JPH07103196B2 - Core shell polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a core-shell polymer for engineering plastics, and a resin composition having a particularly improved low temperature impact resistance obtained by melt-mixing the core-shell polymer.

Prior art and problems to be solved by the invention Polyalkylene terephthalate resins such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PBT), and polyamide resins such as nylon 6 and nylon 66 do not have sufficient impact resistance of molded products. , Many attempts have been made to improve this.

There are many proposals as an impact modifier which is added to a resin and melt-mixed for the purpose of improving the impact resistance. Among them, the core-shell polymer, which has a rubber elastic body as a core and a glassy polymer as a shell, is characterized in that the dispersion state in the resin is not easily affected by the melt-mixing conditions and reproducibility is easily obtained. However, if only high impact resistance is obtained, it may become an excellent impact modifier.

As a core-shell polymer for improving the impact resistance of polyalkylene terephthalate resin, a multiphase polymer containing an epoxy group in the outermost shell phase has been proposed in JP-A-52-74652.

However, the improvement of the impact resistance of the molten mixture with the polyalkylene terephthalate resin is extremely low, and practically a considerable amount of epoxy groups are lost in each step of polymerization and drying, which is not practical.

In JP-A-52-150466, a composition of a core-shell polymer containing no epoxy group and a polyalkylene terephthalate resin is proposed, and a composition having a high notched Izod impact value (thickness 1/8 inch) at 25 ° C or higher. Is included.

However, even this composition having high impact resistance changes from ductile fracture to brittle fracture (brittle ductile transition) at around 20 ° C., and shows a low notched Izod impact value at temperatures below that.

As a core-shell polymer for improving the impact resistance of a polyamide resin, a composition of a core-shell polymer containing a carboxyl group in the outermost shell phase and a polyamide resin has been proposed in JP-A-47-6284. Included is a composition that provides an Izod impact value (thickness 1/8 inch).

However, even this composition having a high impact property causes brittle ductile transition at around 15 ° C., and shows a low Izod impact value at a temperature below that.

On the other hand, when engineering plastics such as polyalkylene terephthalate resin, polyamide resin, modified polyphenylene oxide resin, polyacetal resin, and polycarbonate resin are used for automobile exterior parts, etc., sufficient impact resistance at a low temperature from room temperature to −30 ° C. is obtained. Required.

However, as described above, in the prior art, a polyalkylene terephthalate resin composition or a polyamide resin composition in which a core-shell polymer type impact modifier is melt-mixed has a temperature close to room temperature in a notched Izod impact test (thickness 1/8 inch). However, there was a problem that brittle ductile transformation occurs at a temperature lower than that and only a low Izod impact value is exhibited.

MEANS FOR SOLVING THE PROBLEMS The present inventors have proposed a core-shell polymer type impact modifier that provides a polyalkylene terephthalate resin composition having excellent low-temperature impact resistance, a polyamide resin composition, and other engineering plastics resin compositions. As a result of earnest studies, it was found that the above-mentioned problems could be solved by unexpectedly and melt-mixing a core-shell polymer having the following structure, thereby completing the present invention.

That is, the present invention provides a shell composed of (a) a core having an epoxy group on the surface, and (b) a polymer not containing an epoxy group and a functional group reactive with the epoxy group on the core (a). The present invention relates to a core-shell polymer having the resin composition, a resin composition containing the same, and a molded product obtained by molding the resin composition.

The core referred to in the present invention represents a rubber-like polymer or a rubber-like polymer phase and a phase outside thereof, and each of them has an epoxy group at least on the core surface portion.

If the core is formed solely of a rubbery polymer, a minimum of two stages of emulsion polymerization is performed to produce the core-shell polymer of the present invention.

The first stage polymerization forms the core and the second stage polymerization forms the shell.

In the first-stage polymerization, a conjugated diene or an alkyl acrylate having an alkyl group having 2 to 8 carbon atoms or a mixture thereof and an epoxy group-containing monomer are polymerized to form a rubber-like polymer having a glass transition temperature of −30 ° C. or lower. To do.

When the glass transition temperature of this rubber-like polymer is higher than -30 ° C, the effect of improving low temperature impact resistance may not be sufficient.

Examples of the conjugated diene that constitutes such a core include butadiene, isoprene, and chloroprene, but butadiene is particularly preferably used.

Examples of the alkyl acrylate having an alkyl group of 2 to 8 include ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate and the like, but butyl acrylate is particularly preferably used.

