KR102149011B1 - Thermoplastic resin composition, method for preparing the same and molded article manufactured therefrom - Google Patents

Abstract

The present description relates to a thermoplastic resin composition, a method for producing the same, and a molded article prepared therefrom, and more particularly, A) a diene rubber containing a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a siloxane group (meth ) 10 to 90% by weight of a thermoplastic graft resin in which the acrylate compound is graft-polymerized; And B) 10 to 90% by weight of a thermoplastic resin copolymerized with a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group; relates to a thermoplastic resin composition comprising will be.
According to the present disclosure, there is an effect of providing a thermoplastic resin composition excellent in both transparency and chemical resistance, which are conventionally recognized as a trade-off relationship, while having excellent mechanical strength and processability, a manufacturing method thereof, and a molded article manufactured therefrom.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THE SAME AND MOLDED ARTICLE MANUFACTURED THEREFROM}

The present description relates to a thermoplastic resin composition, a method for producing the same, and a molded article manufactured therefrom, and more particularly, a thermoplastic resin composition having excellent mechanical strength and processability, but excellent in both transparency and chemical resistance, which are conventionally recognized as a trade-off relationship, It relates to providing a method for manufacturing the same and a molded article manufactured therefrom.

The conventional transparent ABS resin composition is prepared by compounding a graft copolymer having a core-shell structure and a transparent thermoplastic resin. At this time, as the refractive indexes of each resin match, the transparency of the transparent ABS resin is improved.

Accordingly, in order to make an ABS resin composition that matches the refractive index of the butadiene rubber used as the core, a methyl methacrylate monomer having a low refractive index is generally used together in the manufacture of a matrix resin. It has the highest content ratio of methyl methacrylate, acrylonitrile and styrene used.

The acrylonitrile is a monomer that improves chemical resistance, but methyl methacrylate is a monomer that decreases chemical resistance. As the content thereof increases, the transparency increases, but there is a problem in that the chemical resistance decreases.

Korean Registered Patent No. 11644752

In order to solve the problems of the prior art as described above, the present substrate provides a thermoplastic resin composition having excellent mechanical strength and processability, but excellent both transparency and chemical resistance, which are conventionally recognized as a trade-off relationship, a method of manufacturing the same, and a molded article manufactured therefrom. It aims to provide.

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

In order to achieve the above object, the present substrate is A) a thermoplastic graft resin in which a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group are graft-polymerized to a diene rubber. 10 to 90% by weight; And B) 10 to 90% by weight of a thermoplastic resin copolymerized with a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group; provides a thermoplastic resin composition comprising a do.

In addition, the present substrate A) 10 to 90% by weight of a thermoplastic graft resin in which a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group are graft-polymerized in a diene rubber; And B) 10 to 90% by weight of a thermoplastic resin copolymerized with a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group; in an extruder and melt-kneading at 220 to 240°C. It provides a method for producing a thermoplastic resin composition comprising the step of.

In addition, the present description provides a molded article manufactured from the thermoplastic resin composition.

According to the present disclosure, there is an effect of providing a thermoplastic resin composition having excellent mechanical strength and processability, and excellent both transparency and chemical resistance, which are conventionally recognized as a trade-off relationship, a manufacturing method thereof, and a molded article manufactured therefrom.

Hereinafter, the thermoplastic resin composition of the present disclosure, a method of manufacturing the same, and a molded article manufactured therefrom will be described in detail.

When preparing a transparent ABS resin, an excessive amount of a methacrylate compound having a low refractive index is used in order to match the refractive index of the butadiene rubber core and the shell, which causes a problem of lowering the chemical resistance of the transparent ABS resin. In order to improve this, the present inventors have continuously researched and found that when a predetermined amount of a (meth)acrylate compound containing a siloxane group is introduced into the shell, etc., the content of the methacrylate compound can be reduced to prevent a decrease in chemical resistance, and It was confirmed that the low flow problem caused by the high molecular weight can be solved by increasing the content of the vinyl compound, and based on this, the present description was completed.

The thermoplastic resin composition of the present disclosure is A) 10 to 90 weight of a thermoplastic graft resin in which a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group are graft-polymerized in a diene rubber. %; And B) 10 to 90% by weight of a thermoplastic resin copolymerized with a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group.

