KR20140114311A - Acrylic copolymer having excellent impact strength - Google Patents

Abstract

The present invention relates to an acrylic based copolymer presenting an effect in improving impact strength of resin, especially low-temperature impact strength without deterioration of other properties such as tensile strength or the like by using polyalkylene glycol diacrylate or polyalkylene based cross linking agent of polyalkylene glycol dimethacrylate in alkyl acrylate-vinylaromatic compound-vinylcyano compound copolymer.

Description

TECHNICAL FIELD [0001] The present invention relates to an acrylic copolymer having improved impact strength,

TECHNICAL FIELD The present invention relates to a process for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer and a thermoplastic resin composition containing the same. More specifically, the present invention relates to a process for producing an alkyl acrylate- And more particularly to an acrylic copolymer which exhibits an effect of further improving the impact strength of the resin, particularly the low temperature impact strength, without deteriorating the heat resistance.

In the case of an automobile exterior material or a cellular phone housing, it is frequently exposed to a low temperature environment in use and is likely to be exposed to a light source such as ultraviolet rays. In addition, these materials require high heat-resistant temperatures to withstand hot sunlight and require high tensile strength.

Examples of the rubber-reinforced thermoplastic resin include ABS (acrylonitrile-butadiene-styrene) resin, ASA (acrylonitrile-styrene-acrylonitrile) resin, MBS (methylmethacrylate-butadiene-styrene) resin and AIM Is formed by graft copolymerization using a rubbery polymer having a core of 0 deg. C or less as a core and considering the compatibility with the matrix resin.

Generally, ABS resin, which is produced by graft copolymerizing styrene and acrylonitrile monomer to a butadiene rubber polymer, has impact resistance, processability, beautiful appearance, excellent mechanical strength, and high heat distortion temperature, , And construction materials.

However, because of the presence of the ethylenically unsaturated polymer in the butadiene rubber used as an impact modifier, the ABS resin is easily oxidized by ultraviolet rays, light, and heat in the presence of oxygen, resulting in changes in the appearance and color of the resin, There is a problem that it is not suitable as an outdoor material.

Therefore, in order to obtain a thermoplastic resin excellent in physical properties and excellent in weather resistance and aging resistance, an ASA resin which is an acrylate-styrene-acrylonitrile ternary copolymer using an acrylic rubber in which an ethylenically unsaturated polymer is not present instead of butadiene rubber as an impact modifier is used have. These ASA resins are used in various fields such as electronics, electric parts, building materials, automobiles, ships, leisure goods, and gardening which are used outdoors.

When producing ASA, it is common to prepare multilayer copolymer graft particles, i.e. core-shell structures. The core mainly uses acrylic rubber to improve the impact, and the shell uses styrene, acrylonitrile, methyl methacrylate or the like to improve the coloring property and dispersibility with the matrix resin.

Therefore, there is an attempt to increase the addition amount of ASA to increase the low temperature impact strength. However, such attempts cause deterioration of other properties such as tensile strength. Therefore, there is a demand for an acrylate-styrene-acrylonitrile resin capable of simultaneously improving low-temperature impact strength without deteriorating other physical properties.

Accordingly, an object of the present invention is to provide a process for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer having excellent impact strength, particularly low temperature impact strength, Vinyl aromatic compound-vinyl cyanide copolymer prepared by the method of the present invention.

The above object of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer comprising a polyalkylene cross-linking agent.

The present invention also relates to a process for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, comprising the steps of: (a) mixing 1 part by weight of a monomer selected from the group consisting of a vinyl aromatic compound, a vinyl cyan compound and an alkyl acrylate Preparing a seed by polymerizing a monomer mixture comprising from 4 to 30 parts by weight of at least one species; (b) polymerizing 20 to 80 parts by weight of an alkyl acrylate monomer and 0.01 to 3 parts by weight of a polyalkylene cross-linking agent in the presence of the seed to produce a rubber core; And (c) 0.01 to 3 parts by weight of a monomer mixture comprising 10 to 70 parts by weight of at least one member selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core and a crosslinking agent to prepare a crosslinked grafted shell Vinyl aromatic compound-vinyl cyanide copolymer, wherein the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer is a copolymer of an alkyl acrylate and a vinyl aromatic compound.

