KR100708965B1 - Acryl-Conjugated Diene Rubber Based Resin for Impact Modifier and Weatherability and Method for Preparing the Same - Google Patents

Abstract

The present invention relates to an acrylic-conjugated diene-based composite rubber impact modifier and a method for manufacturing the same. The present invention relates to an acrylic-conjugated diene-based composite impact modifier, based on 100 parts by weight of the impact modifier, a) 0.01 to 10 Parts by weight; b) 50 to 98 parts by weight of the first acrylic-conjugated diene-based composite rubber core surrounding the seed; And b-2) 60 to 90 parts by weight of an acryl-conjugated diene-based composite rubber core comprising 2 to 50 parts by weight of a second acrylic-conjugated diene-based composite rubber core surrounding the first composite rubber core. And c) 10 to 40 parts by weight of a shell surrounding the acryl-conjugated diene-based composite rubber core including alkyl methacrylate having 1 to 4 carbon atoms of an alkyl group. Provide impact modifiers. Acrylic-conjugated diene-based composite rubber impact modifier according to the present invention has the effect of excellent low temperature impact strength and weather resistance and powder properties.

Impact modifier, vinyl chloride resin, impact resistance, weather resistance, powder flowability, butadiene, alkyl acrylate, alkyl methacrylate

Description

Acryl-Conjugated Diene Rubber Based Resin for Impact Modifier and Weatherability and Method for Preparing the Same}

The present invention relates to an acrylic-conjugated diene-based composite rubber impact modifier having excellent low-temperature impact resistance, weather resistance and powder flow properties, and a method for preparing the same. More specifically, the present invention relates to a small amount of conjugated diene-based rubber with alkyl acrylate rubber. The present invention relates to an acrylic-conjugated diene-based composite rubber impact modifier and a method for producing the same, which are prepared by copolymerizing and applying a crosslinking agent or a grafting agent by applying an alkyl acrylate-conjugated diene-based composite rubber to the outer rubber layer twice. .

Polyvinyl chloride resins are well known because of their excellent and diverse properties, while the impact strength is weak. The so-called MBS resin is prepared by grafting methyl methacrylate butadiene styrene on butadiene rubber and is widely used as an impact modifier of vinyl chloride resin. However, butadiene is easily decomposed by ultraviolet rays due to the presence of double bonds in the molecule and deteriorates the weather resistance of vinyl chloride resin, making it unsuitable for outdoor use.                         

Various methods have been proposed to improve the weakness of the weather resistance, and among them, there is a method of grafting methyl methacrylate, styrene, acrylonitrile, etc. on the acrylic rubber. The use of the impact modifier prepared in this way improves the weather resistance of the vinyl chloride resin, but there is a limit to improving the impact resistance of the vinyl chloride resin. In addition, the crosslinked acrylic rubber has no grafting active site, unlike MBS, resulting in poor grafting efficiency, poor powder flowability, and poor workability. As an improvement for this purpose, the introduction of a crosslinking agent having various reactivity has been proposed.

In addition, grafting of methyl methacrylate, styrene, acrylonitrile, and the like on the alkyl acrylate-conjugated diene copolymer rubber instead of the crosslinked alkyl acrylate rubber has been proposed. The method described in US Pat. No. 3,959,408 and US Pat. No. 4,078,018 also has improved processability, such as impact resistance and powder flow, but has a disadvantage of poor weatherability due to the presence of double bonds in the molecule.

In order to solve the above problems, the present invention is to copolymerize a small amount of conjugated diene-based rubber with an alkyl acrylate rubber to provide an acrylic-conjugated diene-based composite rubber impact modifier that can improve the impact resistance without reducing weather resistance For the purpose of

In addition, an object of the present invention is to provide a manufacturing method that can increase the grafting efficiency by using a crosslinking agent or a grafting agent by using an acrylic-conjugated diene-based composite rubber in the outer rubber layer.                         

