KR102052500B1 - In situ trimodal rubber latex and preparing method thereof - Google Patents

Abstract

The present disclosure relates to an in situ trimodal rubber latex and a method for manufacturing the same, and more specifically, 5 to 25 wt% of rubber having an average particle diameter of 800 to 1500 mm 3, 60 to 89 wt% of rubber having an average particle diameter of 2500 to 3500 mm, average It relates to an in situ trimodal rubber latex comprising 5 to 30% by weight of a rubber having a particle diameter of 3500 to 6000 mm and 0.05 to 3% by weight of a polymer aggregate having an average particle size of 800 to 3000 mm and a manufacturing method thereof.
According to the present invention, in situ (In situ) method is economical, in situ trimodal rubber latex having excellent mechanical properties and surface properties when applied to a thermoplastic copolymer resin, a manufacturing method thereof and a thermoplastic air prepared therein There is an effect of providing the copolymer resin.

Description

INSITU TRIMODAL RUBBER LATEX AND PREPARING METHOD THEREOF {IN SITU TRIMODAL RUBBER LATEX AND PREPARING METHOD THEREOF}

The present disclosure relates to an in situ trimodal rubber latex and a method for manufacturing the same, and more specifically, 5 to 25 wt% of a rubber having an average particle diameter of 800 to 1500 mm 3, and a rubber of 60 to 3500 mm having an average particle diameter of 2500 to 3500 mm In situ trimodal rubber latex comprising 89 wt%, 5-30 wt% of rubber having an average particle diameter of 3500 to 6000 mm, and 0.05 to 3 wt% of polymer aggregate having an average particle size of 800 to 3000 mm 3 and its preparation It is about a method.

For ABS-based graft resins, the most commonly used general purpose resins in TVs, refrigerators, and automobiles, surface glossiness improvement is a potential property of the consumer because the higher the gloss, the higher the quality of the product.

For this purpose, a large-diameter rubber latex was used for the ABS-based graft resin, but there was a limit in surface gloss increase, and the reflection haze was lowered, and in particular, the impact strength was severely lowered. In addition, the use of small-diameter rubber latex has the opposite effect to that of large-diameter rubber latex, so to improve this, the large-diameter and the small-diameter are used in the latex state or by polymerizing the dried particles, respectively, but impact strength, surface gloss And the reflection haze was not satisfactory, the problem that the physical properties vary greatly depending on the injection conditions.

In order to solve this problem, three kinds of particles having average particle size, small diameter, large diameter and super-large diameter were introduced to ABS graft resin, and mainly after polymerizing ABS resin with two kinds of latex having different average particle diameters, Extrusion latex may be mixed during extrusion, or three latexes having different average particle diameters may be prepared first and then mixed during extrusion. However, this method has a disadvantage in that the economic and time loss is large because each particle must be prepared separately.

Korean Patent Publication No. 2005-0067838 (published Jul. 05, 2005)

In order to solve the problems of the prior art as described above, the present invention is to provide an in situ trimodal rubber latex.

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

In order to achieve the above object, the present base material is 5 to 25% by weight of rubber having an average particle diameter of 800 to 1500Å, 60 to 89% by weight of rubber having an average particle size of 2500 to 3500Å, and 5 to 30 rubber having an average particle size of 3500 to 6000Å It provides an in situ trimodal rubber latex comprising a weight%, and 0.05 to 3 weight% of the polymer aggregate having an average particle diameter of 800 to 3000 mm 3.

In addition, the present invention comprises the steps of (i) the first polymerization of 60 to 80 parts by weight of the conjugated diene monomer; (Ii) secondary polymerization by adding 20 to 40 parts by weight of the conjugated diene monomer and 0.1 to 0.8 parts by weight of an emulsifier at a polymerization conversion rate of 30 to 60% during the first polymerization; And (iii) tertiary polymerization by adding 0.05 to 3 parts by weight of a polymer aggregate having an average particle size of 800 to 3000 mm 3 at a polymerization conversion rate of 70 to 90% during the second polymerization. It provides a manufacturing method.