The difference in refractive index between the A) thermoplastic graft resin and the B) thermoplastic resin may be, for example, less than 0.004, less than 0.003, or less than 0.001, and has excellent transparency within this range.

As another example, the thermoplastic resin composition of the present disclosure may include 30 to 70% by weight or 40 to 60% by weight of the A) thermoplastic graft resin and 30 to 70% by weight or 40 to 60% by weight of the B) thermoplastic resin. In addition, within this range, the mechanical strength, processability and transparency balance are good, and there is an effect particularly excellent in chemical resistance.

In the present description, the refractive index of the thermoplastic graft resin is obtained from the calculation formula of the monomer refractive index, and the refractive index of the thermoplastic resin can be measured using an Abbe refractometer.

Hereinafter, the thermoplastic resin composition of the present disclosure will be described in detail for each component.

A) thermoplastic Graft Suzy

The A) thermoplastic graft resin contains 10 to 50% by weight of a methacrylate compound, 5 to 30% by weight of an aromatic vinyl compound, 1 to 20% by weight of a vinyl cyan compound, and a siloxane group in 30 to 70% by weight of a diene rubber. 0.5 to 20% by weight of one (meth)acrylate compound may be a graft-polymerized thermoplastic graft resin, and within this range, there are excellent effects of impact strength, processability, transparency, and chemical resistance.

As another example, the diene-based rubber may be 35 to 65% by weight, 40 to 60% by weight, or 45 to 55% by weight, and within this range, there is an effect of excellent impact strength and transparency.

The diene rubber is for example 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene It may be a polymerized rubber including at least one selected from the group consisting of, and specific examples are butadiene polymer, butadiene-styrene copolymer (SBR), butadiene-acrylonitrile copolymer (NBR), ethylene-propylene-diene copolymer (EPDM) or a polymer derived therefrom, particularly preferably a butadiene polymer or a butadiene-styrene copolymer, and in this case, transparency and impact strength are excellent.

The diene-based rubber may have an average particle diameter of 100 to 500 nm, 100 to 400 nm, or 100 to 300 nm of the latex, and has excellent effects such as transparency and heat resistance within this range.

The method for producing the diene rubber is not particularly limited in the case of a conventional method for producing a diene rubber, for example, a diene compound or a mixture of a diene compound and an ethylenically unsaturated compound, ion exchange water, an emulsifier, a polymerization initiator, an electrolyte. And it may be a method of emulsion polymerization after adding an additive such as a molecular weight modifier, if necessary.

In a specific example, the method of preparing the diene rubber includes 70 to 130 parts by weight of ion-exchanged water, 0.2 to 4 parts by weight of an emulsifier, 0.1 to 0.1 parts by weight of a polymerization initiator, 100 parts by weight of a diene compound or a mixture of a diene compound and an ethylenically unsaturated compound. 1.5 parts by weight, 0.1 to 2 parts by weight of electrolyte, and 0.1 to 2 parts by weight of a molecular weight modifier may be added to the polymerization reactor and reacted at 50°C to 90°C.

The diene compound is, for example, 2,3-dimethyl-1,3-butadiene, 1,3-butadiene, piperylene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, 3-butyl-1 ,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene may be one or more selected from the group consisting of.

The polymerization initiator may be, for example, a water-soluble polymerization initiator, a fat-soluble polymerization initiator, or an oxidation-reduction catalyst may be used alone or in combination, and the water-soluble polymerization initiator may be, for example, a persulfate such as potassium persulfate, sodium persulfate or ammonium persulfate. In addition, the oil-soluble polymerization initiator may be cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutyl nitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide or benzoyl peroxide, for example, and the oxidation -Reduction catalyst is iron (II), iron (III), cobalt (II), cerium (IV), or metal salts containing two or more of them, sodium formaldehyde, sulfoxylate, sodium ethylenediamine tetraacetate, pyrrolic acid It may be sodium, sodium sulfite, dextrose, glucose, fructose, dihydroxyacetone, polyamine, or a mixture of reducing agents including two or more of them.