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention

In acryl-conjugated diene-based composite impact modifier,

For 100 parts by weight of the impact modifier,

a) 0.01 to 10 parts by weight of the seed latex;

b) 100 parts by weight of the acrylic-conjugated diene-based composite rubber core,

b-1) 50 to 98 parts by weight of the first acryl-conjugated diene-based composite rubber core surrounding the sheath; And b-2) 60 to 90 parts by weight of an acryl-conjugated diene-based composite rubber core comprising 2 to 50 parts by weight of a second acrylic-conjugated diene-based composite rubber core surrounding the first composite rubber core. And

c) 10 to 40 parts by weight of a shell surrounding the acryl-conjugated diene-based composite rubber core comprising alkyl methacrylate having 1 to 4 carbon atoms of an alkyl group;

It provides an acrylic conjugated diene-based composite rubber impact modifier comprising a.

The seed is based on 100 parts by weight of the total amount of the monomer iii) 65 to 99.0 parts by weight of the vinyl monomer; Ii) 0.5 to 30 parts by weight of hydrophilic monomers; And iii) 0.5 to 5 parts by weight of a crosslinking monomer.

The first acrylic-conjugated diene-based composite rubbery core is 47.0 to 99.8 parts by weight of an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group, based on 100 parts by weight of the total monomers of the first acrylic-conjugated diene-based composite rubbery core. 0.1 to 50.0 parts by weight of the conjugated diene monomer, and 0.1 to 3.0 parts by weight of the crosslinker monomer.

The second acrylic-conjugated diene-based composite rubbery core is 37.0 to 99.89 parts by weight of an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group, based on 100 parts by weight of the total amount of the second acrylic-conjugated diene-based composite rubbery core. 0.1 to 60.0 parts by weight of the diene monomer, and 0.01 to 3.0 parts by weight of the crosslinking monomer.

The vinyl monomer may be at least one selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, and 3,4-dichloro styrene.

The hydrophilic monomers are ethyl acrylate, butyl acrylate, alkyl acrylates such as 2-ethylhexyl acrylate, methyl methacrylate, alkyl methacrylates such as benzyl methacrylate, acrylonitrile, hydroxyl methyl methacrylate And at least one selected from the group consisting of glycidyl methacrylate.

The crosslinker monomer is divinyl benzene, 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate It may be selected from the group consisting of acrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol dimethacrylate.

The alkyl acrylate may be at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. Can be.

The conjugated diene monomer may be selected from one or more selected from the group consisting of 1,3-butadiene and isoprene.

The crosslinker monomers include 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethyl It may be selected from the group consisting of all propane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and divinylbenzene.

The shell is 0.1 to 20 parts by weight based on 100 parts by weight of the total monomer monomer of at least one auxiliary monomer selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, acrylonitrile, and methacrylonitrile It may further include.

An acrylic-conjugated diene-based composite impact modifier, wherein the acrylic-conjugated diene-based composite rubber core has a glass transition temperature of -40 to 25 ° C.

In addition, the present invention is a method for producing an acrylic conjugated diene-based composite rubber impact modifier,

a) with respect to 100 parts by weight of the total seed monomer,

Iii) 65 to 99.0 parts by weight of vinyl monomers;

Ii) 0.5 to 30 parts by weight of hydrophilic monomers; And                     

Iii) 0.5 to 5 parts by weight of crosslinker monomer;

Preparing a seed latex by crosslinking the emulsion containing emulsion by polymerization;

b) 0.01 to 10 parts by weight of the sheath prepared in step a) (based on 100 parts by weight of the impact modifier)

b-1) 100 parts by weight of the first acrylic-conjugated diene-based composite rubber core total monomer,

Iii) 47.0 to 99.8 parts by weight of alkyl acrylate having 1 to 8 carbon atoms of the alkyl group;

Ii) 0.1 to 50.0 parts by weight of the conjugated diene monomer; And

iii) 0.1 to 3.0 parts by weight of crosslinker monomer;

47 to 79.9 parts by weight of an emulsion comprising a (based on 100 parts by weight of the first total composite rubber core total monomers) and emulsion polymerization to prepare a first acrylic-conjugated diene rubber core latex; And

b-2) to the latex comprising the first acrylic-conjugated diene-based composite rubber core

Based on 100 parts by weight of the second acrylic-conjugated diene-based composite rubber core total monomer,

Iii) 37.0 to 99.89 parts by weight of alkyl acrylate having 1 to 8 carbon atoms of the alkyl group;

Ii) 0.1 to 60 parts by weight of the conjugated diene monomer; And

iii) 0.01 to 3.0 parts by weight of crosslinking monomer;                     

