used. That is, when the amount of the chain transfer agent used is increased, the average molecular weight of the matrix resin decreases, and when the stirring power is increased, the average particle size of the rubber dispersed particles tends to decrease.

The resin obtained by using the rubber component of the present invention can be added to, for example, lauric acid amide, stearic acid amide, behenic acid amide, methylenebislauric acid amide, ethylenebislauric acid amide, methylenebisstearic acid amide, ethylene. Additives of fatty acid amides such as bisstearic acid amide, methylene bisbehenic acid amide, and ethylene bisbehenic acid amide, and aliphatic alcoholic additives such as lauryl alcohol and stearyl alcohol. When mixed or mixed in the range of 0.5 to 4% by weight, the dependency of gloss on the mold temperature, that is, the variation of the gloss value with respect to the change in metal temperature during injection molding is significantly reduced. Incidentally, these additives may be added at a stage in the middle of the polymerization process.

The rubber-modified aromatic vinyl copolymer resin obtained by using the rubber component of the present invention includes organic stabilizers such as phosphite, inorganic stabilizers such as calcium and tin, and phenol. -, Sulfide-based antioxidants, benzophenone-based, phenyl salicylate-based UV absorbers, various polysiloxanes such as dimethyl polysiloxane, fatty acid-based, fatty acid amide-based, ester-based, metal soaps and other lubricants, Mold release agent, other fiber reinforcements, inorganic fillers, pigments, plasticizers, antistatic agents, colorants, etc.
Various additives such as flame retardants may be added, but the additives are not limited to these. Furthermore, when these additives are blended with the resin, the additives may be blended alone, or a plurality of types of additives may be blended. Further, it can be blended with another resin and used for molding. Further, these additives may be added at a stage in the middle of the polymerization process.

[0038]

The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

First, examples of the rubber component will be described. Examples 1 to 6 and Comparative Examples 1 to 4 Cyclohexane 700 dehydrated on 2 m ³ of stainless steel autoclave
kg, 5 kg of styrene and 0.56 kg of butadiene are charged. Furthermore, 0.1 mol of tetramethylethylenediamine was added to 1 mol of n-butyllithium, and 1.847 mol of a polymerization initiator n-butyllithium was added thereto.
Polymerization was carried out at 5 ° C. for 1 hour and 30 minutes. Then, 1.696 mol of n-butyllithium and 94.44 g of butadiene were added, and polymerization was carried out at 75 ° C. for 2 hours to form a polybutadiene block from the active end of polystyrene having an active end, and the added n-butyl was added. Polybutadiene was newly formed by lithium.

After completion of the polymerization, 0.25 mol of tetramethoxysilane was added to 1 mol of n-butyllithium in the polymerization reaction system, and the coupling reaction was further carried out for 3 hours. Thereafter, 0.2 liter of methanol was added to stop the reaction. A rubber-like polymer composition 100 is added to this polymerization reaction system.
After 4-methyl-di-t-butylphenol was added at a ratio of 0.2 parts by weight to parts by weight, the contents of the autoclave were poured into warm water, and degassed while blowing a steam. Coagulation with solvent was performed. The hydrous rubbery polymer composition thus obtained was cut and dried at 60 ° C. for 24 hours under reduced pressure.

The rubbery polymer compositions of Examples 1 to 6 and Comparative Examples 1 to 4 thus obtained were evaluated by the following methods. The results are shown in Table 1. 1) The styrene content and the vinyl content of the polybutadiene portion are determined by infrared spectroscopy [Hampton, Anal. Chem., 21 ,
923 (1949)].

2) The weight average molecular weight, the coupling ratio, and the molecular weight of the styrene block part are determined by gel permeation chromatography (GPC, column: Toso G4).
000H, G5000H; measurement temperature: 38 ° C .; flow rate:
1.0 ml / min; solvent: tetrahydrofuran). The calibration curve was prepared using standard polystyrene manufactured by Toso Co., Ltd., and the weight average molecular weight was determined from this.

3) Cold flow of rubber-like polymer composition
In order to evaluate the property, the rubber-like polymer composition was compression molded (compression pressure: 160 kg / cm ² ; temperature: 60 ° C .; compression time: 30 seconds; leaving time: 3 hours) and left for 3 hours to obtain a molded product. The appearance state of was evaluated according to the following criteria. Evaluation Criteria A: The shape immediately after molding is retained, and the corners of the molded product remain without sagging. B: The shape immediately after molding is retained, but the corners of the molded product are slightly sagging. C: The shape is slightly deformed, and the corners of the molded product hang down. D: The shape immediately after molding cannot be retained and the flow occurs.