The present disclosure also provides a thermoplastic copolymer resin comprising an in situ trimodal rubber latex.

According to the present invention in situ (in situ) method is economical, in situ trimodal rubber latex having excellent mechanical properties and surface properties when applied to a thermoplastic copolymer resin, a manufacturing method thereof and a thermoplastic copolymer prepared therein There is an effect of providing a resin.

Hereinafter, the in situ trimodal rubber latex of the present disclosure and the preparation method thereof will be described in detail.

In situ trimodal rubber latex of the present substrate is 5 to 25% by weight of rubber having an average particle size of 800 to 1500Å, 60 to 89% by weight of rubber having an average particle size of 2500 to 3500Å, and 5 to 30 weight of rubber having an average particle size of 3500 to 6000Å %, And 0.05 to 3% by weight of the polymer agglomerates having an average particle diameter of 800 to 3000 GPa, and excellent stability of rubber latex and thermoplastic copolymer latex including the same within this range, and excellent surface gloss, reflection haze and retention gloss. While the impact strength is excellent.

The in situ trimodal rubber latex of the present disclosure refers to a trimodal rubber latex formed by polymerizing simultaneously or continuously in one reactor, rather than mixing rubber latexes having different average particle diameters.

In another example, in-situ trimodal rubber latex is 5 to 20% by weight rubber having an average particle size of 800 to 1500Å, 65 to 85% by weight rubber having an average particle size of 2500 to 3500 내지, and 5 to 25 rubber having an average particle size of 3500 to 6000Å It includes the weight percent, and 1 to 2% by weight of the polymer aggregate having an average particle diameter of 800 to 3000mm 3, the stability of the rubber latex and the thermoplastic copolymer latex comprising the same within this range, the surface gloss, reflective haze and retention gloss Excellent impact strength is excellent.

The rubber may be, for example, an acrylate rubber, a conjugated diene rubber, or a mixture thereof.

The acrylate rubber is at least one selected from the group consisting of, for example, butyl acrylate rubber, 2-ethylhexyl acrylate rubber, butyl acrylate-styrene copolymer, and 2-ethylhexyl acrylate-acrylonitrile copolymer. Can be.

The conjugated diene rubber may be at least one selected from the group consisting of butadiene polymer, butadiene-styrene copolymer (SBR), butadiene-acrylonitrile copolymer (NBR) and ethylene-propylene copolymer (EPDM). .

Polymer aggregates having an average particle diameter of 800 to 3000 mm 3 are, for example, unsaturated carboxylic acids or ester monomers thereof; And a comonomer having a functional group; and may be a polymerized copolymer.

In addition, the method for producing an in situ trimodal rubber latex of the present disclosure comprises the steps of: (i) 60 to 80 parts by weight of a first conjugated diene monomer; (Ii) secondary polymerization by adding 20 to 40 parts by weight of the conjugated diene monomer and 0.1 to 1.0 parts by weight of an emulsifier at a polymerization conversion rate of 30 to 60% during the first polymerization; And (iii) tertiary polymerization by adding 0.05 to 3 parts by weight of the polymer aggregate having an average particle size of 800 to 3000 Pa at a polymerization conversion rate of 70 to 90% during the second polymerization.

The conjugated diene monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and pyrrylene.

As another example, the conjugated diene monomer may further include an aromatic vinyl monomer, a vinyl cyan monomer, or a mixture thereof, and may be included in an amount of 20 parts by weight or less based on 100 parts by weight of the total monomers.

In the step (i), the first polymerization may include, for example, 1 to 3 parts by weight of an emulsifier, 0.5 to 3 parts by weight of an electrolyte, 0.1 to 0.5 parts by weight of a molecular weight regulator, and 0.1 to 0.5 parts by weight of an initiator.