The emulsifier is not particularly limited, for example, an alkyl aryl sulfonate salt, an alkali methyl alkyl sulfate salt, a sulfonated alkyl ester salt, an alkyl (alkenyl) carboxylate, an alkyl (alkenyl) succinate, and a rosin acid salt. , Oleic acid salt, paty acid salt, toll oil fatty acid salt, and the like, and these can be used alone or in combination of two or more.

Examples of the electrolyte include potassium chloride (KCl), sodium chloride (NaCl), potassium bicarbonate (KHCO3), sodium bicarbonate (NaHCO3), potassium carbonate (K2CO3), sodium carbonate (Na2CO3), potassium hydrogen sulfite (KHSO3), sodium hydrogen sulfite (NaHSO3). ), tetrapotassium pyrophosphate (K4P2O7), tetrasodium pyrophosphate (Na4P2O7), tripotassium phosphate (K3PO4), trisodium phosphate (Na3PO4), dipotassium hydrogen phosphate (K2HPO4), and disodium hydrogen phosphate (Na2HPO4). It may be one or two or more.

The molecular weight modifier is, for example, a-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, mercaptan compounds such as octyl mercaptan, carbon tetrachloride, methylene chloride, halogenated hydrocarbon compounds such as methylene bromide, tetraethyl It may be a sulfur-containing compound such as thiuram disulfide, dipentamethylene thiuram disulfide, diisopropylxanthogen disulfide, and preferably t-dodecyl mercaptan.

The diene rubber may have a gel content of 50% to 90% by weight, 60 to 80% by weight, or 65 to 75% by weight, for example, and has an effect of having an appropriate impact strength within this range.

In the present description, the average particle diameter can be measured by a dynamic laser light scattering method (Laser Scattering Analyzer, Nicomp 370 HPL).

In the present description, the average particle diameter may be, for example, a weight average particle diameter.

In the present description, the gel content (% by weight) is determined by adding methanol to the prepared diene rubber latex, precipitating it with sulfuric acid, washing it, and drying it in a vacuum oven at 60°C for 24 hours. ) 1 g is cut into 100 g of toluene, stored in a dark room at room temperature for 48 hours, separated into a sol and a gel, and measured through Equations 2 and 3 below.

[Equation 2]

Gel content (% by weight) = ((weight of insoluble matter (gel))/(weight of initial rubber fragment)) X100

The graft polymerization is not particularly limited in the method or conditions in the case of a conventional graft polymerization, for example, a diene rubber latex containing a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a siloxane group ( An emulsified graft in which additives such as an emulsifier, a polymerization initiator and, if necessary, a molecular weight modifier, etc., are administered in batches before the start of polymerization, or a part of the meth)acrylate compound is added before the start of polymerization and the remainder after polymerization is started in batches or dividedly It can be polymerization.

In a specific example, the graft polymerization is 30 to 70% by weight of a diene rubber latex (based on solid content), 10 to 50% by weight of a methacrylate compound, 5 to 30% by weight of an aromatic vinyl compound, 1 to 20% by weight of a vinyl cyanide compound , And a total of 100 parts by weight of a monomer mixture comprising 0.5 to 20% by weight of a (meth)acrylate compound containing a siloxane group, 50 to 200 parts by weight of polymerization water, 0.05 to 0.4 parts by weight of a molecular weight modifier, 0.1 to 2 parts by weight of an emulsifier, And 0.01 to 0.5 parts by weight of a polymerization initiator, and polymerization reaction may be performed at a temperature range of 60° C. to 85° C. for 3 to 8 hours.

After the graft polymerization reaction, the graft copolymer in an emulsified state may additionally perform a process of coagulation, washing and drying, for example, and as a specific example, an antioxidant and/or a stabilizer if necessary in a reactor in which the polymerization reaction has been completed. Is added, a coagulant is added at a temperature of 80° C. or higher to coagulate the polymer, followed by dehydration and drying to obtain a powdery thermoplastic graft resin.

The coagulant may be one or two or more of an aqueous calcium chloride solution, an aqueous magnesium sulfate solution, an aqueous sodium chloride solution, an aqueous sulfuric acid solution, an aqueous hydrochloric acid solution, an aqueous formic acid solution, an aqueous acetic acid solution, and the like.