In the first-stage polymerization, a monomer copolymerizable with a conjugated diene and an alkyl acrylate, for example, aromatic vinyl such as styrene, vinyltoluene, α-methylstyrene, vinylidene aromatic, acrylonitrile, vinyl cyanide such as methacrylonitrile, etc. It is also possible to copolymerize vinylidene cyanide, alkyl methacrylate such as methyl methacrylate and butyl methacrylate.

Examples of the epoxy group-containing monomer include glycidyl acrylate, glycidyl methacrylate, 4,5-epoxypentyl acrylate, 4,5-epoxypentyl methacrylate, allyl glycidyl ether, and butadiene monoeposide, but especially glycidyl acrylate, Glycidyl methacrylate is preferably used.

The epoxy group-containing monomer is used in the range of 0.1 to 40% by weight, preferably 0.1 to 10% by weight of the core phase.

Further, it is preferable that the epoxy group-containing monomer is polymerized in the core phase with a concentration gradient such that the concentration becomes higher as the epoxy group-containing monomer is closer to the shell, because a smaller amount of the epoxy group-containing monomer can be efficiently used.

In the case where the conjugated diene is not contained in the first-stage polymerization or when the conjugated diene is contained but is 20% by weight or less of the total amount of the monomers in the first stage, a small amount of the crosslinking monomer and the grafting monomer are used. A high low temperature impact resistance can be achieved.

As the crosslinkable monomer, for example, an aromatic divinyl monomer such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, oligoethylene glycol diacrylate. , Oligoethylene glycol dimethacrylate, trimethylol propane diacrylate, trimethylol propane dimethacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, etc. alkane polyol polyacrylate or alkane polyol polymethacrylate can be mentioned, but especially Butylene glycol diacrylate, hex Emissions diacrylate are preferably used.

Examples of the grafting monomer may include unsaturated carboxylic acid allyl esters such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl itaconate, with allyl methacrylate being particularly preferred.

Such a crosslinkable monomer and a grafting monomer are each 0.01 to 0.01% of the total amount of monomers constituting the rubber-like polymer.
It is used in an amount of 5% by weight, preferably 0.1 to 2% by weight.

Usually, the core is preferably in the range of 50 to 95% by weight based on the whole core-shell polymer.

When the amount of the core is less than or more than this weight range, the effect of improving the impact resistance of the resin composition obtained by melt mixing the produced core-shell polymer may not be sufficient.

The second-stage polymerization forms a so-called shell.

The polymerization is carried out by polymerizing an epoxy group and a monomer containing no functional group reactive with the epoxy group to give a glass transition temperature of 40
Form a glassy polymer above ° C.

When the glass transition temperature of this shell is lower than 40 ° C, handling in each process from dehydration drying of the produced core-shell polymer to melt mixing with the resin becomes extremely difficult due to its tackiness, which may be impractical. .

Preferably, the glass transition temperature of the shell is 60 ° C or higher.

Examples of the functional group reactive with the epoxy group include many polar groups such as amino group, imino group, carboxyl group, carboxylate group, hydroxyl group, isocyanate group, sulfonic acid group, and sulfonate acid.

As the monomer used for the polymerization of the shell, a monomer that does not contain the epoxy group and the functional group reactive with the epoxy group is used.

For example, alkyl acrylate such as ethyl acrylate and butyl acrylate, alkyl methacrylate such as methyl methacrylate and butyl methacrylate, aromatic vinyl such as styrene, vinyltoluene and α-methylstyrene, cyanide such as aromatic vinylidene, acrylonitrile and methacrylonitrile. Examples thereof include vinyl polymerizable monomers such as vinyl and vinylidene cyanide, with methyl methacrylate, styrene and acrylonitrile being particularly preferred.

This shell preferably ranges from 5 to 50% by weight of the total core-shell polymer.

When the number of shells is less than or more than this weight range, the effect of improving the impact resistance of the resin composition obtained by melt mixing the resulting core-shell polymer may not be sufficient.

In the present invention, the core may have a rubbery polymer phase and a phase outside the rubbery polymer phase.

In that case, at least three stages of emulsion polymerization are performed to produce the core-shell polymer.

The first-stage polymerization forms a rubber-like polymer, the second-stage polymerization forms a phase containing an epoxy group on the outside of the rubber-like polymer, and the third-stage polymerization forms a shell. is there.

In the first-stage polymerization, a conjugated diene or an alkyl acrylate having an alkyl group having 2 to 8 carbon atoms or a mixture thereof is polymerized to form a rubbery polymer having a glass transition temperature of -30 ° C or lower.