Adding an emulsion containing 0.1 to 60 parts by weight (based on 100 parts by weight of the second acryl-conjugated diene-based composite rubber core) to prepare a second acryl-conjugated diene-based composite rubber core latex; And

c) 6 to 40 emulsion containing an alkyl methacrylate having 1 to 4 carbon atoms of an alkyl group in 60 to 90 parts by weight (based on 100 parts by weight of an impact modifier) of the acryl-conjugated diene-based composite rubbery core latex of step b). Preparing an acrylic-conjugated diene-based composite rubber impact modifier latex by adding hard parts (based on 100 parts by weight of impact modifier) and emulsifying graft polymerization to form a hard shell on the outside of the rubber core;

It provides an acrylic-conjugated diene-based composite rubber impact modifier manufacturing method comprising a.

The impact modifier latex obtained in step c) is agglomerated with an electrolyte, an organic acid, or an inorganic acid at a temperature of 0 to 100 ° C, followed by filtration and drying to obtain an impact modifier powder.

Moreover, this invention with respect to 100 weight part of vinyl chloride resin compositions,

a) 80 to 99 parts by weight of vinyl chloride resin; And

b) 1 to 20 parts by weight of the acrylic-conjugated diene impact modifier of claim 1;

It provides a vinyl chloride resin composition comprising a.

Hereinafter, the present invention will be described in detail.

The seed of the present invention is based on 100 parts by weight of the total seed monomer                     

Iii) 65 to 99.0 parts by weight of vinyl monomers;

Ii) 0.5 to 30 parts by weight of hydrophilic monomers; And

Iii) 0.5 to 5 parts by weight of crosslinker monomer;

Seed latex is prepared by reacting the emulsion containing the emulsion polymerization.

The vinyl monomer is preferably selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, and 3,4-dichloro styrene.

The hydrophilic monomers are ethyl acrylate, butyl acrylate, alkyl acrylates such as 2-ethylhexyl acrylate, methyl methacrylate, alkyl methacrylates such as benzyl methacrylate, acrylonitrile, hydroxyl methyl methacrylate And at least one selected from the group consisting of glycidyl methacrylate.

The crosslinker monomers include divinylbenzene, 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl meta It is preferable to select at least 1 type from the group which consists of a acrylate, a trimethylol propane triacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol dimethacrylate.

Hereinafter, the acryl-conjugated diene-based composite rubber core will be described.

Acryl-conjugated diene-based composite rubber core is based on 100 parts by weight of the total amount of the core monomers.                     

i) 47.0 to 99.8 parts by weight of alkyl acrylate having 1 to 8 carbon atoms of the alkyl group (based on 100 parts by weight of the first composite rubbery core total monomer);

Ii) 0.1 to 50 parts by weight of the conjugated diene monomer (based on 100 parts by weight of the first composite rubbery core total monomer); And

iii) 50 to 98 parts by weight (based on 100 parts by weight of the first composite rubbery core total monomer) of 0.1 to 3.0 parts by weight of the crosslinking agent monomer (based on 100 parts by weight of the first composite rubbery core total monomer) was added thereto and Put together to produce an acrylic rubber core latex,

In the latex comprising the first acrylic-conjugated diene-based composite rubber core

Iii) 37.0 to 99.89 parts by weight of alkyl acrylate having 1 to 8 carbon atoms of the alkyl group (based on 100 parts by weight of the second composite rubbery core total monomer);

Ii) 0.1 to 60 parts by weight of the conjugated diene monomer (based on 100 parts by weight of the second composite rubbery core total monomer); And

iii) 2 to 50 parts by weight (based on 100 parts by weight of the second composite rubber core total monomer) of 0.01 to 3.0 parts by weight of the crosslinking agent monomer (based on 100 parts by weight of the second composite rubber core total monomer) were added and In combination, an acrylic-conjugated diene-based composite rubbery core latex is prepared.

Of course, the emulsion polymerization may be used a conventional emulsifier or polymerization initiator.

The glass transition temperature (Tg) of the rubber core latex thus prepared is -40 to 25 ° C.

The alkyl acrylate may be at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. Can be. Especially preferred are ethyl acrylate, 2-ethylhexyl acrylate, butyl acrylate, or mixtures thereof.

The conjugated diene monomer may be used alone or in mixture of 1,3-butadiene and isoprene.