In the step (ii), when the polymerization conversion rate is 30 to 60%, for example, the average particle size may be 2300 to 2700 mm 3, or 2400 to 2600 mm 3, and within this range, the balance between small and large particle generation is excellent, and thus the mechanical properties and The surface characteristics are excellent.

In the step (ii), the second polymerization may include, for example, 0.1 to 1.0 parts by weight, or 0.3 to 0.8 parts by weight of an emulsifier. Within this range, the small diameter and the large diameter generated during the secondary polymerization have an efficient ratio. As a result, after the tertiary polymerization, the ratio of the small diameter, the large diameter and the large diameter is optimized.

In the step (ii), the second polymerization may use, for example, 0.05 to 0.5 parts by weight of an initiator.

In the step (iii), the polymer agglomerates may be introduced at 70 to 90%, 70 to 80%, or 70 to 75%, for example, in which case the latex is stable and a part of the small diameter is large diameter, Some of them have an excellent effect of bloating with super-caliber.

In the step (iii), the tertiary polymerization may include, for example, 0.05 to 3 parts by weight, 0.5 to 2.5 parts by weight, or 1 to 2 parts by weight of the polymer aggregate, and within this range, the latex is stable and the polymer The aggregate is combined with a small diameter and a part of a large diameter so that a part of the small diameter becomes a large diameter, and a part of the large diameter is enlarged to a super large diameter.

For example, the first polymerization may be performed at 65 to 70 ° C., the second polymerization may be performed at 70 to 75 ° C., and the third polymerization may be performed at 80 to 85 ° C., for example. There is a synergistic effect.

The polymer aggregate having an average particle size of 800 to 3000 mm 3 is, for example, an unsaturated carboxylic acid polymer or an unsaturated carboxylic acid ester polymer, and specific examples include: (a) polymerizing 10 to 20 parts by weight of an unsaturated carboxylic acid or an ester monomer thereof; (b) polymerizing by adding an emulsion of 75 to 85 parts by weight of an unsaturated carboxylic acid or its ester monomer and 5 to 10 parts by weight of a comonomer having a functional group in an emulsion form at 80 to 95% of the polymerization conversion rate; And (c) terminating the polymerization at a polymerization conversion rate of 98% or more during the polymerization.

The unsaturated carboxylic acid or ester monomer thereof may be, for example, an ethylenic carboxylic acid, an ester thereof, an acrylate monomer, or a mixture thereof.

The unsaturated carboxylic acid polymer may further include one or more comonomers selected from the group consisting of C _4-6 conjugated double bond monomers, monovinyl aromatic hydrocarbon monomers and vinyl cyan monomers, for example, various rubbers. It is applicable to latex and has the effect of improving mechanical properties and surface properties.

The ethylenically unsaturated carboxylic acid may be at least one selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid.

The unsaturated carboxylic ester monomer may be, for example, an alkyl ester of the unsaturated carboxylic acid, ie an alkyl unsaturated carboxylic ester.

The functional group may be at least one selected from the group consisting of, for example, an amide group, an alcohol group, a carboxylic acid group, a sulfonic acid group, a phosphate group, and a boric acid group, and in this case, deteriorates the role of an emulsifier in the rubber latex or prevents ionic bonding. It is effective in causing the particles to collide effectively and make the particles grow larger.

The comonomer having the functional group may be at least one selected from the group consisting of methacrylic amide, acrylamide, methacrylic acid and acrylic acid.

The step (a) may be an emulsion polymerization at 75 to 85 ° C. using 0.1 to 0.5 parts by weight of an emulsifier, 0.05 to 0.02 parts by weight of an initiator and 60 to 70 parts by weight of ion-exchanged water.

The step (b) may be an emulsion polymerization using, for example, 1 to 5 parts by weight of an emulsifier, 30 to 40 parts by weight of ion-exchanged water, and 0.5 to 2 parts by weight of an initiator.

The emulsifiers described herein are at least one selected from the group consisting of, for example, allyl aryl sulfonates, alkali methyl alkyl sulfonates, sulfonated alkyl esters, fatty acid soaps, and rosin acid alkali salts.