The conjugated diene and alkyl group used at this time have 2 carbon atoms.
The same alkyl acrylates as those described above are used.

Further, a monomer copolymerizable with the conjugated diene and the alkyl acrylate, a crosslinkable monomer, and a grafting monomer are also used.

The second stage polymerization forms the outer phase of the rubbery polymer and is carried out using a monomer containing an epoxy group.

As the epoxy group-containing monomer, the same ones as described above are used.

In this case, the epoxy group-containing monomer may be used alone or may be copolymerized with another monomer.

Examples of the copolymerization monomer include ethyl acrylate,
Alky acrylates such as butyl acrylate, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, aromatic vinyls such as styrene, vinyltoluene and α-methylstyrene, vinylidene aromatics, vinyl cyanide such as acrylonitrile and methacrylonitrile, vinylidene cyanide. Examples thereof include vinyl polymerizable monomers that do not contain a functional group reactive with an epoxy group.

Preferably ethyl acrylate, butyl acrylate,
Methyl methacrylate is used.

Furthermore, the crosslinkable monomers and grafted monomers exemplified in the first-stage polymerization can also be appropriately used.

The amount of monomers containing epoxy groups in this phase is 5-10.
It is preferably 0% by weight, preferably 20-100% by weight. The amount of the epoxy group-containing monomer is 0.1 to 40% by weight, preferably 0.1 to 10% by weight, based on the total weight of the core.
Used in the range of.

The ratio of the rubber-like polymer phase to the epoxy group-containing phase in the core is appropriately selected depending on the type of monomer used.

Particularly preferably, 0.1 to 40% by weight of the epoxy group-containing phase is used with respect to the entire core. Further, preferably, the epoxy group-containing phase is composed only of a monomer containing an epoxy group, and the ratio of the phase to the core is 0.1 to 1
0% by weight is good.

When the amount of the epoxy group-containing monomer is less than or more than the above weight range, the effect of improving impact resistance of the resin composition obtained by melt-mixing the core-shell polymer produced may not be sufficient.

A rubbery polymer having a glass transition temperature of −30 ° C. or lower and one or more other intermediate phases having a glass transition temperature higher than −30 ° C. can be included between this phase. The presence of other mesophases may relax the core-shell strain at low temperatures and improve low temperature impact resistance.

This core is also 50 to 95% of the entire core-shell polymer as above.
A weight% range is preferred.

The third stage of polymerization is to form a shell, which is a polymerization of the epoxy group and a monomer that does not contain a functional group reactive with the epoxy group to form a glassy polymer with a glass transition temperature of 40 ° C or higher. To do.

When the glass transition temperature of this shell is lower than 40 ° C., handling in each step from dehydration drying of the produced core-shell polymer to melt mixing with the resin becomes extremely difficult due to its adhesiveness, which may be impractical. .

Preferably, the glass transition temperature of the shell is 60 ° C or higher.

The same monomer as described above is used as the monomer containing no epoxy group or functional group reactive with the epoxy group.

This shell is also preferably in the range of 5 to 50% by weight based on the whole core-shell polymer.

When the number of shells is less than or more than this weight range, the effect of improving the impact resistance of the resin composition obtained by melt mixing the resulting core-shell polymer may not be sufficient.

The core-shell polymer in the present invention can be taken out in the form of granules, flakes or powder by freeze-thawing a latex produced by a known seed emulsion polymerization method or separating the polymer by salting out, followed by centrifugal dehydration and drying.

The core shell polymer can also be removed directly from the latex by spray drying with a spray dryer.

The core-shell polymer thus taken out may be further pelletized by an extruder and a pelletizer, or may be used as a resin composition by incorporating it as an impact modifier into engineering plastics by means such as melt mixing. You can

The engineering plastics may be resins usually used, and examples thereof include polyamide resins, polyalkylene terephthalate resins, modified polyphenylene oxide resins, polyacetal resins, and polycarbonate resins, but those containing functional groups reactive with epoxy groups. It is more suitable.

As the polyalkylene terephthalate resin which is one of the engineering plastics used in the present invention,
For example, PET, polypropylene terephthalate, PBT and the like can be mentioned, but PBT is particularly preferably used. Many types of polyalkylene terephthalate resins are commercially available. The core-shell polymer of the present invention can be applied to these commercially available molding polyalkylene terephthalate resins.

The polyalkylene terephthalate resin is often used as a polymer alloy by melt-mixing with other plastics such as polycarbonate resin and modified polyphenylene oxide resin. Impact resistance is achieved.