The crosslinker monomers include 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethyl It is preferable to select at least one from the group consisting of all propane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and divinylbenzene. Especially preferred are 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, or mixtures thereof.

The crosslinking agent is preferably used 0.1 to 3.0 parts by weight of the monomer used in the first composite rubbery core layer of the present invention. When the content of the crosslinking agent is less than 0.1 part by weight, the matrix and the spherical particles are easily deformed during processing, and the weather resistance is poor due to the double bonds remaining in the molecule.When the content of the crosslinking agent is used in excess of 3.0 parts by weight, the core exhibits brittle characteristics and impacts. The reinforcing effect is lowered.                     

By using a small amount of conjugated diene-based monomer in the acryl-conjugated diene-based composite rubbery core, it is possible to lower the glass transition temperature of the entire impact modifier due to the rubber of butadiene having a low glass transition temperature, thereby improving low-temperature impact resistance. You can. If butadiene is used more than the critical amount, the double bond remaining causes deterioration of weather resistance of the impact modifier, so that both impact and weather resistance can be satisfied by using an appropriate amount.

In addition, the butadiene double bond remaining in the second composite rubber core improves the grafting efficiency, thereby making it possible to use less crosslinking agent or grafting agent. The increase in the grafting efficiency may improve the flowability of the final powder, thereby improving workability and the like.

Examples of the crosslinking agent or grafting monomer of the second composite rubber core include 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, and 1,4-butanediol dimethacrylate. It is preferable to select at least one from the group consisting of allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and divinylbenzene. Of these, the grafting efficiency can be improved by using a small amount of mixed monomers having three or more functional groups.

The crosslinking agent or grafting monomer of the second composite rubbery core is preferably used in an amount of 0.01 to 3 parts by weight. If the crosslinking agent or the grafting agent is less than 0.01 part by weight, the graft efficiency of the hard shell is reduced and the dispersion in the matrix is lowered, so the impact resistance is reduced, and when used in excess of 3.0 parts by weight, it is disadvantageous in terms of cost.

Hereinafter, the formation of the shell will be described.

The shell of the present invention is an alkyl-conjugated diene-based rubber core latex containing a silicone rubber core 60 to 90 parts by weight (based on 100 parts by weight total impact modifier monomer) of alkyl methacrylate having 1 to 4 carbon atoms of the alkyl group An emulsion-conjugated diene-based composite impact modifier latex is prepared by adding 10 to 40 parts by weight of an emulsion including the impact modifier (based on 100 parts by weight of the total monomer) to form a hard shell on the outside of the rubber core.

Of course, the emulsion graft polymerization may be used a conventional emulsifier or polymerization initiator.

This shell graft polymerization allows the alkyl methacrylate monomer, such as methyl methacrylate, that is compatible with vinyl chloride resin to be grafted onto the surface of the rubber core to enclose the rubber core, in particular methyl methacrylate. It has a relatively high glass transition temperature, which serves to improve the cohesive properties of the final acrylic impact modifier, and has excellent compatibility with the vinyl chloride resin matrix to promote dispersion of the impact modifier particles during processing.

Such shells may be modified with acrylonitrile or methacryl to further increase compatibility with methyl acrylates, ethyl acrylates, alkyl acrylates such as butyl acrylate, or matrices to control the glass transition temperature of the shell components. Supplementary monomers of nitrile components such as nitrile may also be used. The auxiliary monomers may be used by selecting one or more kinds, and may be used by mixing within 0.1 to 20 parts by weight based on 100 parts by weight of the total monomers of the shell.

In order to prepare the acrylic-conjugated diene-based composite rubber impact modifier of the present invention as a final powder, the prepared impact modifier latex is agglomerated with an electrolyte, an organic acid or an inorganic acid at room temperature of 25 ° C., and then filtered and dried to separate the impact modifier powder. Can be obtained. In the case of aggregation, inorganic electrolytes such as calcium chloride and magnesium sulfate may be used as the electrolyte, which is the same as that of the conventional acrylic impact modifier latex.

The acrylic-conjugated diene-based composite rubber impact modifier powder thus prepared is dispersed in the vinyl chloride resin, which is a matrix resin, when it is added to a vinyl chloride-based resin, and thus rubber content, glass transition temperature, particle size and impact are important factors of impact resistance. Simultaneously satisfying the distance between the reinforcing agents to express excellent low temperature impact resistance and weather resistance, powder flow properties.