4) In order to evaluate the hot flow property of the rubber-like polymer composition, a tensile test piece No. 3 type dumbbell described in JIS K6301 was molded, and one end of the No. 3 type dumbbell was placed in a high temperature tank at 100 ° C. It was fixed and hung, and in order to shorten the measurement time, a weight was attached to the remaining end of the dumbbell, and the time until it extended 100 mm was measured and evaluated.

5) In order to evaluate steam stripping property and dehydration property, a polymer solution of the rubber-like polymer composition shown in Table 1 (polymer concentration 20% by weight) was prepared. These polymer solutions are sent to the coagulation tank at a rate of 200 liters / hour. 180 before polymer solution enters coagulation tank
A steam at a temperature of ° C was sprayed onto the polymer solution at a rate of 250 kg / hour. Temperature of coagulation tank is 105 ℃, pressure is 1k
Water and steam were fed into a coagulation tank so that the g / cm ² G and crumb concentration were 3% by weight, the polymerization solvent was stripped, and the slurry suspended in hot water of the target polymer mixture was continuously added. Manufactured to. Crumbs were sampled and the appearance was evaluated according to the following criteria. Further, the obtained crumbs were put into an extrusion type dehydrator, the water content at the outlet of the dehydrator was measured, and evaluation was made based on the following criteria in consideration of the crumb shape and the water content of the dehydrator. Also, dry using an expansion type dryer,
The water content after drying was measured. The results are shown in Table 1.

Evaluation Criteria A: The rubber-like polymer particles had the size of the little fingernail (corresponding to the above-mentioned appropriate particle diameter, which is a preferable particle diameter), and were applied to the stripper wall and the stirrer. There is very little adhesion and the transfer pump does not clog. It also has excellent dehydration properties. B: The rubber-like polymer particles have the size of a thumb nail and are larger than those of A, but the amount of adhesion to the stripper wall and the stirrer is small and the transfer pump does not clog. Dehydration is normal. C: The rubber-like polymer particles have a large fist and adhere to the wall of the stripper and the stirrer to cause clogging in the transfer pump. Dehydration is poor. D: The rubber-like polymer particles have the size of a little fingernail, and the adhesion to the wall of the stripper and the stirrer is extremely small, and they are not clogged by the transfer pump. However, the dehydration property is extremely poor.

[0047]

[Table 1]

Next, examples of the rubber-modified styrene resin using the rubber component of the present invention will be described. [Examples 7 to 9] 30 parts by weight of ethylbenzene and 1 part of rubber component with respect to 100 parts by weight of a monomer mixture having a styrene content of 75% by weight and an acrylonitrile content of 25% by weight.
3 to 18 parts by weight, an organic peroxide-based polymerization initiator is 0.0
85 to 0.1 parts by weight, and t-dodecyl mercaptan (chain transfer agent) in the range of 0.20 to 0.5 parts by weight, respectively, are mixed in the raw material liquid, and the complete mixing tank and the plug flow are mixed.
In a continuous polymerization process that combines type reactors in series,
After continuous solution polymerization until the polymerization conversion rate of the monomer mixture reached about 60 to 80%, the volatile matter was removed by a devolatilizer to produce an ABS resin having a rubber component content of about 13 to 18% by weight. As the rubber component, the block butadiene-styrene rubber having a solution viscosity SV of 20.1 cps obtained in Example 2 was used. The physical properties of the obtained resin were measured. The results are shown in Table 2.

Example 10 20 parts by weight of ethylbenzene and 1 part of rubber component to 100 parts by weight of styrene monomer
2 parts by weight, 0.050 parts by weight of an organic peroxide-based polymerization initiator, and t-dodecyl mercaptan (chain transfer agent).
After 25 parts by weight of the raw material liquid was continuously solution polymerized by a continuous polymerization process in which a complete mixing tank and a plug flow type reactor were combined in series until the polymerization conversion rate of the monomer mixture reached about 80%. Then, the volatile matter was removed with a devolatilizer to produce a HI resin having a rubber component content of about 13% by weight.
As the rubber component, the same rubber as used in Example 7 was used. The physical properties of the obtained resin were measured. The results are shown in Table 2.