The thermoplastic resin composition comprising the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer prepared according to the present invention has an excellent impact strength, particularly a low temperature impact strength.

FIG. 1 and FIG. 2 are graphs showing the results of ¹ HRMAS NMR spectroscopy of an acrylic copolymer according to an embodiment of the present invention.

In order to achieve the above object, there is provided an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer comprising a polyalkylene crosslinking agent.

The polyalkylene crosslinking agent may contain a unit represented by the following formula (1).

[Chemical Formula 1]

_{- [-O-CH 2 -CH 2} -] n -

In Formula 1, n is an integer of 1 to 50, and specifically, n is an integer of 5 to 25.

Hereinafter, the present invention will be described in more detail.

The unit represented by the formula (1) in the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer according to the present invention may have an -H peak in the range of 3.0 to 3.8 ppm, specifically, 3.6 to 3.7 ppm .

The number of total -H units in the unit represented by the formula (1) may be 0.1 to 3 based on the total number of -H units of the terminal (-CH ₃ ) of the alkyl group contained in the alkyl acrylate unit, 0.9 to 1.4.

The alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer may be a core-shell structure.

The polyalkylene cross-linking agent may be included in the core, shell, or both.

The polyalkylene cross-linking agent may be selected from the group consisting of polyalkylene glycol diacrylate and polyalkylene glycol dimethacrylate. Specific examples thereof include polyethyleneglycol diacrylate (PEGDA), polyethylene glycol At least one selected from the group consisting of polyethyleneglycol dimethacrylate (PEGDMA), polypropylene glycol dimethacrylate (PPGDA), and polypropylene glycol dimethacrylate (PPGDMA). For example, polyethylene glycol diacrylate is used, but not limited thereto. Further, the polyalkylene cross-linking agent may have a number average molecular weight of 250 to 1,000.

The aromatic vinyl compound may be at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene. Specifically, styrene is used, but the present invention is not limited thereto.

The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. Specifically, acrylonitrile may be used, but the present invention is not limited thereto.

The alkyl acrylate may include an alkyl group having 2 to 8 carbon atoms. For example, methyl acrylate, ethyl acrylate or butyl acrylate having 1 to 4 carbon atoms in the alkyl moiety may be used, It is not.

An example of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer may be acrylate-styrene-acrylonitrile (ASA).

The alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer of the present invention preferably contains a seed having an average particle diameter of 0.1 to 0.3 탆. When the average particle diameter is less than 0.1 탆, the low temperature impact strength is lowered. There is a problem that the stability of the latex is deteriorated. In addition, the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer of the present invention preferably includes a rubber core having an average particle diameter of 0.15 to 0.5 μm.

The polyalkylene cross-linking agent is added at the time of preparing the alkacrylate-vinyl aromatic compound-vinylene compound copolymer, and the time of the addition is not limited.

The copolymer may further contain additives such as dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, plasticizers or matting agents which are conventionally used depending on the application.

The present invention provides a thermoplastic resin composition comprising the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer as described above, and further provides a molded article comprising the thermoplastic resin composition described above .

The thermoplastic composition may or may not use an acrylonitrile-styrene copolymer depending on the application to be used.

One embodiment of the process for producing the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer of the present invention is a process for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, comprising: (a) a step of reacting a monomer comprising at least one member selected from the group consisting of a vinyl aromatic compound, Preparing a seed by polymerizing the mixture; (b) polymerizing a monomer mixture comprising an alkyl acrylate monomer and a polyalkylene cross-linker in the presence of said seed to produce a rubber core; And (c) polymerizing a monomer mixture comprising at least one member selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound and a crosslinking agent in the presence of the rubber core to prepare a crosslinked grafted shell .

