KR101452020B1 - Thermoplastic resin composition with excellent weatherability and a method for preparing thereof - Google Patents
Thermoplastic resin composition with excellent weatherability and a method for preparing thereof Download PDFInfo
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Abstract
The present invention relates to a thermoplastic resin composition having excellent weatherability and a method for producing a thermoplastic resin composition using the same. More specifically, the present invention relates to a thermoplastic resin composition comprising a) an aromatic vinyl compound and a vinyl cyanide compound 20 to 40 parts by weight of a hydrogenated modified core-shell graft copolymer to which hydrazine, a peroxide compound and an acid catalyst are added to the grafted core-shell graft copolymer, b) 60 to 80 parts by weight of a styrene-acrylonitrile (SAN) resin having a weight-average molecular weight of 1,000 to 180,000, and c) 1 to 3 parts by weight of CaCO 3 based on 100 parts by weight of the total of a) and b) Which has an effect of providing a thermoplastic resin composition excellent in impact resistance, rigidity and weather resistance.
Description
The present invention relates to a thermoplastic resin composition having excellent weather resistance and a method for producing a thermoplastic resin composition using the same. More particularly, the present invention relates to a thermoplastic resin composition which is excellent in weatherability, A thermoplastic resin excellent in impact resistance, strength and weather resistance comprising hydrazine, a peroxide compound and an acid catalyst added to the hydrogenated modified core-shell graft copolymer and containing styrene-acrylonitrile resin and CaCO 3 Compositions and methods of making the same.
ABS resin based on conjugated diene rubber is processed and processed into a desired shape through extrusion and injection process of powder made by emulsion polymerization and styrene-acrylonitrile copolymer prepared by solution polymerization. General ABS resin has excellent workability, mechanical properties and appearance properties and is widely used for interior and exterior parts of electric and electronic products, automobiles, small toys, furniture, and building materials.
However, due to the double bonds of the butadiene rubber component used as an impact modifier, the weatherability is poor. Double bonds tend to be oxidized and discolored because they are easily broken because the amount of energy required to break one chain is smaller than that of a single bond. Therefore, in the environment where ABS is directly exposed to ultraviolet rays like outdoor, the appearance and color of the resin are changed, and the mechanical properties are rapidly deteriorated. The deterioration of the ABS resin is attributed to the butadiene component, as the hydrogen of -CH 2 - adjacent to the remaining double bond in the molecule becomes the starting point of the oxidation reaction by the action of light or oxygen and the main chain causes a crosslinking reaction to be.
In order to obtain a balanced resin by adding weather resistance while maintaining various excellent properties of the ABS resin, methods such as addition of an ultraviolet stabilizer, painting, plating and the like are usually taken, but this is not an essential improvement. Here, various resins were developed in which the butadiene component, which is the cause of deterioration, was removed and replaced with a rubber having no unsaturated bond instead. Representative resins include ASA resins using acrylic rubber instead of butadiene rubber and AES resins using EPDM rubber. However, since the production process and basic physical properties tend to be lower than those of ABS, researches have been made to improve the weather resistance of ABS resins using a method of adding additives to ABS.
Stabilizer formulations for improving the thermal stability and the like of ABS resins are well known in the international application PCT / EP / 2003/008189. The improvement of thermal stability through the combination of primary antioxidants, organic phosphites and benzofuranone derivatives as an antioxidant during polymerization is disclosed in US Pat. No. 6,752,226, which discloses the improvement of discoloration through the addition of dioxopiperazine derivatives Lt; / RTI > In addition, Korean Patent Laid-Open Publication No. 10-2007-0047073 discloses a method for producing a styrene-acrylonitrile (SAN) resin by adding a first phosphite-based antioxidant to a base resin composed of an acrylonitrile-butadiene-styrene copolymer (g- , A second phosphite-based antioxidant and an alkali metal phosphate which are different from each other in the temperature range of oxidation reaction with the first phosphite-based antioxidant to improve the thermostability, the initial color discoloration resistance and the weather resistance. However, the improvement of weatherability by the addition of such additives and the improvement of weatherability by the combination change occur as a main factor of cost increase, and when additives such as pressure extrusion are blown out by gas, impurities are seen on the surface of the molded article And thus the product value of the molded article is deteriorated.