[0050]

[Table 2]

[Comparative Example 5] The styrene content was 10% by weight, and the viscosity of a 5% by weight styrene solution at 25 ° C was 25 cp.
s, and a resin was produced under the same conditions as in Example 7 except that a styrene-butadiene rubber having no branched structure was used. The physical properties of the obtained resin were measured. The results are shown in Table 3. It can be seen that the IZ is particularly low.

Comparative Example 6 Example 7 was repeated except that a rubber having a 5 wt% styrene solution viscosity at 25 ° C. of 4 cps was used.
A resin was produced under the same conditions as above. The physical properties of the obtained resin were measured. The results are shown in Table 3.

[Comparative Example 7] A resin was produced under the same conditions as in Example 7, except that the molecular weight of the matrix resin was lowered by adding a chain transfer agent. The physical properties of the obtained resin were measured. The results are shown in Table 3.

[Comparative Example 8] A resin was produced under the same conditions as in Example 7, except that the molecular weight distribution of the matrix resin was widened by adding a chain transfer agent midway. The physical properties of the obtained resin were measured. The results are shown in Table 3.

[0055]

[Table 3]

[Comparative Example 9] A resin was produced under the same conditions as in Example 7, except that the number of revolutions of stirring was reduced to increase the diameter of rubber particles. The physical properties of the obtained resin were measured. The results are shown in Table 4.
Shown in.

Comparative Example 10 A resin was produced under the same conditions as in Example 7, except that different rubber particle diameters were produced by changing the stirring rotation speed, and then the polymerization liquid was mixed to widen the rubber particle diameter distribution. The physical properties of the obtained resin were measured. The results are shown in Table 4.

[Comparative Example 11] A resin was produced under the same conditions as in Example 7, except that the reaction was terminated at a polymerization conversion rate of 34%. The physical properties of the obtained resin were measured. The results are shown in Table 4.

Comparative Example 12 A resin was produced under the same conditions as in Example 7, except that the devolatilization temperature was lowered and the swelling ratio was increased. The physical properties of the obtained resin were measured. The results are shown in Table 4.

[0060]

[Table 4]

In Tables 2 to 4, IZ is AS.
Izod impact strength measured according to TM-D-256, MI is melt flow rate (220 ° C, 10 kg) measured according to JIS-K-7210, and gloss value is J
The respective values measured according to IS-K-7105 are shown. The average particle diameter (Dw) of the rubber-dispersed particles was determined by staining the resin with osmium tetroxide, measuring 200 to 1000 rubber particle diameters from transmission electron microscope photographs by the ultrathin section method, and determining the weight average particle diameter. In the case of an elliptical shape, the average of the major axis a and the minor axis b, that is, (a +
The particle size was defined as b) / 2. Further, for the particle size distribution (Dw / Dn) of the rubber-dispersed particles, the number average particle size was obtained in the same manner as the weight average particle size was obtained, and the particle size distribution was calculated by the weight average particle size / number average particle size.

Further, the graft ratio (g) is the same as that of sample A (about 1
g was precisely weighed) in 30 cc of acetone, the insoluble matter was separated by a centrifugal separation method and dried, and the weight (B) of the acetone insoluble matter was precisely weighed and calculated by the following formula 1. However, C shows the content rate of the rubber-like polymer in the sample A. Grafting rate (g) = [(B / A) -C] / C [Formula 1] The swelling ratio was 1 by adding Sample D (about 1 g was precisely weighed) to 30 cc of 1/1 mixed solvent of toluene / methyl ethyl ketone. After stirring for dissolution for a period of time, centrifugation was performed to remove the supernatant, and the weight (E) of the remaining swollen material was precisely weighed and calculated by the following [Formula 2]. Swelling ratio = E / D [Formula 2]

[0063]

The rubber-modified aromatic vinyl-based copolymer resin containing the conjugated diene rubber-like polymer composition of the present invention as a rubber component has good gloss, impact resistance and fluidity. . Further, according to the method for producing a rubber-modified aromatic vinyl-based copolymer resin of the present invention, it is possible to easily produce a resin having good gloss characteristics, impact resistance and fluidity.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroaki Matsuda 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd. Research and Development Center

Claims (4)