As a specific example of the method for producing the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer of the present invention, 100 parts by weight of the total monomers used in the preparation of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer (A) 0.001 to 1 part by weight of an electrolyte, 0.01 to 3 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of a grafting agent, 0.01 to 3 parts by weight of a crosslinking agent, To 3 parts by weight of an initiator, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier; (b) polymerizing a monomer mixture comprising 20 to 80 parts by weight of an alkyl acrylate monomer and 0.01 to 3 parts by weight of a polyalkylene cross-linking agent, 0.01 to 3 parts by weight of an initiator and 0.01 to 5 parts by weight of an emulsifier, ; And (c) 0.01 to 3 parts by weight of an initiator and 0.01 to 5 parts by weight of an emulsifier, wherein the monomer comprises at least one member selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core, And polymerizing the mixture to prepare a crosslinked grafted shell.

In another embodiment of the method for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide compound copolymer, 0.01 to 3 parts by weight of a polyalkylene cross-linking agent added in the step of (b) ) Shell may be added to the step of making.

The aromatic vinyl compound used in the steps (a) and (c) may be selected from the group consisting of styrene, -methylstyrene, p-methylstyrene and vinyltoluene. Styrene is preferably used, But is not limited thereto.

The vinyl cyan compound used in the steps (a) and (c) may be selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, preferably acrylonitrile , But is not limited thereto.

The alkyl acrylate in the above steps (a) and (b) is characterized by containing an alkyl group having 2 to 8 carbon atoms, preferably methyl acrylate having 1 to 4 carbon atoms in the alkyl moiety, ethyl acrylate or butyl Acrylate, but is not limited thereto.

In the present invention, a polyalkylene type crosslinking agent having a number average molecular weight of 250 or more may be used in step (b), and for example, a crosslinking agent having a number average molecular weight of 250 to 1,000 may be used. Specific examples of the polymer include polyethyleneglycol diacrylate (PEGDA), polyethyleneglycol dimethacrylate (PEGDMA), polypropyleneglycol diacrylate (PPGDA) and polypropyleneglycol dimethacrylate , PPGDMA) is used to further improve the low-temperature impact strength of a resin composition comprising an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, by using a polyalkylene-based crosslinking agent selected from the group consisting of

Further, a grafting agent may be added to the polyalkylene-based cross-linking agent. The grafting agent may be allyl methacrylate (AMA), triallyl isocyanurate (TAIC), triallylamine (TAA) or diallyl amine (DAA).

The crosslinking agent used in the step (c) may be at least one selected from the group consisting of divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate , Ethylene glycol diacrylate, hexanediol ethoxylate diacrylate, hexanediol ethoxylate diacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacrylate Acrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylpropaneethoxylate triacrylate, trimethylpropane propoxylate triacrylate, pentaerythritol ethoxy Triacrylate, pentaerythritol propoxylate tri Methacrylate and vinyl triethoxysilane may be one or more selected from the group consisting of silane, preferably a single use of divinylbenzene, and the like.

The emulsifier used in the above steps (a), (b) and (c) is not particularly limited, but an anionic surfactant, a nonionic surfactant, a cationic surfactant, a positive surfactant and the like can be used .

Of these, anionic surfactants selected from the group consisting of alkenyl succinate metal salts, alkyl benzene sulfonic acid salts, aliphatic sulfonic acid salts, sulfuric acid ester salts of higher alcohol,? -Olefin sulfonic acid salts and alkyl ether sulfuric acid ester salts are particularly preferably used .

In the electrolyte is _{KCl, NaCl, KHCO 3, NaHCO} 3, K 2 CO 3, Na 2 CO 3, KHSO 3, NaHSO 4, Na 2 S 2 O 7, K 4 P 2 O 7, K 3 PO 4, Na ₃ PO ₄ or Na ₂ HPO _4, etc. alone, or two or more kinds may be mixed.

The initiator used in the above steps (a), (b) and (c) is not particularly limited, but a radical initiator can be preferably used. Examples of the radical initiator include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthol hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide, t-butyl peroxyisobutyrate; At least one member selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyl acid) methyl, Inorganic peroxides are more preferable, and persulfates are particularly preferably used.