U.S. Patent No. 4,452,950 discloses that hydrogenation of nitrile-butadiene rubber (NBR) latex using hydrazine and hydrogen peroxide improves oxidation and deterioration prevention. However, this also has not helped to improve weatherability and discoloration resistance.
In order to solve the problems of the prior art as described above, the present inventors have found that, in the production of a thermoplastic resin composition, the conjugated diene rubber latex core is modified by hydrogenation using hydrazine, a peroxide compound and an acid catalyst, When the styrene-acrylonitrile resin mixture is appropriately blended therein, it is confirmed that the weather resistance is significantly improved without deteriorating impact strength, tensile strength and flexural strength as described in the following examples, and the present invention is completed on the basis thereof .
That is, an object of the present invention is to modify a core-shell graft copolymer based on a conjugated diene-based rubber latex core by hydrogenation, formulate a styrene-acrylonitrile resin with a filler, And weather resistance, and a process for producing a thermoplastic resin composition using the thermoplastic resin composition.
In order to achieve the above object,
a) adding a hydrazine, a peroxide compound and an acid catalyst to a core-shell graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber latex core having an average particle diameter of 200 to 500 nm, 20 to 40 parts by weight of an addition-modified core-shell graft copolymer,
b) 60 to 80 parts by weight of a styrene-acrylonitrile (SAN) resin having a weight average molecular weight of 100,000 to 180,000, and
c) 1 to 3 parts by weight of CaCO 3 based on 100 parts by weight of the total of a) and b).
In addition,
A first step of preparing a core-shell graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber latex core having an average particle diameter of 200 to 500 nm;
A second step of adding hydrazine, a peroxide compound and an acid catalyst to the core-shell graft copolymer to obtain a hydrogenated modified core-shell graft copolymer; And
And a third step of blending the styrene-acrylonitrile resin having a weight average molecular weight of 100,000 to 180,000 and a glass transition temperature of 60 ° C or higher as the remainder in the hydrogenated modified core-shell graft copolymer with CaCO 3 , The present invention also provides a method for producing a thermoplastic resin composition having excellent weather resistance.
Hereinafter, the present invention will be described in detail.
a-1) core-shell Graft Copolymer
The core-shell graft copolymer of the present invention is produced as a core-shell type by grafting an aromatic vinyl compound and a vinyl cyan compound onto a conjugated diene rubber latex core.
The conjugated diene rubber latex core preferably has an average particle diameter in the range of 200 to 500 nm in view of securing physical properties such as impact and coloration and stability of latex. That is, when the thickness is less than 200 nm, the physical properties are deteriorated. When the thickness is more than 500 nm, the latex stability is deteriorated and the coloring property is also remarkably deteriorated.
As the aromatic vinyl compound, styrene, styrene derivatives such as alpha-methylstyrene, para-methylstyrene, and vinyltoluene may be used, and styrene is preferable. The content of the core-shell graft copolymer is preferably 25 to 50 parts by weight based on 100 parts by weight of the core-shell graft copolymer.
As the vinyl cyan compound, acrylonitrile, methacrylonitrile or ethacrylonitrile may be used, and ethacrylonitrile is preferable in consideration of rigidity. And the content thereof is preferably 10 to 25 parts by weight based on 100 parts by weight of the core-shell graft copolymer.
Examples of usable additives include emulsifiers, initiators, activators, molecular weight regulators, and the like. Examples of the emulsifier include, but are not limited to, fatty acid-based emulsifiers such as oleic acid, stearic acid, lauric acid, and sodium or potassium salts of mixed fatty acids, and general anionic emulsifiers such as rosin acid. Can be mixed and used.
As the initiator, an inorganic or organic peroxide compound may be used, and a water-soluble initiator including potassium persulfate, sodium persulfate, ammonium persulfate and the like or an oil-soluble initiator including cumene hydroperoxide, benzoyl peroxide and the like may be used have.
In order to accelerate the initiation reaction of the peroxide with the initiator, an activator may be used. Examples of the activator include sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate or dextrose, Can be mixed and used.