The melt mixing of the core-shell polymer with the polymer alloy containing such a polyalkylene terephthalate resin is naturally included in the present invention.

Further, even if the core-shell polymer according to the present invention is melt-mixed with a polyamide resin, a modified polyphenylene oxide resin, a polyacetal resin or a polycarbonate resin, the impact resistance is remarkably improved.

Polyamide resin, modified polyphenylene oxide resin,
Polyacetal resin and polycarbonate resin are often used as a polymer alloy by being melt-mixed with each other or with other plastics such as ABS resin, and at this time, high impact resistance is achieved by melt-mixing the core-shell polymer according to the present invention. To be done.

In order to obtain such a resin composition, it is preferable to use 2 to 50% by weight of the core-shell polymer, and more preferably 5 to 35% by weight, based on the total amount of the resin composition.

When the amount of the core-shell polymer is less than 2% by weight, the effect of improving the impact resistance of the molded product produced from the obtained resin composition may not be seen. If it is more than 50% by weight, the rigidity and heat resistance of the molded product may be impaired.

The engineering plastic resin composition according to the present invention is produced by melt mixing.

Melt mixing is usually done by melting the resin between 200 and 300 ° C,
Moreover, an appropriate temperature range is selected so that the viscosity is not extremely low. This temperature is, for example, 230 to 260 ° C. for polybutylene terephthalate.

Melt mixing can be performed by using a heating roll, a Banbury mixer, or a single-screw or multi-screw extruder.

Furthermore, the resin composition according to the present invention may contain an appropriate amount of additives.

Examples of such additives include flame retardants, mold release agents, weather resistance imparting agents, antioxidants, antistatic agents, heat resistance imparting agents,
Colorants, reinforcing agents, surfactants, inorganic fillers, lubricants and the like can be mentioned.

In particular, when an antioxidant is used, the engineering plastics molded product has excellent heat resistance, which is preferable.

Examples of the antioxidants used include butylated hydroxytoluene, n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, tocopherol, 2 as phenolic compounds. , 2 ′
-Methylenebis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4]
-Hydroxyphenyl) propionate] methane and the like, as phosphorus compounds, tris (mixed, mono- and dinonylphenyl) phosphite, di-stearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) Phosphite, 4,4'-butylidene bis (3-methyl-6-t-butylphenyl) di-
As sulfur compounds such as tridecyl phosphite,
Examples thereof include dilauryl-3,3'-thiodipyrropionate and distearyl-3,3'-thiodipropionate.

These antioxidants may be added to the core-shell polymer in the latex state, or may be added when the core-shell polymer is melt-mixed to obtain a resin composition.

The amount added is 0.01 to 10 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the resin composition.

The resin composition obtained as described above is molded by a usual molding method to obtain a desired engineering plastics molded product.

For example, by injection molding, extrusion molding, compression molding, or the like, it can be molded into a desired form in the temperature range of 200 to 300 ° C.

Examples of such molded products include bumpers, fenders,
It can be used for automobile parts such as door handles, OA equipment, and home appliances.

Effects of the Invention The core-shell polymer according to the present invention is melt-mixed with an engineering plastic to obtain room temperature (15 ° C to
It is possible to provide a molded article that exhibits a high impact resistance that cannot be achieved by a conventional core-shell polymer at a low temperature of 25 ° C to -30 ° C.

Further, the core-shell polymer according to the present invention can be melt-mixed with a polyamide resin, a modified polyphenylene oxide resin, a polyacetal resin, a polycarbonate resin, or a blend of these resins to provide a molded article having high impact resistance.

The engineering plastic resin composition according to the present invention has a low temperature at which the ductile fracture changes to the brittle fracture, and exhibits a high notched Izod impact value even in the brittle fracture region, thereby exhibiting excellent low-temperature impact resistance.

In addition, when an antioxidant is contained in the core-shell polycarbonate, a molded product having even better heat resistance can be obtained.

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples.
The present invention is not limited to these examples. All "parts" in Examples and Comparative Examples represent parts by weight. Abbreviations used in Examples and Comparative Examples are as follows.