An activator may be used to promote the initiation reaction of the peroxide with the polymerization initiator. Examples of the activator include sodium formaldehyde, sulfoxylate, sodium ethylenediamine, tetraacetate, ferrous sulfate, dextrose, Sodium or sodium sulfite, etc. are preferably used alone or in combination of two or more.

The grafting agent in the step (a) may be allyl methacrylate (AMA), triallyl isocyanurate (TAIC), triallylamine (TAA) or diallylamine (DAA).

The polymerization temperature during the emulsion polymerization is not particularly limited, but is usually from 50 to 85 캜, preferably from 60 to 80 캜.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

Example 1

Hard hard polymer seed preparation step

40 parts by weight of distilled water was added to the polymerization reactor purged with nitrogen and the temperature was raised to 75 캜. Then, 0.025 part by weight of potassium persulfate was added thereto in a total amount of 5 parts by weight. Styrene 5 parts by weight, Na ₂ CO ₃ 0.05 parts by weight, 0.025 part by weight of acrylate, 0.025 part by weight of allyl methacrylate and 0.05 part by weight of sodium laurylsulfate were continuously added at 75 DEG C to prepare a hard polymer seed having an average particle diameter of 0.1 mu m.

Rubber polymer core preparation step

60 parts by weight of distilled water, 55 parts by weight of butyl acrylate, 0.3 part by weight of polyethylene glycol diacrylate (molecular weight 258), 0.3 part by weight of allyl methacrylate, 0.5 part by weight of cumene hydroperoxide 0.5 And 0.5 part by weight of sodium laurylsulfate were continuously added at 75 DEG C to prepare a rubber polymer core having an average particle diameter of 0.3 mu m.

Cross-linked grafted shell manufacturing steps

50 parts by weight of distilled water, 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.5 parts by weight of divinylbenzene, 0.5 parts by weight of cumene hydroperoxide and 0.65 parts by weight of sodium lauryl sulfate were mixed in the presence of the rubber polymer core prepared above The mixture was subjected to polymerization reaction at 75 캜 continuously. After the addition of the mixture was completed, the mixture was further reacted at 75 DEG C for 1 hour and cooled to 60 DEG C to complete the polymerization reaction, thereby preparing a graft copolymer latex. The polymerization conversion ratio of the prepared graft copolymer latex was 98% and the solid content was 40%.

Preparation of Graft Copolymer Powder

The acrylate-styrene-acrylonitrile graft copolymer latex prepared above was agglomerated at 80 ° C. by using an aqueous sulfuric acid solution, aged at 95 ° C., dehydrated and washed, and dried by hot air at 90 ° C. for 30 minutes Acrylate-styrene-acrylonitrile graft copolymer powder was prepared.

Example 2

Except that 0.3 part by weight of polyethylene glycol dimethacrylate (molecular weight: 330) was used instead of PEGDA in the preparation of the rubber polymer core of Example 1, to prepare a graft copolymer powder .

Example 3

A graft copolymer powder was prepared in the same manner as in Example 1 except that 0.3 part by weight of PEGDA (molecular weight: 575) was used instead of PEGDA (molecular weight: 258) in the preparation of the rubber polymer core of Example 1.

Example 4

A graft copolymer powder was prepared in the same manner as in Example 1 except that 0.3 part by weight of PEGDA (molecular weight: 700) was used instead of PEGDA (molecular weight: 258) in the preparation of the rubber polymer core of Example 1.

Example 5

A graft copolymer powder was prepared in the same manner as in Example 1 except that 1 part by weight of divinylbenzene was used instead of 0.5 part by weight of divinylbenzene in the step of preparing the crosslinked grafted shell of Example 1 .

Example 6

A graft copolymer powder was prepared in the same manner as in Example 1, except that divinylbenzene was not used in the step of preparing the crosslinked graft shell of Example 1.

Comparative Example 1

A graft copolymer powder was prepared in the same manner as in Example 1 except that 0.3 part by weight of EGDA (ethylene glycol diacrylate) was used instead of PEGDA (molecular weight 258) in the preparation of the rubber polymer core of Example 1 .