Examples of the molecular weight regulator include terpines such as mercaptans, tabinolenes, dipentenes and t-terpenes, and halogenated hydrocarbons such as chloroform and carbon tetrachloride.
a-2) Hydrogenation Reformed Core-shell Graft Copolymer
The core-shell graft copolymer thus prepared is modified through hydrogenation, which is a technical feature of the present invention. That is, for the hydrogenation reaction, 0.1 to 100 parts by weight of hydrazine, 0.1 to 70 parts by weight of the peroxide compound and 0.01 to 10 parts by weight of the acid catalyst are added to the core-shell graft copolymer in the latex state, .
Hydrazine hydrate, hydrazine acetate, hydrazine sulfate, hydrazine hydrochloride and the like may be used as the hydrazine, and it is preferably used in an amount of 0.1 to 100 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the resin . If it is used in an amount of less than 0.1 part by weight, the effect of improving weatherability is poor. If it is more than 20 parts by weight, a gel is formed during the reaction, which may adversely affect appearance and the like.
As the peroxide compound that can be used, hydroperoxides and the like can be mentioned. In view of the efficiency of the hydrogenation reaction, the peroxide compound is preferably used in an amount of 0.1 to 70 parts by weight, more preferably 2 to 20 parts by weight, .
Examples of the acid catalyst that can be used include, but are not limited to, boric acid and the like. It is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the resin.
In addition, dimethyl siloxane (commercial product name: siloxane) may be further added for the purpose of suppressing generation of nitrogen gas during latex modification. At this time, it is preferable to use the used amount within the range of 0.1 to 3 parts by weight based on 100 parts by weight of the resin, which is undesirable because excessive use may lower the thermal stability and degrade during processing to adversely affect the surface characteristics.
According to the present invention, a reaction scheme in which a diimide formed from a hydrogene and a hydroperoxide form a diimide and a formed double bond of a butadiene into a single bond is as follows. As shown in the following reaction equation, nitrogen gas is generated during the process.
[Reaction Scheme 1]
After the reaction, the core-shell graft copolymer thus modified is subjected to atmospheric pressure agglomeration using sulfuric acid or magnesium sulfate (MgSO 4 ) as a coagulant, followed by dehydration, washing and drying to obtain a powder Particles.
b) Styrene- Acrylonitrile Suzy
The styrene-acrylonitrile resin used in the present invention is a hard matrix which can be melt-kneaded with a hydrogen-modified core-shell graft copolymer and is composed of a hard polymer having a glass transition temperature of at least 60 ° C., A compound containing a unit derived from a vinyl cyan compound, a methyl methacrylate or the like, or a compound capable of forming a polycarbonate polymer, or the like, or a mixture of two or more thereof.
The styrene-acrylonitrile resin has a weight average molecular weight of 100,000 to 180,000 and a glass transition temperature of at least 60 DEG C or more. More preferably, the styrene-acrylonitrile resin has a weight average molecular weight of 100,000 to 120,000, 20 to 60 parts by weight of a resin, and a second resin having a high molecular weight having a weight average molecular weight of 150,000 to 180,000 may be mixed in a total amount of 20 to 60 parts by weight. When two kinds of styrene-acrylonitrile resins are mixed with the above-mentioned composition, appropriate fluidity and mechanical properties can be obtained.
At this time, when the glass transition temperature is too low, the physical properties such as rigidity are lowered. Therefore, the lower limit value is set at 60 ° C. In this case, the glass transition temperature of the first highly flowable resin is 100 to 105 ° C, and the glass transition temperature of the second high molecular weight resin is more preferably 105 to 110 ° C.
c) CaCO 3
CaCO 3 is the most suitable among various inorganic fillers according to the present invention. Specifically, CaCO 3 plays a role of blocking UV radiant energy and not only improves weatherability but also improves rigidity because it is inorganic. It is most preferable that the CaCO 3 is used in an amount of 1 to 3 parts by weight based on 100 parts by weight of the sum of the g-ABS resin and the SN resin, in view of improving the weatherability and rigidity as described in the following examples.
Acrylonitrile resin, 60 to 80 parts by weight, and wherein c) CaCO 3 - thermoplastic resin composition of the present invention are hydrogenated modified core of the a) - shell graft copolymer of 20 to 40 parts by weight of the b) styrene . Particularly, when the content of the hydrogenated modified core-shell graft copolymer of a) is less than 20 parts by weight, impact resistance and weather resistance are lowered, while when it exceeds 40 parts by weight, gloss, scratch resistance and rigidity are deteriorated It is therefore important to maintain this ratio between a) and b).