Butadiene Bd Ethyl Acrylate EA n-Butyl Acrylate BA 2-Ethyl Exyl Acrylate 2EHA Methyl Methacrylate MMA Styrene St Glycidyl Methacrylate GMA Allyl Methacrylate AlMA Allyl Maleate AlMl 1,4-Butylene Glycol Diacrylate BGA 1,6-Hexanediol Diacrylate HGA Deionized water DIW Dioctyl sulfosuccinate sodium salt SSS Dodecyl biphenyl ether sulfonic acid sodium salt
DBES Sodium persulfate SPS Cumene hydroperoxide CHP Formaldehyde sulfoxylate sodium salt SF
S Ethylenediaminetetraacetic acid sodium salt EDTA Sodium hydrogencarbonate SHC Polybutylene terephthalate PBT Polyoxyethylene nonylphenyl ether NPEa 2,2'-azobis (methylisobutyrate) AMI Glass transition temperature Tg Weight average particle diameter Dav Glass transition temperature of 10Hz Tan in dynamic viscoelasticity in tensile mode (measured with VEF-3 manufactured by Iwamoto Seisakusho)
The peak temperature of δ was used.

The weight average particle diameter of the core-shell polymer was measured by Coulter Model N-4 manufactured by Coulter Electronics.

[Example 1] Production of core-shell polymer A DIW 540 g, SSS 1% in a 2-liter polymerization vessel equipped with a reflux condenser
Aqueous solution 18.4 g and SHC 1% aqueous solution 36 g were charged, and the temperature was raised to 70 ° C. with stirring under a nitrogen stream.

36 g of a first-stage monomer mixture having the following composition was added and dispersed for 10 minutes, and then 76.5 g of a 2% aqueous solution of SPS was added to start seed polymerization.

First-stage monomer BA 762 g AlMA 1.5 g BGA 1.5 g Subsequently, the remaining 729 g of the first-stage monomer mixture, SSS 1% aqueous solution
A monomer emulsion consisting of 257 g, SHC 1% aqueous solution 40.5 g, and DIW 27 g was continuously fed for 3 hours.

After raising the temperature to 80 ° C. and aging for 1 hour, it was cooled to 70 ° C. and the second stage polymerization was started.

13.5 g of a 2% SPS aqueous solution was added, and 206.1 g of a second stage monomer emulsion having the following composition was fed over 30 minutes.

Second-stage monomer emulsion MMA 94.5g EA 13.5g GMA 27.0g SSS 1% aqueous solution 48.6g SHC 1% aqueous solution 13.5g DIW 9.0g After aging for 1 hour at 70 ° C, add SPS 2% aqueous solution 9.0g and add the following composition 148.5 g of the third stage monomer emulsion was fed over 30 minutes.

Third stage monomer emulsion MMA 90.0g SSS 1% aqueous solution 31.5g SHC 1% aqueous solution 9.0g DIW 18.0g As it is, aging at 70 ° C for 1 hour, cooling to room temperature, 300
46.4% solid content after filtering with stainless steel mesh of mesh,
A core-shell polymer latex having a weight average particle diameter of 290 nm was obtained.

This latex was coagulated by freeze-thawing, washed with water, dehydrated and dried to obtain a core-shell polymer A.

[Examples 2 to 5] Manufacture of core-shell polymers Emulsion polymerization and freeze-thawing, washing with water, dehydration and drying with the same composition as shown in Table 1 to prepare core-shell polymers B, C, D and E. Got

[Example 6] Production of core-shell polymer DIW (540 g) and DBES (2.4 g) were placed in a 5-liter autoclave, and the temperature was raised to 50 ° C with stirring under a nitrogen stream.

St7.5g, Bd19.5g added, CHP0.24g and SFS5.0g / EDTA
1.1 g of an activating solution consisting of 0.5 g / ferrous sulfate 0.05 g / DIW 50 g
Added to initiate seed polymerization.

After the reaction was completed, 1000 g of DIW was added, and 2024 g of a monomer emulsion having the following composition, 2.4 g of CHP, and 11 g of the activating solution were continuously fed for 5 hours, 8 hours, and 8 hours, respectively, to carry out the first stage polymerization.

First-stage monomer emulsion St 375g Bd 1,125g DBES 24g DIW 500g The temperature was raised to 70 ° C to start the second-stage polymerization.

54 g of a 2% SPS aqueous solution was added, and 412 g of a second-stage monomer emulsion having the following composition was fed over 30 minutes.

Second-stage monomer emulsion MMA 189g EA 27g GMA 54g DBES 1g SHC 1% aqueous solution 27g DIW 114g After aging at 70 ° C for 1 hour, add 18% SPS 2% aqueous solution and add 297g of the third-stage monomer emulsion 297g with the following composition I fed in minutes.