The initiator of the present disclosure may be at least one selected from the group consisting of, for example, a water-soluble polymerization initiator, a fat-soluble polymerization initiator, and an oxidation-reduction catalyst.

The water-soluble polymerization initiator may be, for example, a persulfate salt, and the persulfate salt may be, for example, one or more selected from the group consisting of potassium persulfate, sodium persulfate, and ammonium persulfate.

The fat-soluble polymerization initiator may be, for example, a peroxy compound, and in another example, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide It may be at least one selected from the group consisting of, and benzoyl peroxide.

The redox-based catalyst may be, for example, at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylene diamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite.

The electrolyte is, for example, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , K ₂ SO ₄ , NaHSO ₃ , K ₂ P ₂ O ₇ , Na ₂ P ₂ O ₇ , At least one selected from the group consisting of K ₃ PO ₄ , Na ₃ PO _{4 ,} and K ₂ HPO ₄ .

The molecular weight modifier may be, for example, mercaptans.

In addition, the substrate may be a thermoplastic copolymer resin polymerized including the in situ trimodal rubber latex.

The thermoplastic copolymer resin may be, for example, an ABS copolymer resin in which an aromatic vinyl compound and a vinyl cyan compound are graft-polymerized on the in situ trimodal rubber latex.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Example  One

<Polymer Aggregate Preparation>

After filling the reactor with nitrogen or argon gas, 15 parts by weight of ethyl acrylate, 0.3 parts by weight of fatty acid soap (oleic acid potassium salt) as an emulsifier, 0.01 parts by weight of initiator potassium persulfate, and 65 parts by weight of ion-exchanged water were added at a temperature of 80 ° C. Emulsion polymerization was carried out at. In the emulsion polymerization, the polymerization conversion rate of 90% (based on the batch monomer conversion) 80% by weight of ethyl acrylate and 5 parts by weight of methacrylamide, 3 parts by weight of fatty acid soap (oleic acid potassium salt) as an emulsifier, 35 parts by weight of ion-exchanged water It was made in the form of 3 hours, and on the other side, 1 part by weight of initiator potassium persulfate and 165 parts by weight of ion-exchanged water were added for 3 hours, followed by emulsion polymerization at 80 ° C. The polymerization was terminated at the polymerization conversion rate of 98% or more during the emulsion polymerization, and the obtained polymer aggregate had an average particle diameter of 1970 mm 3.

Preparation of In situ Trimodal Rubber Latex

60 parts by weight of ion-exchanged water, 75 parts by weight of 1,3-butadiene, 1 part by weight of potassium rosin salt as emulsifier, 0.8 part by weight of fatty acid soap, 1.5 parts by weight of sodium sulfate as electrolyte, in a nitrogen-substituted polymerization reactor (autoclave) 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as the molecular weight regulator and 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as the initiator were polymerized at a reaction temperature of 70 ° C., and then at 1, at a polymerization conversion rate of 40%. 25 parts by weight of 3-butadiene and 0.15 parts by weight of potassium persulfate were collectively administered, and when the average particle diameter was 2300 to 2700 mm at a polymerization conversion rate of 45%, 0.8 parts by weight of an emulsifier Latemul ASK (Kao Kao Co., Ltd.) was administered. After the reaction was carried out up to 60%, the temperature was raised to 80 ° C, and the polymerization was carried out by adding 1.5 parts by weight of the polymer aggregate prepared above at a polymerization conversion rate of 75%, and the reaction was terminated at the polymerization conversion rate of 97%. Prepared. The pH of the final latex was adjusted to the general level of 10.7.

 Capillary Hydrodynamic Fractionation (CHDF) confirmed that three in situ trimodal rubber latexes having different average particle diameters were prepared.