It is obvious to those skilled in the art that the thermoplastic resin composition of the present invention may further comprise a lubricant, a hindered phenol antioxidant, a UV stabilizer, an antistatic agent or other additives commonly used in accordance with the application, in addition to the above components.
The lubricant may be ethylene bis stearamide, stearic acid, alkali metal stearate, or low molecular weight polyethylene. The lubricant may be used in an amount of 1 to 5 parts by weight per 100 parts by weight of the thermoplastic resin composition, By weight.
Examples of the hindered phenolic antioxidants include stearyl-? - (3,5-di-t-butyl-4-hydroxylphenyl), octadyl-3- (4-hydroxy- Butylphenyl) -propionate or 2,2-methylenebis (4-methyl-6-butylphenol), and the hindered phenol antioxidant may be used in combination with a thermoplastic resin composition 0.1 to 0.5 parts by weight based on 100 parts by weight of the composition.
Tris (2,4-di-t-butylphenyl) phosphite or the like can be used as the phosphite antioxidant, and the phosphite antioxidant can be used in a total amount of 100 wt.% Of the thermoplastic resin composition a) and b) 0.1 to 0.5 parts by weight based on 100 parts by weight of the composition.
As the ultraviolet stabilizer, bis (2,2,6,6-tetramethyl-4-piperidinyl) or 2- (2-hydroxy-5-methylphenyl) Benzotriazole and the like can be used. The ultraviolet stabilizer can be included in the thermoplastic resin composition in an amount of 0.1 to 0.5 part by weight based on 100 parts by weight of the total of a) and b) resins. As a UV absorber which is a type of ultraviolet ray inhibitor, 2- (5-chloro-2-benzotriazole) -4,6-bis (1,1-dimethylethyl) phenol is used as a UV absorber in the thermoplastic resin composition, And 0.1 to 0.5 parts by weight based on 100 parts by weight of the total weight of the composition.
The above-mentioned thermoplastic resin composition can be obtained by melt-kneading all components such as the core-shell graft copolymer of a), the styrene-acrylonitrile resin of b) and CaCO 3 of c), or kneading one component And then melt-kneading the remaining components. Specifically, the method of manufacturing is as follows:
In the first step, an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber latex core having an average particle diameter of 200 to 500 nm to prepare a core-shell graft copolymer.
As one example, 60 parts by weight of a butadiene polymer having an average rubber particle diameter of 200 to 500 nm was mixed with 30 parts by weight of styrene and 10 parts by weight of acrylonitrile using rosin acid salt and cumene hydroperoxide, Lt; RTI ID = 0.0 > lactone < / RTI >
Next, as a second step, 0.1 to 100 parts by weight of hydrazine, 0.1 to 70 parts by weight of peroxide compound and 0.01 to 10 parts by weight of an acid catalyst are added to the core-shell graft copolymer in the latex state, And a hydrogenated modified core-shell graft copolymer is obtained. Particularly, it is preferable that the hydrogenation reforming process is carried out at 50 to 80 ° C for 1 to 3 hours within the range of 250 to 300 rpm. In order to suppress the generation of nitrogen in the hydrogenation reforming, dimethylsiloxane is added to 100 parts by weight of the copolymer 0.1 to 3 parts by weight may be used together.
Specifically, as described in the Examples, 1 part by weight of hydrazine hydrate was mixed with 100 parts by weight of the prepared copolymer latex at 50 to 80 ° C, and then 0.7 parts by weight of hydroperoxides and 0.07 parts by weight of boric acid were mixed at 250 ° C To 300 rpm for 1 to 3 hours, and then agglomerated to obtain modified core-shell graft copolymer powder particles.
That is, 1 part by weight of hydrazine hydrate was mixed with 100 parts by weight of copolymer latex at 70 캜, 0.7 part by weight of hydroperoxides and 0.07 parts by weight of boric acid were placed in a batch at 270 rpm, Agitation may be carried out for a period of time.