In particular, it is very useful for the production of a product using a vinyl chloride-based resin that requires both efficient processing, impact resistance, and weather resistance, such as PVC siding (PVC siding), PVC window profile (etc.). The amount of the acryl-conjugated diene-based composite rubber impact modifier of the present invention to the vinyl chloride resin may be added in an amount of 1 to 20 parts by weight based on 80 to 99 parts by weight of the vinyl chloride resin, including workability, impact resistance, weather resistance, powder flow resistance, This is preferable considering the economic aspect.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

Example 1

(Seed latex manufacturer)

First, prepare a reactor of a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a circulation condenser, 48 parts by weight of deionized water (DDI water), 0.038 parts by weight of sodium laulry sulfate (SLS), And 0.025 parts by weight of potassium persulfate. The reactor internal temperature was raised to 70 ° C. under a nitrogen atmosphere. When the reactor reached 70 ° C, 2.23 parts by weight of styrene (ST), 0.25 parts by weight of acrylonitrile (AN), and 0.0175 parts by weight of aryl methacrylate (AMA) were added at once to seed latex. Was prepared.

The conversion rate of the prepared latex was 99%, the average particle diameter was 75nm, and the total solid content (TSC) was about 5% by weight.

(Formation of First Acrylic-Conjugated Diene-based Composite Rubber Core)

20 parts by weight of deionized water (DDI water), 71.92 parts by weight of butyl acrylate (BA), butadiene, prepared in advance to form an acryl-conjugated diene-based composite rubbery core in the prepared latex (Butadiene; BD) 5 parts by weight of aryl methacrylate (AMA), 0.58 parts by weight of sodium lauryl sulfate (SLS), a monomer pre-emulsion containing a separate potassium persulfate (Potassium persulfate) ) 0.95 parts by weight was added simultaneously for 4 hours at a temperature of 70 ℃ to proceed with the reaction. After completion of the monomer preemulsion and potassium persulfate (Potassium persulfate) is aged at 55 ℃ temperature for 1 hour to complete the acrylic-conjugated diene rubber core part.

(Formation of Second Acrylic-Conjugated Diene-based Composite Rubber Core)

10 parts by weight of deionized water (DDI water), 4.9 parts by weight of butyl acrylate (BA), and butadiene (Butadiene) previously prepared in the first acrylic-conjugated diene-based composite rubbery core polymer prepared above. BD) 0.075 parts by weight, 0.025 parts by weight of aryl methacrylate (AMA), monomeric free emulsion containing 0.02 parts by weight of sodium lauryl sulfate (SLS) and 0.55 parts by weight of potassium persulfate The part was simultaneously introduced at a temperature of 70 ° C. for 4 hours to proceed with the reaction. After the addition of the monomer preemulsion and potassium persulfate, the mixture is aged at 55 ° C. for 1 hour to complete the second acrylic-conjugated diene rubber core part.

(Formation of hard cells)

10 parts by weight of deionized water, 15 parts by weight of methyl methacrylate, 0.04 parts by weight of sodium lauryl sulfate (SLS), 0.015 parts by weight of n-dodecyl mercaptane (nDDM), A cell monomer preemulsion containing 0.09 parts by weight of tert-butyl hydroperoxide (TBHP) was prepared.

The reactor temperature was raised to 55 ° C., 0.1 parts by weight of disodium ethylenediaminetetraacetate (EDTA), 0.0079 parts by weight of ferrous sulfate (FeS), and formaldehyde sodium sulfoxylate (SFS). 0.235 parts by weight is added. The reaction was carried out by adding a monomer pre-emulsion at a time. The final acrylic-conjugated diene composite latex particle size was 256 nm and the total solid content was 45 wt%.

Example 2

The same process as in Example 1 was carried out except that 10 parts by weight of butadiene and 66.92 parts by weight of butyl acrylate were used in the first acryl-conjugated diene-based composite rubbery core.

Example 3

The same process as in Example 1 was carried out except that 15 parts by weight of butadiene and 61.92 parts by weight of butyl acrylate were used in the first acrylic-conjugated diene-based composite rubbery core.