Comparative Example 2

Except that 0.6 weight parts of allyl methacrylate (AMA) was used in place of PEGDA (molecular weight 258) in the preparation of the rubber polymer core of Example 1, to prepare a graft copolymer Powder.

Comparative Example 3

A graft copolymer powder was prepared in the same manner as in Comparative Example 1, except that divinylbenzene was not used in the step of preparing the crosslinked grafted shell of Comparative Example 1.

[Test Example]

* Izod impact strength (1/8 "notched at (23 ° C., -30 ° C.), kg · cm / cm) - Measured according to ASTM D256 The low temperature impact strength was put into the low temperature chamber for at least 5 hours at -30 ° C. After the sample was taken out of the low temperature chamber for accurate measurement, it was measured within 3 seconds.

Tensile strength (50 mm / min, kg / cm ² ): Measured according to ASTM D638.

<PC / ASA alloy resin manufacturing>

12 parts by weight of the graft copolymer powder prepared in Examples 1 to 5 and Comparative Examples 1 to 3, 18 parts by weight of hard matrix styrene-acrylonitrile copolymer 90HR (manufactured by LG Chemical Co., Ltd.), polycarbonate PC1300-10 2 parts by weight of an antioxidant and 3 parts by weight of an ultraviolet stabilizer were added to and mixed with 70 parts by weight of an antioxidant. This was molded into a pellet shape at a cylinder temperature of 300 DEG C using a 40 pie extrusion kneader and then injected with the pellet to prepare a physical property specimen.

Test Example One 2 3 4 5 6 7 8 Graft copolymer
(ASA) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 The tensile strength
(kg / cm ² ) 556 554 553 554 553 554 552 548 Impact strength
(23 ° C)
(kgcm / cm) 76.7 77 79 81.5 85.5 76.7 73.6 61.9 Cold shock
burglar
(-30 ° C)
(kgcm / cm) 28.3 28.0 29.2 30.1 24.5 22.1 21.1 19

Styrene-acrylonitrile copolymer prepared by using a crosslinking agent such as PEGDA in the core portion of the polycarbonate resin according to Test Examples 1 to 5, it was confirmed that when the polyalkylene-based crosslinking agent was not used It can be seen that the effect of increasing the impact strength, particularly the low temperature impact strength at -30 캜, can be confirmed as compared with those of Examples 6 to 8, and it can be maintained without lowering physical properties such as tensile strength.

On the other hand, in Test Example 8 in which a crosslinking agent is not used in the graft shell preparation step without using a crosslinking agent of PEGDA in the production of the core, both the room temperature and the low temperature impact strength are reduced.

<PC manufacture including impact modifier>

3 parts by weight of the graft copolymer powder prepared in Examples 1 to 5 and Comparative Examples 1 to 3, 97 parts by weight of polycarbonate PC1300-10 (manufactured by LG Chemical), 2 parts by weight of the lubricant, 2 parts by weight of the antioxidant, And 3 parts by weight of a stabilizer were added and mixed. The pellets were prepared in the form of pellets using a 40 psi extrusion kneader at a cylinder temperature of 300 ° C, and the pellets were injected to prepare physical specimens, and the following properties were measured and are shown in Table 2.

Test Example 9 10 11 12 13 14 15 16 Graft copolymer
(ASA) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 The tensile strength
(kg / cm ² ) 596 597 594 593 598 588 594 591 Impact strength
(23 ° C)
(kgcm / cm) 83.2 84.1 84.5 85.2 86.3 82.3 81.1 76.3 Cold shock
burglar
(-30 ° C)
(kgcm / cm) 16.8 16.8 16.9 17.2 16.8 15.2 15.8 15.5

When the polycarbonate resin according to Test Examples 9 to 13 contains an acrylate-styrene-acrylonitrile copolymer prepared by using a crosslinking agent such as PEGDA in the core portion, a test example in which the PEGDA crosslinking agent is not used It is possible to confirm the effect of increasing the impact strength of the resin, particularly the low temperature impact strength at -30 캜, as compared with those of Test Example 14 to 16, and it is possible to maintain the same without deteriorating physical properties such as tensile strength.