Further, 1 part by weight of hydrazine hydrate and 0.2 part by weight of siloxane were mixed in 100 parts by weight of the copolymer latex at 70 DEG C, 0.7 parts by weight of hydroperoxides and 0.07 parts by weight of boric acid were placed under 270 rpm, and stirred for 1 hour 2 parts by weight of hydrazine hydrate, 0.4 parts by weight of siloxane, 1.5 parts by weight of hydroperoxide and 0.15 part by weight of boric acid were added to 100 parts by weight of the copolymer latex at 70 DEG C and 270 rpm, followed by stirring for 1 hour .
An antioxidant and an antioxidant may then be added to the copolymer modified prior to the third step.
As a third step, 20 to 40 parts by weight of the modified core-shell graft copolymer is mixed with the styrene-acrylonitrile resin balance having a weight average molecular weight of 100,000 to 180,000 and a glass transition temperature of 60 ° C or higher and CaCO 3 So that they are blended sequentially.
In the third step, one or more additives selected from the group consisting of a lubricant, a hindered phenol antioxidant, an ultraviolet ray inhibitor, a UV absorbent and an antistatic agent may be further added. Specifically, 30 parts by weight of the modified core-shell graft copolymer powder and 35 parts by weight of a high-melt SAN resin having a weight average molecular weight of 100,000 to 120,000 and a glass transition temperature of 100 to 105 DEG C as a hard matrix, 100 parts by weight of a SAN resin consisting of 70 parts by weight of a high molecular weight SAN resin having a glass transition temperature of 150 to 180,000 and a glass transition temperature of 105 to 110 DEG C and 1 to 3 parts by weight of CaCO 3 per 100 parts by weight of the base resin , 1.0 part by weight of ethylenebisstearamide as a lubricant, 0.5 part by weight of stearyl-? - (3,5-di-t-butyl-4-hydroxylphenyl) as a hindered phenol antioxidant, 0.5 part by weight of zeta tris (2,4-di-t-butylphenyl) phosphite, 0.3 part by weight of bis (2,2,6,6-tetramethyl-4-piperidinyl) -Hydroxy-5-methylphenyl) benzotriazole was added and mixed To obtain a thermoplastic resin composition.
The thermoplastic resin composition thus obtained was prepared into a pellet shape at a cylinder temperature of 220 캜 by using an extrusion kneader, and the pellet was injected to produce a test piece. The weather resistance was remarkably improved by maintaining the Izod impact strength, tensile strength and bending strength Thereby obtaining an improved thermoplastic resin. The thermoplastic resin obtained according to the present invention is not only excellent in impact resistance and rigidity but also excellent in weather resistance, so that it can be used as an exterior material, an automobile part, an electric-electronic part, or a building material.
According to the present invention, in a resin composition comprising two kinds of SAN resins and CaCO 3 having different weight average molecular weights from grafted ABS resin, grafted ABS is modified by hydrogenation reaction and used, There is an effect of providing a thermoplastic resin composition excellent in rigidity and weather resistance.
Example One
Example 1-1: core-shell Graft Copolymer production
(G-ABS) latex prepared by grafting 30 parts by weight of styrene and 10 parts by weight of acrylonitrile using 60 parts by weight of a butadiene polymer having an average rubber particle diameter of 300 nm using rosin acid and cumene hydroperoxide .
Example 1-2: latex modification
1 part by weight of hydrazine hydrate was mixed with 100 parts by weight of the prepared core-shell graft copolymer latex at 70 캜, and then 0.7 part by weight of hydroperoxides and 0.07 parts by weight of boric acid were mixed with stirring at 270 rpm for 1 hour After the reaction was carried out by introducing into the reactor, it was agglomerated to obtain modified graft copolymer powder particles.
Example 1-3: Preparation of Thermoplastic Resin Composition
30 parts by weight of the modified graft copolymer powder and 35 parts by weight of a high-performance SAN resin (product name: '81HF', manufactured by LIG Chemical Co., Ltd.) having a weight average molecular weight of 100,000 and a glass transition temperature of 100 to 105 ° C, the average molecular weight of 150,000 and a glass transition temperature of 105 ~ 110 ℃ high molecular weight SAN resin (㈜LG chemical, product name '92HR') CaCO to 35 parts by weight of SAN resin the base resin consisting of 70 parts by weight to 100 parts by weight 33 parts by weight , 1.0 part by weight of ethylenebisstearamide as a lubricant, 0.5 part by weight of stearyl-? - (3,5-di-t-butyl-4-hydroxylphenyl) as a hindered phenol antioxidant, 0.5 part by weight of tris (2,4-di-t-butylphenyl) phosphite, 0.3 part by weight of bis (2,2,6,6-tetramethyl-4-piperidinyl) Hydroxy-5-methylphenyl) benzotriazole was added and mixed to prepare a thermoplastic resin composition.