Example 4

The same process as in Example 1 was repeated except that 45 parts by weight of butadiene and 31.92 parts by weight of butyl acrylate were used in the first acryl-conjugated diene-based composite rubbery core.

Comparative Example 1

The same process as in Example-1 was carried out except that 0 parts by weight of butadiene was used in the first acrylic-conjugated diene-based composite rubbery core.

Comparative Example 2

The same process as in Example 1 was performed except that 60 parts by weight of butadiene and 16.92 parts by weight of butyl acrylate were used in the first acryl-conjugated diene-based composite rubbery core.

Comparative Example 3

The same operation as in Example 1 was carried out except that butadiene was 76.9 parts by weight in the first acrylic-conjugated diene-based composite rubbery core.

Example 5

(Production of vinyl chloride resin)                     

Polyvinyl chloride resin (PVC; LS-100 manufactured by LG Chem, polymerization degree = 1000) 100 parts by weight, 4.0 parts by weight of heat stabilizer (DLP), 0.9 parts by weight of calcium stearate (Ca-St), polyethylene wax (PE Wax) 1.36 Part by weight, 1.0 part by weight of processing aid (PA-821 manufactured by LG Chemical), 5.0 parts by weight of CaCO _{3 and} 4.0 parts by weight of TiO ₂ were added to a mixer at room temperature, and then kneaded while heating up to 115 ° C. at 1000 rpm. . When reached to 115 ℃ was lowered to 400 rpm and cooled to 40 ℃ to prepare a master batch (master batch).

After adding 6 parts by weight of the impact modifier to the masterbatch, using a two roll mill was milled at 190 ° C for 7 minutes to prepare a sheet (0.6 mm thick).

The sheet is cut to a size of 140 X 140 mm and then laminated to a 150 X 150 mm thick mold with a constant milling direction, preheated for 7 minutes using a 180 ° C. heating press (pressure 5 bar), 1 After compression for 2 minutes (pressure 50 bar), compression for 2 minutes (pressure 100 bar), compression for 3 minutes (pressure 200 bar), and cooling for 10 minutes (pressure 200 bar) to prepare a vinyl chloride resin sheet having a thickness of 2 mm.

The sheet was cut to prepare test specimens (6.5 × 1.0 × 1.8 / inch) for QUV accelerated weathering analysis and Izod impact strength (ASTM D256) test. QUV promoted climatic conditions were performed by ASTM D4329 Cycle C (Q-UVA 340 light source; 8 hours light, 4 hours light decondensation with condensation at 50 ° C.). As a result of QUV-promoted climate experiments, ΔYI was measured by measuring color retention by measuring changes in light transmission and color using a Hunter Lab colorant (Hunter Associates Laboratory, Inc., Reston, Virginia). The procedure for measuring these values is described in Instruction Manual: HUNTER LAB TRISTIMULUS COLORIMETER MODEL D25P-9 (rev. A). Measurements were taken after a minimum of 0 hours and after 300 hours of exposure. Powder flowability was measured by the funnel flow test of ASTM D-1895.

Example 6

A second acryl-conjugated diene-based composite rubbery core was prepared in the same manner as in Example 1 except that 0.75 parts by weight of butadiene and 4.75 parts by weight of butyl acrylate.

Example 7                     

A second acryl-conjugated diene-based composite rubbery core was prepared in the same manner as in Example 1 except that 0.15 parts by weight of butadiene and 4.825 parts by weight of butyl acrylate.

[Comparative Example 4]

A second acryl-conjugated diene-based composite rubbery core was applied in the same manner as in Example-1 except for applying butadiene to 4.875 parts by weight of butyl acrylate.

[Comparative Example 5]

A second acryl-conjugated diene-based composite rubbery core was applied in the same manner as in Example 1 except for applying butyl acrylate to 4.975 parts by weight of butadiene.

(Sol-gel separation)

The acrylic-silicone composite impact modifiers prepared in Examples and Comparative Examples were separated into particles, dried, swelled in toluene at room temperature for 24 hours, and then centrifuged at 0 ° C. and 12000 rpm for 120 minutes for toluene insoluble gel. And toluene dissolved sol was taken and dried in a hot air dryer to obtain a value from the following equation.

Gel content% = (weight of dry gel / total weight of impact modifier) × 100

Graft Efficiency% = (total weight of grafted monomer / total weight of cell monomer) × 100

Example 8

The second acrylic-conjugated diene-based composite rubbery core was subjected to the same method as Example-1 except that the aryl methacrylate content was 0.013 parts by weight.