On the other hand, in Test Example 16 in which the crosslinking agent is not used in the graft shell preparation step without using the crosslinking agent of PEGDA in the production of the core, both the room temperature and the low temperature impact strength are reduced.

<ASA resin production>

To 40 parts by weight of the graft copolymer powder prepared in Examples 1 to 4 and Comparative Examples 1 and 2 and 60 parts by weight of styrene-acrylonitrile copolymer 90HR (manufactured by LG Chemical Co., Ltd.) as a hard matrix, 2 parts by weight of a lubricant, 2 parts by weight of an inhibitor and 3 parts by weight of a UV stabilizer were added and mixed. The resulting mixture was pelletized at a cylinder temperature of 220 캜 using a 40-pie extrusion kneader, and the pellets were injected to prepare physical specimens. The properties shown in Table 3 were measured.

* Izod impact strength (1/8 ", 1/4" notched at (23 ° C), kg · cm / cm) - measured according to ASTM D256.

Tensile strength (50 mm / min, kg / cm ² ): Measured according to ASTM D638.

Test Example 17 18 19 20 21 22 Graft copolymer
(ASA) Example 1 Example 2 Example 3 Example 5 Comparative Example 1 Comparative Example 2 Tensile strength (kg / cm ² ) 430 425 424 425 408 411 Impact strength (1/8 "
(kgcm / cm) 21.3 22.3 22.0 23 18.5 17 Impact strength (1/4 "
(kgcm / cm) 15.6 15.8 15.6 16.4 14.3 14.6

Styrene-acrylonitrile copolymer prepared by using a crosslinking agent such as PEGDA in the core portion of the acrylonitrile-styrene resin according to Test Examples 17 to 20, the crosslinking agent of PEGDA was not used It is possible to confirm the effect of increasing the impact strength of the resin as compared with those of Test Examples 21 to 22, and it is possible to maintain the same without deteriorating physical properties such as tensile strength.

Claims (25)