The kinds of polymerization initiators, emulsifiers, molecular weight modifiers, etc. used in the graft polymerization are as described above.

The methacrylate compound may be 15 to 40% by weight, 20 to 35% by weight, or 20 to 30% by weight as another example, and there is an effect of excellent transparency within this range.

The methacrylate compound is, for example, methyl methacrylic acid, ethyl methacrylic acid, propyl methacrylic acid, butyl methacrylic acid, hexyl methacrylic ester, 2-ethylhexyl methacrylic ester, methacrylic acid. It may be one or more selected from the group consisting of decyl ester and methacrylic acid lauryl ester, particularly preferably methyl methacrylate, and there is an effect of excellent transparency within this range.

The aromatic vinyl compound may be, for another example, 10 to 25% by weight, 10 to 20% by weight, or 12 to 16% by weight, and has excellent processability and transparency within this range.

The aromatic vinyl compound is, for example, styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, and vinyltoluene. It may be one or more selected from.

The vinyl cyan compound may be 3 to 15% by weight, 5 to 15% by weight, or 5 to 10% by weight as another example, and has excellent effects in chemical resistance and transparency within this range.

The vinyl cyan compound may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

The (meth)acrylate compound containing the siloxane group is another example of a thermoplastic graft in which 1 to 15% by weight, 1 to 10% by weight, 2 to 8% by weight, or 2 or more or less than 7% by weight is graft-polymerized It may be a resin, has excellent processability within this range, and has an effect of excellent chemical resistance and transparency that were in a conventional trade-off relationship.

The (meth)acrylate compound containing the siloxane group may be, for example, a compound represented by the following formula (1), and in this case, it has excellent processability, and excellent chemical resistance and transparency, which were in a conventional trade-off relationship.

[Formula 1]

(The R is bonding or alkylene having 1 to 10 carbon atoms, and R1 to R5 are independently hydrogen or an alkyl group having 1 to 10 carbon atoms, wherein n is an integer of 1 to 3, and m is 0 It is an integer of 2, and n+m is 3.)

Preferably, R is an alkylene having 1 to 5 or 2 to 4 carbon atoms, R1 is hydrogen, and R2 to R5 are independently an alkyl group having 1 to 5 or 1 to 3 carbon atoms, and n is 2 Or 3, and m is 0 or 1, and n+m is 3, and within this range, the processability is excellent, and chemical resistance and transparency are excellent in a conventional trade-off relationship.

As another example, the (meth)acrylate compound containing a siloxane group may be a compound represented by the following formula (2), and in this case, it has excellent processability, and excellent chemical resistance and transparency, which have been in a conventional trade-off relationship.

[Formula 2]

(The R is bonding or alkylene having 1 to 10 carbon atoms, and R1 to R4 and R6 to R11 are independently hydrogen or an alkyl group having 1 to 10 carbon atoms.)

Preferably, R is an alkylene having 1 to 5 or 2 to 4 carbon atoms, R1 is hydrogen, and R2 to R4 and R6 to R11 are independently an alkyl group having 1 to 5 or 1 to 3 carbon atoms, Within this range, the processability is excellent, and there is an effect of excellent chemical resistance and transparency, which were conventionally traded off.

In order for the A) thermoplastic graft resin to have transparency, the refractive index of the diene rubber used as the core for grafting and the refractive index of the copolymer grafted thereto should be similar, preferably the refractive index of the diene rubber and the graph It is good that the refractive indices of the copolymer to be matched match. Therefore, it is preferable that the difference between the refractive index of the diene-based rubber and the copolymer grafted thereon is less than 0.01, less than 0.005, or less than 0.001.

In addition, the refractive index of the A) thermoplastic graft resin may be calculated as follows.

RI = ∑ Wti * RIi

Wti = weight fraction of each component in the copolymer (%)

RIi = refractive index of the polymer of each component of the copolymer

Here, the refractive index of the butadiene polymer is 1.518, the refractive index of the methyl methacrylate polymer is 1.49, the refractive index of the styrene polymer is 1.59, the refractive index of the acrylonitrile polymer is 1.52, and 3-[tris(trimethylsiloxy)silyl] The refractive index of the polymer of propyl methacrylate is 1.431.