Third-stage monomer emulsion MMA 180g DBES 1g SHC 1% aqueous solution 18g DIW 98g After aging at 70 ° C for 1 hour, cool to room temperature, filter with 300 mesh stainless wire mesh, and solid core 46.5%, weight average particle size 240nm core shell A polymer latex was obtained. This latex is coagulated by freeze-thawing, washed with water, dehydrated,
A core-shell polymer F was obtained by drying.

[Example 7] Production of core-shell polymer DIW520g, SSS 1% in a 2-liter polymerization vessel equipped with a reflux condenser
20 g of an aqueous solution and 40 g of a 1% SHC aqueous solution were charged, and the temperature was raised to 70 ° C while stirring under a nitrogen stream.

After adding 40 g of the first-stage monomer (a) having the following composition and dispersing it for 10 minutes, 70 g of a 2% SPS aqueous solution was added to initiate shield polymerization.

1st stage monomer (a) BA 697.2g AlMA 1.4g BGA 1.4g 1st stage monomer emulsion (A) 1st stage monomer (a) 660g SSS 1% aqueous solution 230g SHC 1% aqueous solution 30g 1st stage monomer emulsion ( B) 1st stage monomer (b) BA 119.4g GMA 30 g AlMA 0.3g BGA 0.3g SSS 1% aqueous solution 54 g SHC 1% aqueous solution 15 g DIW 10 g Then, 1st stage monomer emulsion (A) 920 g After continuous field for 150 minutes, SPS 2% aqueous solution 1 immediately
5 g was added and 229 g of the first-stage monomer emulsion (B) was fed for 30 minutes.

After aging at 70 ° C. for 1 hour, the second-stage polymerization was started.
15 g of a 2% aqueous SPS solution was added, and 244 g of a second-stage monomer emulsion having the following composition was fed over 40 minutes and aged at 70 ° C. for 1 hour.

Second-stage monomer emulsion Second-stage monomer MMA 135g EM 15g SSS1% aqueous solution 54g SHC1% aqueous solution 15g DIW 10g After cooling to room temperature, it is filtered through a 300-mesh stainless wire mesh to have a solid content of 45.6% and a core shell with a weight average particle size of 284 nm. A polymer latex was obtained.

This latex was coagulated by freeze-thawing, washed with water, dehydrated and dried to obtain a core-shell polymer G.

[Examples 8 and 9] Production of core-cell polymers H and I Emulsion polymerization was carried out in the same manner as in Example 7 with the feed composition shown in Table 1, coagulated by freeze-thawing, washed with water, dehydrated and dried. , Core-shell polymers H and I were obtained.

[Example 10] Production of core-shell polymer J DIW (450 g) and DBES (2.4 g) were charged into a 5-liter autoclave, and the temperature was raised to 50 ° C with stirring under a nitrogen stream.

St7.5g, Bd19.5g added, CHP0.24g and SFS5.0g / EDTA
1.1 g of an activating solution consisting of 0.5 g / ferrous sulfate 0.05 g / DIW 50 g
Added to initiate seed polymerization.

After completion of the reaction, 1,000 g of DIW was added, 2,024 g of a monomer emulsion having the following composition, 2.4 g of CHP and 1.1 g of the above-mentioned activating solution were continuously fed for 5 hours, 8 hours, and 8 hours, respectively, to carry out the first stage polymerization. Was done.

First-stage monomer emulsion St 300g Bd 1,050g GMA 150g DBES 24g DIW 500g The temperature was raised to 70 ° C and the second-stage polymerization started.

54 g of a 2% SPS aqueous solution was added, and 631 g of a second stage monomer emulsion having the following composition was fed over 60 minutes.

Second-stage monomer emulsion MMA 337.5g EA 37.5g DBES 1 g SHC 1% aqueous solution 54 g DIW 200 g After aging at 70 ° C for 1 hour, cool to room temperature, filter through a 300 mesh stainless wire mesh, and solid content 46.5% A core-shell polymer latex having a weight average particle diameter of 240 nm was obtained.

This latex was coagulated by freeze-thawing, washed with water, dehydrated and dried to obtain a core-shell polymer J.

[Example 11] Production of PBT resin composition (1) 100 parts of PBT (PBT1401x04 manufactured by Toray Industries, Inc.) and 25 parts of the core-shell polymer A produced in Example 1 were dried to a water content of 0.03% or less. Twin-screw extruder manufactured by Ikegai Tekko Co., Ltd.
Using PCM-30, the mixture was melt-mixed at a cylinder temperature of 245 ° C and a die head temperature of 250 ° C to obtain pellets of PBT resin composition (1).