Wherein the polyalkylene crosslinking agent comprises at least one member selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate and polypropylene glycol dimethacrylate, Vinyl aromatic compound-vinyl cyanide copolymer. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method according to claim 1,
Wherein the polyalkylene-based crosslinking agent comprises a unit represented by the following formula (1).
[Chemical Formula 1]
_{- [-O-CH 2 -CH 2} -] n-
In Formula 1, n is an integer of 2 to 50. 3. The method of claim 2,
The alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer according to claim 1, wherein the unit represented by the formula (1) has a -H peak measured by ¹ H NMR of 3.0 to 3.8 ppm. 3. The method of claim 2,
Wherein the unit represented by the formula (1) has a total of -H groups in an amount of 0.1 to 3 based on 100 total-H groups of an alkyl group terminal (-CH ₃ ) contained in the alkyl acrylate-based unit. Vinyl aromatic compound-vinyl cyanide copolymer. The method according to claim 1,
The alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer is a core-shell structure. 6. The method of claim 5,
Wherein the polyalkylene-based crosslinking agent is contained in the core, the shell, or both of the core and the shell. The method according to claim 1,
Wherein the polyalkylene cross-linking agent has a number average molecular weight of 250 to 1,000. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method according to claim 1,
The aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene. The method according to claim 1,
Wherein the vinyl cyanide compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer is preferably at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The method according to claim 1,
The alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer is characterized in that the alkyl acrylate comprises an alkyl group having 2 to 8 carbon atoms. (a) preparing a seed by polymerizing a monomer mixture comprising at least one selected from the group consisting of a vinyl aromatic compound, a vinyl cyan compound, and an alkyl acrylate;
(b) polymerizing a monomer mixture comprising an alkyl acrylate monomer and a polyalkylene cross-linker in the presence of said seed to produce a rubber core; And
(c) preparing a graft shell using a mixture of monomers comprising at least one member selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core, wherein the polyalkylene cross- At least one selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate and polypropylene glycol dimethacrylate and having a number average molecular weight of 250 to 1,000. Acrylate-vinyl aromatic compound-vinyl cyanide copolymer. (a) preparing a seed by polymerizing a monomer mixture comprising at least one selected from the group consisting of a vinyl aromatic compound, a vinyl cyan compound, and an alkyl acrylate;
(b) polymerizing a monomer mixture comprising an alkyl acrylate monomer in the presence of said seed to produce a rubber core; And
(c) preparing a crosslinked grafted shell by polymerizing a monomer mixture comprising at least one member selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound and a polyalkylene crosslinking agent in the presence of the rubber core, , The polyalkylene crosslinking agent is at least one selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate and polypropylene glycol dimethacrylate, and has a number average molecular weight Vinyl aromatic compound-vinyl cyanide copolymer. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 13. The method according to claim 11 or 12,
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene. 13. The method according to claim 11 or 12,
Wherein the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 13. The method according to claim 11 or 12,
Wherein the alkyl acrylate comprises an alkyl group having 2 to 8 carbon atoms. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 12. The method of claim 11,
A method for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, which comprises further adding a crosslinking agent to the monomer mixture of (c). 17. The method of claim 16,
The crosslinking agent may be at least one selected from the group consisting of divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate, ethylene glycol diacrylate, hexanediol Hexanediol ethoxylate diacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate Acrylate, trimethylol propane trimethacrylate, trimethylol methane triacrylate, trimethyl propane ethoxylate triacrylate, trimethyl propane propoxylate triacrylate, pentaerythritol ethoxylate triacrylate, pentaerythritol propoxy Triacrylate and vinyltrimethoxysilane Characterized in that the at least one selected from the group consisting of silane-alkyl acrylate-vinyl aromatic compound process for producing a vinyl cyan compound copolymer. 13. The method according to claim 11 or 12,
The monomer mixture of (a) is selected from the group consisting of vinyl aromatic compounds, vinyl cyan compounds and alkyl acrylates, based on 100 parts by weight of the total monomers used in the preparation of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer. Vinyl aromatic compound-vinyl cyanide copolymer of claim 1, wherein the amount of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer is from 4 to 30 parts by weight. 13. The method according to claim 11 or 12,
The monomer mixture of (a) is used in an amount of 0.001 to 1 part by weight of an electrolyte, 0.01 to 3 parts by weight of a crosslinking agent, 100 parts by weight of a grafting agent 0.01 to 3 parts by weight of an initiator, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier. 17. The method of claim 16,
Based on 100 parts by weight of the total monomers used in the preparation of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, the monomer mixture of (b) comprises 20 to 80 parts by weight of an alkyl acrylate monomer and 0.01 to 10 parts by weight of a polyalkylene cross- Wherein the monomer mixture of (c) comprises at least 10 to 70 parts by weight of at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound, and from 0.01 to 3 parts by weight of a crosslinking agent. A process for producing a vinyl aromatic compound-vinyl cyanide copolymer. 13. The method of claim 12,
The monomer mixture of (b) comprises 20 to 80 parts by weight of an alkyl acrylate monomer and 0.01 to 3 parts by weight of a crosslinking agent, based on 100 parts by weight of the total monomers used in the preparation of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, Wherein the monomer mixture of (c) comprises at least 10 to 70 parts by weight of at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound, and from 0.01 to 3 parts by weight of a polyalkylene crosslinking agent. A process for producing a vinyl aromatic compound-vinyl cyanide copolymer. 13. The method according to claim 11 or 12,
The monomer mixture (b) further comprises 0.01 to 3 parts by weight of an initiator and 0.01 to 5 parts by weight of an emulsifier, based on 100 parts by weight of the total monomers used in the preparation of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer Vinyl aromatic compound-vinyl cyanide copolymer. 13. The method according to claim 11 or 12,
The monomer mixture (c) further comprises 0.01 to 3 parts by weight of an initiator and 0.01 to 5 parts by weight of an emulsifier based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile copolymer Vinyl aromatic compound-vinyl cyanide copolymer. A thermoplastic resin composition comprising an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer according to claim 1. A molded article comprising the thermoplastic resin composition according to claim 24.

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