Example 9

A second acrylic-conjugated diene-based composite rubbery core was prepared in the same manner as in Example-1 except that the aryl methacrylate content was 2.5 parts by weight.

Example 10

The second acrylic-conjugated diene-based composite rubbery core was prepared in the same manner as in Example 1 except that the content of butylene glycol dimethacrylate was 0.025 parts by weight instead of aryl methacrylate.

Example 11

The second acrylic-conjugated diene-based composite rubbery core was prepared in the same manner as in Example 1 except that the content of ethylene glycol dimethacrylate was 0.025 parts by weight instead of aryl methacrylate.

Example 12

The second acrylic-conjugated diene-based composite rubbery core was prepared in the same manner as in Example 1 except that the trimethylolpropane triacrylate content was 0.025 parts by weight instead of aryl methacrylate.

Example 13

A second acryl-conjugated diene-based composite rubbery core was used in the same manner as in Example 1 except that 0.013 parts by weight of aryl methacrylate and 0.013 parts by weight of trimethylolpropanetriacrylate were used simultaneously.

Comparative Example 6

The second acrylic-conjugated diene-based composite rubber core was carried out in the same manner as in Example 1 except that no crosslinking agent or grafting agent was used.

Comparative Example 7

The second acrylic-conjugated diene-based composite rubbery core was subjected to the same procedure as in Example-1 except that the butadiene content was 5 parts by weight without using a butyl acrylate, a crosslinking agent, or a grafting agent.

Comparative Example 8

The second acrylic-conjugated diene-based composite rubbery core was prepared in the same manner as in Example 1 except that the butylacrylate content was 5 parts by weight without using butadiene, a crosslinking agent, or a grafting agent.

As described above, the acrylic-conjugated diene-based composite rubber impact modifier according to the present invention is a useful invention having an effect having excellent low temperature impact resistance and weather resistance and powder flowability.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (15)