The PBT used in this example was subjected to a plastic flow test using a flow tester CFT-500 manufactured by Shimadzu Corporation in accordance with JIS K-7210. The Q value was 0.19 (ml).
/ s).

Measurement conditions Set temperature: 250 ℃ Load: 100kgf Dye: Diameter 1mm, length 10mm This Q value is one of the standard of the average molecular weight of the resin, and the larger the value, the smaller the average molecular weight.

[Examples 12 to 20] Production of PBT resin compositions (2) to (10) In the same manner as in Example 11 except that core shell polymers B to J were used instead of the core shell polymer A in Example 11.
Pellets of PBT resin compositions (2) to (10) were obtained.

[Comparative Examples 1 and 2] Production of core-shell polymers K and L Core-shell polymers K and L having the compositions shown in Table 1 were produced by emulsion polymerization.

The core-shell polymer K contains an epoxy group derived from GMA in the outermost shell phase.

The core-shell polymer L is a core-shell two-phase polymer containing no epoxy group and exhibits a high notched Izod impact value when melt-mixed with PBT at room temperature or higher.

[Comparative Examples 3 and 4] Production of PBT resin compositions (11) and (12) The core-shell polymers K and L were used in place of the core-shell polymer A in Example 11, and the PBT resin composition was prepared in the same manner as in Example 11. Pellets of the products (11) and (12) were obtained.

[Test Example 1] Impact resistance test PBT pellets of PBT resin compositions (1) to (12) were heated to 120 ° C.
After drying for 4 hours, the cylinder temperature and nozzle temperature were respectively set to 250 ° C and 260 ° C using an injection molding machine TS-100 manufactured by Nissei Plastic Co., Ltd.
A 3.2 mm-thick Izod impact test piece specified in JIS K7113 was prepared by forming a notch by molding and cutting at ℃.

With this test piece, 30 ℃, 20 ℃, 10 ℃, 0 ℃, -10 ℃,-
The impact value at each temperature of 30 ° C. was measured by the method according to JIS K7113. The results are shown in Table 2.

[Examples 21 to 23] Production of core-shell polymers M, N and O With the composition shown in Table 3, emulsion-polymerization and freeze-thawing, washing with water, dehydration and drying were carried out in the same manner as in Example 1 to give core-shell polymers M, N. And O were obtained.

Examples 24 and 25 Preparation of Core Shell Polymers P and Q Tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane (Mark AO-60; ADEKA ARGUS) Company, antioxidant) 2
Emulsify 0 g, 20 g of toluene and 20 g of 1% DBES aqueous solution,
Obtain an emulsion.

Then Example 10 (core shell polymer J) or 24
Core-shell polymer latex obtained during the production of (core-shell polymer N) (amount corresponding to solid content of 1,000 g)
And the emulsion were mixed and stirred to perform latex-latex blending.

Then, the mixed latex is coagulated by freeze-thawing,
It was washed with water, dehydrated and dried to obtain core-shell polymers P and Q.

[Examples 26 to 30] Production of PBT resin compositions (13) to (17) In the same manner as in Example 11 except that the core-shell polymers A to Q were used instead of the core-shell polymer A in Example 11.
PBT resin compositions (13) to (17) were obtained as pellets.

[Example 31] Production of PBT resin composition (18) Instead of the PBT used in Example 11, PBT (PBT1 manufactured by Toray Industries, Inc.) was used.
Pellets of the PBD resin composition (18) were obtained in the same manner as in Example 11 except that the core-shell polymer M prepared in Example 21 was used as the core-shell polymer.

The plastic flow test result of the PBT used in this example was 0.23 (ml / s) (Q value).

[Example 32] Production of PBT resin composition (19) PBT (Duranex 2002 manufactured by Polyplastics Co., Ltd.) was used in place of the PBT used in Example 11, and the core-shell polymer was the core-shell polymer M produced in Example 21. Using this, pellets of the PBT resin composition (19) were obtained in the same manner as in Example 11.

The plastic flow test result of the PBT used in this example was 0.36 (ml / s) (Q value).

Comparative Example 5 Production of PBT Resin Composition (20) PBT (PBT1401 × 06 manufactured by Toray Industries, Inc.) and the core-shell polymer L produced in Comparative Example 2 were used in the same manner as in Example 11.
A pellet of PBT resin composition (20) was obtained.