Example 1-4: Production of thermoplastic resin
The thermoplastic resin composition was prepared in the form of pellets using an extrusion kneader (product of ENGEL, under 150 rpm) at a cylinder temperature of 220 DEG C, and the specimens prepared by injection of the pellets were subjected to Izod impact strength, tensile strength, flexural strength , And weather resistance, and the obtained results are summarized together in Table 1 below.
Example 2
The same procedure as in Example 1 was repeated except that hydroperoxides and boric acid were placed in batches in the latex modification step of Example 1-2 and then stirred for 1 hour. The obtained samples were subjected to Izod impact strength , Tensile strength, flexural strength and weather resistance were measured, and the obtained results are summarized together in Table 1 below.
Example 3
The same procedure as in Example 1 was repeated except that 0.2 part by weight of siloxane was stirred together at the time of hydrazine hydrate stirring in the latex modification step of Example 1-2, and Izod impact strength, tensile strength, flexural strength , And weather resistance, and the obtained results are summarized together in Table 1 below.
Example 4
In the same manner as in Example 1 except that 2 parts by weight of hydrazine hydrate, 0.4 parts by weight of siloxane, 1.5 parts by weight of hydroperoxides and 0.15 parts by weight of boric acid were added together in the latex modification step of Example 1-2, The Izod impact strength, tensile strength, flexural strength, and weather resistance were measured with the obtained specimens. The results obtained are summarized in Table 1 below.
Example 5
The Izod impact strength, tensile strength, flexural strength and weatherability were measured with the specimens obtained by repeating the same processes as in Example 1, except that 1 part by weight of CaCO 3 was added in the step of preparing the thermoplastic resin of Example 1-4. And the results obtained are summarized together in Table 1 below.
Comparative Example 1: latex The reforming process If not done
The Izod impact strength, tensile strength, flexural strength and weather resistance were measured with the specimens obtained by repeating the procedures of Examples 1-1, 1-3, and 1-4 in this order, except for the latex modification step of Example 1-2, The results are summarized in Table 1 below.
Comparative Example 2: latex Reforming process without Phosphite system When adding antioxidants and phosphates
30 parts by weight of styrene and 10 parts by weight of acrylonitrile were grafted to 60 parts by weight of a butadiene polymer having an average rubber particle diameter of 300 nm using rosin acid and cumene hydroperoxide to prepare and coagulate a core- Copolymer powder particles were obtained.
30 parts by weight of the graft copolymer powder obtained above and a weight average molecular weight of 100,000 as a hard matrix 35 parts by weight of a high-flow SAN resin having a glass transition temperature of 100 to 105 DEG C, and 70 parts by weight of a SAN resin consisting of 35 parts by weight of a high molecular weight SAN resin having a weight average molecular weight of 150,000 and a glass transition temperature of 105 to 110 DEG C , 3 parts by weight of CaCO 3 , 2.0 parts by weight of ethylenebisstearamide as a lubricant, 0.3 parts by weight of 2,2-methylenebis (4-methyl-6-butylphenol) as a hindered phenol antioxidant, 0.25 parts by weight of bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite as second antioxidant, distearylpentaerythritol diphosphite as second antioxidant, and 0.25 parts by weight of sodium phosphate as alkali metal phosphate 0.25 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidinyl) as an ultraviolet stabilizer and 0.25 parts by weight of 2- (5-chloro-2-benzotriazole) 1,1-dimethylethyl) phenol were added and mixed to obtain a thermoplastic resin A hydrous product was prepared.
The thermoplastic resin composition was prepared in the form of a pellet using a 40 psi extrusion kneader at a cylinder temperature of 220 캜, and the pellet was injected to prepare a specimen. The properties of the specimen were measured and are shown in Table 1 below.
Comparative Example 3: latex Without modification High dynamic range Styrene- Acrylonitrile When only resin is used
The same procedure as in Comparative Example 2 was carried out except that 70 parts by weight of a first inherent silicone resin having a weight average molecular weight of 100,000 was used in Comparative Example 2, and the obtained results are summarized in Table 1 below.