<ABS resin manufacturing>

65 parts by weight of the in-situ trimodal latex prepared above and 100 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 10 parts by weight of acrylonitrile, 25 parts by weight of styrene, and 20 parts by weight of ion-exchanged water. , 0.1 part by weight of t-butyl hydroperoxide, 1.0 part by weight of potassium rosinate and 0.3 part by weight of tertiary dodecyl mercaptan, 0.054 part by weight of dextrose, 0.004 part by weight of pyrolate, and ferrous sulfate 0.0002 The weight part was added at 70 ° C. for 3 hours. After the addition was completed, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrolate, 0.001 parts by weight of ferrous sulfate, and 0.005 parts by weight of t-butyl hydroperoxide were collectively added to the polymerization reactor and heated up to 80 ° C. for 1 hour. After the reaction was terminated to prepare ABS latex. At this time, the polymerization conversion rate was 98%. The prepared ABS latex was agglomerated with sulfuric acid, dehydrated and dried to obtain an ABS powder, and then mixed with a SAN resin in a weight ratio of 26:74 to produce a specimen for measurement of physical properties.

Example  2

Except for using the emulsifier Latemul ASK (Kao Kao Co., Ltd.) in the polymerization conversion rate of 45% to prepare the in-situ trimodal rubber latex in Example 1 in the same manner as in Example 1.

Comparative example  One

The same experiment as in Example 1 except that the polymer aggregate was not administered in Example 1.

Comparative example  2

1.5 parts by weight of potassium carbonate was used as the electrolyte in Example 1, and the same experiment as in Example 1 was performed except that the polymer aggregate and the emulsifier Latemul ASK were not administered.

Comparative example  3

Except for the use of the emulsifier Latemul ASK (Kao Kao Co., Ltd.) in the polymerization conversion rate 45% in the preparation of in situ trimodal rubber latex in Example 1 was carried out in the same manner as in Example 1.

Comparative example  4

Except that the polymer agglomerate in 4.0 parts by weight in Example 1 was the same as in Example 1.

 [Test Example]

The properties of the specimens prepared in Example 1 and Comparative Examples 1 to 4 were measured by the following method, and the results are shown in Table 1 below.

How to measure

* Polymerization Conversion Rate (%): 1.5 g of the prepared latex was dried in a 150 ° C. hot air dryer for 15 minutes, and then weighed to obtain a total solids content (TSC). The polymerization conversion rate was calculated by the following Equation 1, and the average The particle size was measured by diluting the prepared latex 1 g in distilled water 100 g, using a light scattering measuring device (Nicomp), and recorded the number average particle diameter of the measuring device.

[Equation 1]

* Average particle diameter (Å) and its content (% by weight): measured using Capillary Hydrodynamic Fractionation (CHDF, Matec Applied Science, Model 1100).

* Solidified solid content (% by weight): After filtering the latex produced by the emulsion polymerization method in a 100 mesh (mesh) wire mesh filter and the polymer that did not pass on the wire mesh in a hot air dryer at 100 ℃ for 1 hour, the total monomer and It is expressed as a ratio with respect to the theoretical total amount of the additive (emulsifier, etc.).

* Latex stability (% by weight): The latex stability of the rubbery polymer is obtained by filtering 500 g of the final polymerized latex obtained by using a 100 mesh net and leaving it to stand for 60 minutes in a homo-mixer (TK Robomics) 10,000 RPM. The coagulum suspended in the mesh nets was reported in weight percent relative to the theoretical total solids content. In addition, the graft copolymer was recorded by measuring the time the polymer is solidified at 15,000 RPM conditions and classified as a stable latex for the polymer over 60 minutes.

* Izod impact strength (1/4 ″, kgf · cm / cm): measured in accordance with ASTM D256.

* Flow index (MI; g / 10 min): measured according to ASTM D1238 under the condition of 220 ° C./10 kg.

* Tensile strength (kgf / cm ² ): was measured according to ASTM D638.

* Surface gloss: measured according to ASTM D528 at 45 ° angle.