[Comparative Example 6] Production of PBT resin composition (21) Using PBT (Duranex 2002 manufactured by Polyplastics Co., Ltd.) and using the core-shell polymer L produced in Comparative Example 2, PBT resin was obtained in the same manner as in Example 11. A pellet of composition (21) was obtained.

[Test Example 2] Impact resistance test Pellets of the PBT resin compositions (13) to (21) were subjected to an impact resistance test in the same manner as in Test Example 1. The results are shown in Table 4.

[Example 33] Production of core-shell polymer R DIW1.125 g, NPEa1 in a polymerization vessel N equipped with a 5-liter reflux condenser.
Charge 135 g of 0% aqueous solution, and stir under nitrogen stream to 70
The temperature was raised to ° C.

90g of 1st stage monomer mixture with the following composition, NPEa10
% Aqueous solution 45 g and DIW 90 g of a mixed solution was sufficiently emulsified with a disper, and then the mixed solution was added to a polymerization vessel,
The dispersion was carried out for 10 minutes, and then 3.6 g of AMI was added to carry out seed emulsion polymerization.

First-stage monomer BA 1,729.5g AlMa 3.5g BGA 3.5g Then, NPEa10 was added to the remaining 1,646.5g of the first-stage monomer mixture.
% 1,500 g of an aqueous solution and 525 g of DIW were mixed and fed continuously for 250 minutes to carry out seed polymerization.

This was heated to 90 ° C., aged for 1 hour, cooled to 70 ° C., and subjected to the second stage polymerization.

Next, 1.0 g of AMI was added, and 267.5 g of a second-stage monomer emulsion having the following composition was continuously fed over 60 minutes to perform seed polymerization.

Second stage monomer GMA 67.5 g NPEa 10% aqueous solution 100 g DIW 100 g After aging at 70 ° C. for 40 minutes, the third stage polymerization was started.

Finally, 1.5 g of AMI was added, and the next third-stage monomer emulsion 1,0
12.6 g was continuously fed over 200 minutes to carry out seed polymerization.

Third stage monomer MMA 303.8 g EA 33.8 g NPEa 10% aqueous solution 362.0 g DIW 313.0 g After aging at 70 ° C. for 1 hour, the mixture was cooled to room temperature and filtered through a 300 mesh stainless wire mesh to obtain a core-shell polymer latex.

This latex was frozen at -15 ° C, filtered through a glass filter, and then air-dried at 60 ° C for 24 hours to obtain a core-shell polymer R.

Claims (16)

[Claims] 1. A core having (a) an epoxy group on the surface, and (b) a shell composed of a polymer containing no epoxy group and a functional group reactive with the epoxy group on the core (a). Coma shell polymer. 2. The core-shell polymer according to claim 1, wherein the core having an epoxy group on the surface is a core containing a phase composed of a rubber-like polymer and a phase having an epoxy group-containing polymer on the outside thereof. 3. The total weight of the core-shell polymer is 50.
A core-shell polymer according to claim 1) which comprises -95 wt% core and 5-50 wt% shell. 4. In the core, 0.1 to 4 relative to the total weight of the core
The core-shell polymer according to claim 1) containing 0% by weight of an epoxy group-containing monomer. 5. The core-shell polymer according to claim 1, wherein the glass transition temperature of the shell is 40 ° C. or higher. 6. The core-shell polymer according to claim 1, wherein the rubber-like polymer constituting the core has a glass transition temperature of −30 ° C. or lower. 7. A resin composition comprising engineering plastics containing the core-shell polymer according to claim 1). 8. The resin composition according to claim 2, wherein the engineering plastic is an engineering plastic containing a functional group reactive with an epoxy group. 9. The resin composition according to claim 3, wherein the engineering plastics containing a functional group reactive with an epoxy group is a polyalkylene terephthalate resin. 10. The resin composition according to claim 7, which contains the core-shell polymer in an amount of 2 to 50% by weight based on the total weight of the resin composition. 11. The resin composition according to claim 7, which further comprises an antioxidant. 12. 0.01 to 1 per 100 parts by weight of the resin composition.
The resin composition according to claim 11), which comprises 0 part by weight of an antioxidant. 13. A resin composition obtained by melt-mixing an engineering plastic with the core-shell polymer according to claim 2). 14. The resin composition according to claim 13, wherein the engineering plastic is an engineering plastic containing a functional group reactive with an epoxy group. 15. The resin composition according to claim 14, wherein the engineering plastic containing a functional group reactive with an epoxy group is a polyalkylene terephthalate resin. 16. A resin molded product obtained by molding the resin composition according to claim 7) or 13).