[Claims] 1. When polymerizing an aromatic vinyl monomer and a conjugated diene monomer using an organic alkali metal catalyst, the weight ratio of the total amount of the aromatic vinyl monomer (A) to the total amount of the conjugated diene monomer (B) [(A ) Vs. (B)] is 3:
In the first step, the total amount of the aromatic vinyl monomer (A) and a part of the conjugated diene monomer (B) used in the first step are (A) to (B) 9: 9. 1 to
The mixture was charged at a ratio of 5: 5 and polymerized in an organic solvent in the presence of 2 to 60 mol% of the total amount of the organic alkali metal catalyst to be used to prepare an aromatic vinyl polymer having an active terminal and a conjugated diene monomer. A copolymer is formed, and subsequently, in the second step, the total amount of the remaining organic alkali metal catalyst and the total amount of the remaining conjugated diene monomer are added and polymerized in an organic solvent to obtain an aromatic vinyl monomer having an active terminal. A block copolymer with a conjugated diene monomer and a conjugated diene polymer having an active terminal are formed, and a coupling agent is added to the polymerization reaction system containing the active polymer in the third step to obtain a total active polymer amount of 60 to 99. A) the content of aromatic vinyl monomer is 3 to 15% by weight, b) the vinyl bond content of the conjugated diene portion is 10 to 45% by weight, and c) 5% by weight. The viscosity of the ethylene solution is 5 to 30 cps, d) the content of the block aromatic vinyl monomer is 90% or less of the content of the aromatic vinyl monomer, and e) the content of the coupling polymer component is 60 to 99% by weight. A method for producing a conjugated diene-based rubbery polymer composition, which comprises obtaining a rubbery polymer composition. 2. Obtained by the method according to claim 1, a) the content of aromatic vinyl monomer is 3 to 15% by weight, b) the vinyl bond content of the conjugated diene moiety is 10 to 45% by weight, and c). The viscosity of a 5 wt% styrene solution at 25 ° C is 5-50.
cps, d) A conjugated diene rubbery polymer composition having a blocked aromatic vinyl monomer content of 90% or less of the aromatic vinyl monomer content, and e) a coupling polymer component content of 60 to 99% by weight. object. 3. An aromatic vinyl monomer, or a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer, or a copolymer of an aromatic vinyl monomer, a vinyl cyanide monomer, and a vinyl monomer copolymerizable therewith. Is a rubber-modified aromatic vinyl-based copolymer resin in which 3 to 30 parts by weight of a rubber component are dispersed in a particulate form, relative to 100 parts by weight of the matrix resin. 60 to 100% by weight
And a vinyl cyanide monomer content of 0 to 40% by weight, and a weight average molecular weight of 60,000 to
180,000 and the molecular weight distribution is 3.1 or less,
In addition, the rubber component contains a) aromatic vinyl monomer content of 3 to 15% by weight, b) vinyl bond content of conjugated diene portion of 10 to 45% by weight, and c) 5% by weight at 25 ° C.
A cup comprising a styrene solution having a viscosity of 5 to 50 cps, a block aromatic vinyl monomer content of 90% or less of an aromatic vinyl monomer content, and an e) coupling polymer component content of 60 to 99% by weight. A rubber-modified polymer composition containing a ring block copolymer, wherein the dispersed particles have an average particle diameter (Dw) of 0.2 to 2 μm. resin. 4. The aromatic vinyl monomer content is 60 to 1.
00% by weight and vinyl cyanide monomer content of 0
A content of the aromatic vinyl monomer as a rubber component is 3 to 15% by weight, and b) the vinyl bond content of the conjugated diene portion is 10 to 45% by weight, based on 100 parts by weight of the monomer mixture of 40 to 40% by weight, c) The viscosity of the 5 wt% styrene solution at 25 ° C. is 5 to 50 cps, and d) the content of the block aromatic vinyl monomer is 9 of the aromatic vinyl monomer content.
0% or less, e) The content of the coupling polymer component is 60
3 to 30 parts by weight of a rubber-like polymer composition containing a coupling block copolymer in the range of 100 to 99% by weight, and
A raw material liquid is prepared by mixing 2 to 100 parts by weight of a solvent, a polymerization initiator and a chain transfer agent are added to the raw material liquid, and then bulk polymerization or polymerization is performed until the polymerization conversion rate of the monomer mixture is 40 to 90%. A method for producing a rubber-modified aromatic vinyl-based copolymer resin, which comprises performing solution polymerization and removing a volatile component from the obtained polymerization reaction mixture.