In acryl-conjugated diene-based composite impact modifier, For 100 parts by weight of the impact modifier, a) 0.01 to 10 parts by weight of the seed latex; b) 100 parts by weight of the acrylic-conjugated diene-based composite rubber core, b-1) 50 to 98 parts by weight of the first acryl-conjugated diene-based composite rubber core surrounding the sheath; And b-2) 60 to 90 parts by weight of an acryl-conjugated diene-based composite rubber core comprising 2 to 50 parts by weight of a second acrylic-conjugated diene-based composite rubber core surrounding the first composite rubber core. And c) 10 to 40 parts by weight of a shell surrounding the acrylic-conjugated diene-based composite rubbery core containing alkyl methacrylate having 1 to 4 carbon atoms of an alkyl group; Here, the seed is 대하여) 65 to 99.0 parts by weight of the vinyl monomer relative to 100 parts by weight of the total seed monomer; Ii) 0.5 to 30 parts by weight of hydrophilic monomers; And iii) 0.5 to 5 parts by weight of a crosslinker monomer, The first acrylic-conjugated diene-based composite rubbery core is 47.0 to 99.8 parts by weight of an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group, based on 100 parts by weight of the total monomers of the first acrylic-conjugated diene-based composite rubbery core. 0.1 to 50.0 parts by weight of a diene monomer, and 0.1 to 3.0 parts by weight of a crosslinker monomer, The second acrylic-conjugated diene-based composite rubbery core is 37.0 to 99.89 parts by weight of an alkyl acrylate having 1 to 8 carbon atoms of an alkyl group, based on 100 parts by weight of the total amount of the second acrylic-conjugated diene-based composite rubbery core. An acrylic-conjugated diene-based composite rubber impact modifier comprising 0.1 to 60.0 parts by weight of a diene monomer and 0.01 to 3.0 parts by weight of a crosslinking monomer. delete delete delete The method of claim 1, The vinyl monomer is an acrylic-conjugated diene-based composite rubber impact modifier, characterized in that at least one selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, and 3,4-dichloro styrene. The method of claim 1, The hydrophilic monomers are ethyl acrylate, butyl acrylate, alkyl acrylates such as 2-ethylhexyl acrylate, methyl methacrylate, alkyl methacrylates such as benzyl methacrylate, acrylonitrile, hydroxyl methyl methacrylate And, and acrylic-conjugated diene-based composite rubber impact modifier, characterized in that at least one selected from the group consisting of glycidyl methacrylate. The method of claim 1, The crosslinker monomer is divinyl benzene, 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate An acrylic-conjugated diene-based composite rubber impact modifier, characterized in that at least one selected from the group consisting of acrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol dimethacrylate. The method of claim 1, The alkyl acrylate is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate. Acrylic-conjugated diene-based composite rubber impact modifier, characterized in that. The method of claim 1, The conjugated diene-based monomer is acrylic, conjugated diene-based composite impact modifier, characterized in that at least one selected from the group consisting of 1,3-butadiene and isoprene. The method of claim 1, The crosslinker monomers include 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethyl An acryl-conjugated diene-based composite impact modifier, characterized in that at least one selected from the group consisting of all propane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and divinylbenzene. The method of claim 1, The shell is 0.1 to 20 parts by weight based on 100 parts by weight of the total monomer monomer of at least one auxiliary monomer selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, acrylonitrile, and methacrylonitrile Acrylic-conjugated diene-based composite rubber impact modifier further comprising. The method of claim 1, An acrylic-conjugated diene-based composite impact modifier, wherein the acrylic-conjugated diene-based composite rubber core has a glass transition temperature of -40 to 25 ° C. In the manufacturing method of the acrylic conjugated diene-based composite rubber impact modifier, a) with respect to 100 parts by weight of the total seed monomer, Iii) 65 to 99.0 parts by weight of vinyl monomers; Ii) 0.5 to 30 parts by weight of hydrophilic monomers; And Iii) 0.5 to 5 parts by weight of crosslinker monomer; Preparing a seed latex by crosslinking the emulsion containing emulsion by polymerization; b) 0.01 to 10 parts by weight of the sheath prepared in step a) (based on 100 parts by weight of the impact modifier) b-1) 100 parts by weight of the first acrylic-conjugated diene-based composite rubber core total monomer, Iii) 47.0 to 99.8 parts by weight of alkyl acrylate having 1 to 8 carbon atoms of the alkyl group; Ii) 0.1 to 50.0 parts by weight of the conjugated diene monomer; And iii) 0.1 to 3.0 parts by weight of crosslinker monomer; 47 to 79.9 parts by weight of an emulsion comprising a (based on 100 parts by weight of the first composite rubber core total monomers) and emulsion polymerization to prepare a first acrylic-conjugated diene rubber core latex; And b-2) to the latex comprising the first acrylic-conjugated diene-based composite rubber core Based on 100 parts by weight of the second acrylic-conjugated diene-based composite rubber core total monomer, Iii) 37.0 to 99.89 parts by weight of alkyl acrylate having 1 to 8 carbon atoms of the alkyl group; Ii) 0.1 to 60 parts by weight of the conjugated diene monomer; And iii) 0.01 to 3.0 parts by weight of crosslinking monomer; Adding an emulsion containing 0.1 to 60 parts by weight (based on 100 parts by weight of the second acryl-conjugated diene-based composite rubber core) to prepare a second acryl-conjugated diene-based composite rubber core latex; And c) 6 to 40 emulsion containing an alkyl methacrylate having 1 to 4 carbon atoms of an alkyl group in 60 to 90 parts by weight (based on 100 parts by weight of an impact modifier) of the acryl-conjugated diene-based composite rubbery core latex of step b). Preparing an acrylic-conjugated diene-based composite rubber impact modifier latex by adding hard parts (based on 100 parts by weight of impact modifier) and emulsifying graft polymerization to form a hard shell on the outside of the rubber core; Acrylic-conjugated diene-based composite rubber impact modifier manufacturing method comprising a. The method of claim 13, Agglomeration of the impact modifier latex obtained in step c) with an electrolytic, organic or inorganic acid at a temperature of 0 to 100 ° C., followed by filtration and drying to obtain an impact modifier powder. Diene composite rubber impact modifier manufacturing method. To 100 parts by weight of the vinyl chloride resin composition, a) 80 to 99 parts by weight of vinyl chloride resin; And b) 1 to 20 parts by weight of the acrylic-conjugated diene impact modifier of claim 1; Vinyl chloride-based resin composition comprising a.