Comparative Example 4 : CaCO 3 If you have not used it at all
The same procedure as in Example 1 was carried out except that no CaCO 3 was added to the thermoplastic resin production process of Example 1-4, and the obtained results are summarized in Table 1 below.
Comparative Example 5: CaCO 3 In a small amount
The same procedure as in Example 1 was carried out except that 0.5 parts by weight of CaCO 3 was added to the thermoplastic resin production process of Example 1-4, and the obtained results are summarized together in Table 1 below.
Comparative Example 6: CaCO 3 Is used excessively
The procedure of Example 1 was repeated, except that 3.5 parts by weight of CaCO 3 was added to the thermoplastic resin production process of Example 1-4, and the obtained results are summarized in Table 1 below.
Comparative Example 7: CaCO 3 To Nano By clay Replaced
The procedure of Example 1 was repeated except that CaCO 3 was replaced with nano-clay in the process of manufacturing the thermoplastic resin of Example 1-4, and the obtained results are summarized in Table 1 below.
The physical properties of the thermoplastic resin composition specimens prepared in Examples 1-5 and Comparative Examples 1-7 were measured by the following methods.
How to measure property:
A) Izod impact strength (1/4 "notched at 23 ° C, kg-cm / cm) - measured according to ASTM D256.
B) Tensile strength (50 mm / min, kg / cm2) - Measured according to ASTM D638.
B) Flexural strength (15 mm / min, kg / cm 2) - Measured according to ASTM D790.
D) Weathering - UV-accelerated test, 0.55 W / ㎡, Atlas UV2000 After 600 hours of testing, the discoloration of the specimens was measured by ΔE using a colorimeter. The smaller the value of ? E, the less discoloration and better weatherability.
As shown in Table 1, the thermoplastic resin compositions of Examples 1 to 5 containing the modified latex through the hydrogenation reaction according to the present invention had an impact strength, a tensile strength and a flexural strength without deteriorating the weatherability (Comparative Example 2), but the mechanical properties of the resin itself were lowered, and when the hydrogenated styrene-butadiene styrene-butadiene styrene-butadiene copolymer was used, When the acrylonitrile resin alone was used (Comparative Example 3), the mechanical properties such as impact properties were deteriorated.
In addition, when the content of CaCO 3 is smaller than the proper amount (Comparative Example 5) and the amount of CaCO 3 is excessively added (Comparative Example 6), the balance between mechanical properties and weatherability can not be obtained. In addition, when the same amount of nano-clay was added in place of CaCO 3 (Comparative Example 7), neither the weatherability nor the mechanical properties were effectively improved.
Claims (14)
b) 60 to 80 parts by weight of a styrene-acrylonitrile resin having a weight average molecular weight in the range of 100,000 to 180,000 and a glass transition temperature of 60 ° C or more, and
c) 1 to 3 parts by weight of CaCO 3 based on 100 parts by weight of the total of the components a) and b).
Wherein the hydrazine is selected from hydrazine hydrate, hydrazine acetate, hydrazine sulfate, or hydrazine hydrochloride.
Wherein the peroxide compound is hydroperoxides.
Wherein the acid catalyst is boric acid.
The styrene-acrylate resin (b)
(b-1) 20 to 60 parts by weight of a first styrene-acrylate resin having a weight average molecular weight of 100,000 to 120,000 and a glass transition temperature of 100 to 105 占 폚; And
(b-2) 20 to 60 parts by weight of a second styrene-acrylate resin having a weight average molecular weight of 150,000 to 180,000 and a glass transition temperature of 105 to 110 占 폚; Characterized in that
Thermoplastic resin composition.
Wherein the thermoplastic resin composition further comprises at least one additive selected from the group consisting of a lubricant, a hindered phenol antioxidant, a phosphite antioxidant, a UV stabilizer, a UV absorber, and an antistatic agent. .
The thermoplastic resin composition is prepared by blending 1 to 5 parts by weight of a lubricant, 0.1 to 0.5 parts by weight of a hindered phenol-based antioxidant, 0.1 to 0.5 parts by weight of a phosphite-based antioxidant, based on 100 parts by weight of a total of a) and b) 0.1 to 0.5 parts by weight of a UV stabilizer, 0.1 to 0.5 parts by weight of an ultraviolet stabilizer, and 0.1 to 0.5 parts by weight of a UV absorber.