* Retention gloss: The pellet obtained from the extruder is placed in the injection molding machine and held for 15 minutes at 250 ° C. After that, a gloss specimen is obtained, and the gloss is measured at 45 ° with the specimen injected without staying at 200 ° C. Measured. At this time, the smaller the measured value, the better the retention gloss.

Reflection haze: Measurements were made using 512 diodes arranged in a straight line profiling the reflected light in a large arc from 14 ° to 27 ° using a Rhopoint IQ apparatus. It was calculated by Equation 2 below at an angle of 20 °.

[Equation 2]

* Retention Discoloration (ΔE): For the gloss specimen obtained by the same method of specifying the retention gloss, using the Suga color computer, L, a, b values for the specimens before and after the retention were obtained and The degree of discoloration was calculated. At this time, the smaller the measured value is, the less the discoloration of discoloration.

[Equation 3]

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Go
radish
quality

la
Tech
S Polymerization conversion rate
(%) 97.6 98 97.3 98.2 98.3 97 Latex Stability 0.02 0.05 0.02 0.03 0.01 3.2 Solid coagulant
(weight%) 0.02 0.24 0.01 0.02 <0.01 8 Average particle size distribution
(weight%) 4500
(25% by weight) 4510
(7% by weight)) 2870
(73% by weight)
2930
(100
weight%) 4470
(5% by weight) 4630
(10% by weight) 2830
(65% by weight) 2910
(85% by weight) 1020
(27% by weight) 2790
(46% by weight) 2871
(83% by weight) 980
(10% by weight) 1001
(8% by weight) - 1030
(49% by weight) 993
(7% by weight)) A
B
S

Number
G
Polymerization conversion rate
(%) 98 97.7 97.4 98.2 98.1 Not measurable Latex Stability 0.02 0.05 0.02 0.03 0.01 Not measurable Solid coagulant
(weight%) 0.03 0.04 0.02 0.05 0.07 Mass produce Impact strength 34.8 32.2 26.7 31 22 - Flow index 22.1 21.6 21.5 21 21.5 - The tensile strength 452 467 472 465 483 - Surface gloss 95 94 96 88 97 - Reflection haze 2.4 2.7 2.3 3.2 2.6 - Discoloration 2.1 2.5 2.7 3 3 - Staying gloss 4.2 5 5.4 7 8.3 -

As shown in Table 1, Examples 1 and 2 of the present disclosure not only had excellent mechanical and tensile strength and impact strength, but also had excellent workability, thermal stability, surface gloss, and reflection haze (surface sharpness).

On the other hand, Comparative Examples 1 (bimodal) to 2 (monomodal) were all deteriorated in mechanical properties and surface gloss, reflection haze, retention discoloration and retention gloss. In particular, the mechanical strength and the surface properties (surface gloss, reflection haze) is in a trade-off relationship, the introduction of in situ trimodal rubber latex was confirmed that the synergistic effect of improving both mechanical properties and surface properties can be obtained.

In addition, Comparative Example 3 containing an excessive amount of an emulsifier in the preparation of in situ trimodal rubber latex produced a large amount of super-diameter, so that the surface characteristics such as impact strength and retention discoloration and retention gloss was lowered, compared with the use of polymer aggregates in excess In Example 4, the stability of the rubbery latex was reduced and a large amount of solid coagulum was produced.

Claims (17)

5 to 25% by weight of rubber having an average particle diameter of 800 to 1500 mm, 60 to 89% by weight of rubber having an average particle diameter of 2500 to 3500 mm, 5 to 30% by weight of rubber having an average particle diameter of 3500 to 6000 mm, and an average particle diameter of 800 to 3000 mm Including 0.05 to 3% by weight of the polymer aggregate,
The polymer aggregates may be unsaturated carboxylic acids or ester monomers thereof; And comonomer having a functional group; including a polymerized copolymer,
The unsaturated carboxylic acid or ester monomer thereof is an ethylenically unsaturated carboxylic acid, ester thereof, acrylate monomer or a mixture thereof,
The functional group is in situ trimodal rubber latex, characterized in that at least one member selected from the group consisting of amide group, alcohol group, carboxylic acid group, sulfonic acid group, phosphate group, and boric acid group.
The method of claim 1,
In-situ trimodal rubber latex, characterized in that the rubber is an acrylate rubber, conjugated diene rubber or a mixture thereof.
delete (i) first polymerizing 60 to 80 parts by weight of the conjugated diene monomer;
(Ii) secondary polymerization by adding 20 to 40 parts by weight of the conjugated diene monomer and 0.1 to 0.8 parts by weight of an emulsifier at a polymerization conversion rate of 30 to 60% during the first polymerization; And
(Iii) tertiary polymerization by adding 0.05 to 3 parts by weight of the polymer aggregate having an average particle size of 800 to 3000 Pa at a polymerization conversion rate of 70 to 90% during the second polymerization.
The polymer aggregate is (a) polymerizing 10 to 20 parts by weight of an unsaturated carboxylic acid or ester monomer thereof; (b) polymerizing by introducing an emulsion form of 75 to 85 parts by weight of unsaturated carboxylic acid or its ester monomer and 5 to 10 parts by weight of a comonomer having a functional group in an emulsion form at 80 to 95% of the polymerization conversion rate; And (c) terminating the polymerization at a polymerization conversion rate of 98% or more during the polymerization.
The unsaturated carboxylic acid or ester monomer thereof is an ethylenically unsaturated carboxylic acid, ester thereof, acrylate monomer or a mixture thereof,
The functional group is an in situ trimodal rubber latex production method, characterized in that at least one member selected from the group consisting of amide group, alcohol group, carboxylic acid group, sulfonic acid group, phosphate group, and boric acid group.
delete The method of claim 4, wherein
Step (a) is an in situ trimodal rubber latex, characterized in that the emulsion polymerization at 75 to 85 ℃ using 0.1 to 0.5 parts by weight of emulsifier, 0.05 to 0.02 parts by weight of initiator and 60 to 70 parts by weight of ion-exchanged water Way.
The method of claim 4, wherein
The step (b) is a method for producing an in situ trimodal rubber latex, characterized in that the emulsion polymerization using 1 to 5 parts by weight of emulsifier, 30 to 40 parts by weight of ion-exchanged water and 0.5 to 2 parts by weight of initiator.
delete delete The method of claim 4, wherein
Wherein said emulsifier is at least one selected from the group consisting of allyl aryl sulfonate, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps and rosin acid alkali salts.
The method of claim 4, wherein
Step (ii) is a method for producing an in situ trimodal rubber latex, characterized in that when the polymerization conversion rate is 30 to 60%, the average particle diameter is 2300 ~ 2700Å.
The method of claim 4, wherein
In the step (i) the first polymerization is in situ trimodal rubber, characterized in that 1 to 3 parts by weight of emulsifier, 0.5 to 3 parts by weight of electrolyte, 0.1 to 0.5 parts by weight of molecular weight regulator and 0.1 to 0.5 parts by weight of initiator Method for producing latex.
The method of claim 4, wherein
The secondary polymerization in step (ii) is a method for producing an in situ trimodal rubber latex, characterized in that using 0.05 to 0.5 parts by weight of the initiator.
The method of claim 4, wherein
The first polymerization is 65 to 70 ℃, the second polymerization is 70 to 75 ℃ and the third polymerization is a method of producing an in situ trimodal rubber latex, characterized in that carried out at 80 to 85 ℃.
The method of claim 4, wherein
The conjugated diene monomer is a method for producing in situ trimodal rubber latex, characterized in that at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and pyrrylene.
The method of claim 4, wherein
The conjugated diene monomer is a method for producing an in situ trimodal rubber latex, characterized in that it further comprises an aromatic vinyl compound monomer, vinyl cyan monomer or a mixture thereof.
A thermoplastic copolymer resin comprising the in situ trimodal rubber latex of claim 1.