0.1 to 100 parts by weight of hydrazine, 0.1 to 70 parts by weight of peroxide compound, 0.01 to 10 parts by weight of an acid catalyst and 0.1 to 3 parts by weight of dimethylsiloxane are added to 100 parts by weight of the core-shell graft copolymer, A second step of obtaining a shell graft copolymer; And
Of the resin 60 to 80 nitrile acrylic parts by weight of CaCO 3-hydride-modified core-shell graft copolymer of 20 to 40 parts by weight of the balance weight average molecular weight of from 100,000 to 180,000 range and the styrene glass transition less than the temperature 60 ℃ as the Mixing the graft copolymer and the styrene-acrylonitrile resin in an amount of 1 to 3 parts by weight based on 100 parts by weight of the total of the graft copolymer and the styrene-acrylonitrile resin; Based on the total weight of the thermoplastic resin composition.
Wherein the hydrogenation reforming step is carried out at 50 to 80 ° C for 1 to 3 hours within a range of 250 to 300 rpm in the second step.
The styrene-acrylate resin in the third step
(b-1) 20 to 60 parts by weight of a first styrene-acrylate resin having a weight average molecular weight of 100,000 to 120,000 and a glass transition temperature of 100 to 105 占 폚; And
(b-2) 20 to 60 parts by weight of a second styrene-acrylate resin having a weight average molecular weight of 150,000 to 180,000 and a glass transition temperature of 105 to 110 占 폚.
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| EP3342817A1 (en) | 2016-12-30 | 2018-07-04 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article manufactured using the same |
| WO2018124594A1 (en) | 2016-12-27 | 2018-07-05 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article manufactured therefrom |
| WO2019124857A2 (en) | 2017-12-22 | 2019-06-27 | 롯데첨단소재(주) | Thermoplastic resin composition and molded product manufactured therefrom |
| US10472490B2 (en) | 2016-10-25 | 2019-11-12 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article produced thereform |
| US10544278B2 (en) | 2016-11-02 | 2020-01-28 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article produced therefrom |
| US10787532B2 (en) | 2016-12-22 | 2020-09-29 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article manufactured using the same |
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| US11365304B2 (en) | 2016-12-23 | 2022-06-21 | Lotte Chemical Corporation | Foaming resin composition, preparation method therefor, and foam using same |
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| KR101972220B1 (en) | 2017-07-14 | 2019-04-24 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
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| US10472490B2 (en) | 2016-10-25 | 2019-11-12 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article produced thereform |
| US10544278B2 (en) | 2016-11-02 | 2020-01-28 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article produced therefrom |
| US10787532B2 (en) | 2016-12-22 | 2020-09-29 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article manufactured using the same |
| US10815368B2 (en) | 2016-12-23 | 2020-10-27 | Lotte Advanced Materials Co., Ltd. | Ionizing radiation resistant thermoplastic resin composition and article comprising the same |
| US11365304B2 (en) | 2016-12-23 | 2022-06-21 | Lotte Chemical Corporation | Foaming resin composition, preparation method therefor, and foam using same |
| WO2018124594A1 (en) | 2016-12-27 | 2018-07-05 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article manufactured therefrom |
| US11124643B2 (en) | 2016-12-27 | 2021-09-21 | Lotte Chemical Corporation | Thermoplastic resin composition and molded article manufactured therefrom |
| EP3342817A1 (en) | 2016-12-30 | 2018-07-04 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article manufactured using the same |
| US10472510B2 (en) | 2016-12-30 | 2019-11-12 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article manufactured using the same |
| US11505674B2 (en) | 2017-11-08 | 2022-11-22 | Lotte Chemical Corporation | Thermoplastic resin composition and molded article produced from same |
| WO2019124857A2 (en) | 2017-12-22 | 2019-06-27 | 롯데첨단소재(주) | Thermoplastic resin composition and molded product manufactured therefrom |
| US11661510B2 (en) | 2017-12-22 | 2023-05-30 | Lotte Chemical Corporation | Thermoplastic resin composition and molded product manufactured therefrom |
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| KR20120059668A (en) | 2012-06-11 |
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