The A) thermoplastic graft resin may have, for example, a refractive index of 1.510 to less than 1.520, 1.512 to 1.519, or 1.513 to 1.518, respectively, and has excellent transparency within this range.

B) Thermoplastic resin

The B) thermoplastic resin is, for example, 30 to 85% by weight of a methacrylate compound, 10 to 45% by weight of an aromatic vinyl compound, 1 to 20% by weight of a vinyl cyan compound, and 0.5 to 20 of a (meth)acrylate compound containing a siloxane group. The weight% may be a copolymerized thermoplastic resin, and within this range, mechanical properties, processability, transparency, and chemical resistance are all excellent.

As another example, the methacrylate compound may be 40 to 80% by weight, 50 to 70% by weight, or 60 to 65% by weight, and there is an effect of excellent transparency within this range.

In another example, the aromatic vinyl compound may be 15 to 40% by weight, 20 to 35% by weight, or 25 to 30% by weight, and there is an effect of excellent transparency and processability within this range.

As another example, the vinyl cyan compound may be 3 to 15% by weight, 5 to 15% by weight, or 5 to 10% by weight, and within this range, there is an effect of excellent chemical resistance and transparency.

In another example, the (meth)acrylate compound containing the siloxane group may be 1 to 15% by weight, 1 to 10% by weight, or 3 to 7% by weight, and has excellent processability within this range, and a conventional trade-off relationship It has excellent chemical resistance and transparency.

The types of the methacrylate compound, the aromatic vinyl compound, the vinyl cyan compound, and the (meth)acrylate compound containing a siloxane group contained in the above B) thermoplastic resin are as described in the above A) thermoplastic graft resin.

The method of manufacturing the thermoplastic resin is not particularly limited, but suspension polymerization or block polymerization is suitable, and in particular, continuous block polymerization is the best method in terms of manufacturing cost.

The manufacturing method of the thermoplastic resin is not particularly limited if it is a manufacturing method commonly applied in this technical field, for example, by bulk polymerization, an organic solvent as a reaction medium to the monomer mixture, and additives such as a molecular weight modifier and a polymerization initiator, if necessary. It may be a method of polymerization by introducing.

In a specific example, the method for producing the thermoplastic resin includes 30 to 85 weight of a methacrylate compound, 10 to 45 weight% of an aromatic vinyl compound, 1 to 20 weight% of a vinyl cyan compound, and 0.5 (meth)acrylate compound containing a siloxane group. Mixing 20 to 40 parts by weight of a reaction medium and 0.05 to 0.5 parts by weight of a molecular weight modifier and performing a polymerization reaction for 2 to 4 hours while maintaining a reaction temperature of 130 to 170°C. It may include.

The reaction medium is not particularly limited if it is a solvent commonly used in this technical field, and may be an aromatic hydrocarbon-based compound such as ethylbenzene, benzene, toluene, and xylene.

The manufacturing method of the thermoplastic resin is, for example, a raw material injection pump, a continuous stirring tank in which the reaction raw material is continuously added, a preheating tank for preliminarily heating the polymerization liquid discharged from the continuous stirring tank, an unreacted monomer and/or a reaction medium. It can be carried out in a continuous process machine consisting of a volatilization tank that volatilizes, a polymer transfer pump, and an extrusion machine for producing a polymer in a pellet form.

The B) thermoplastic resin may have, for example, a refractive index of 1.510 or more to less than 1.520, 1.512 to 1.519, or 1.513 to 1.518, respectively, and has excellent transparency within this range.

Thermoplastic resin composition

The thermoplastic resin composition may further include one or more selected from the group consisting of a heat stabilizer, a UV stabilizer, a lubricant, an antioxidant, a processing aid, a pigment and a colorant, for example.

The additive may be included in an amount of 0.01 to 5 parts by weight, 0.1 to 3 parts by weight, 0.5 to 2 parts by weight, or 1.0 to 2.0 parts by weight, respectively, based on 100 parts by weight of a total of A) a thermoplastic graft resin and B) a thermoplastic resin. And within this range, there is an effect of expressing the natural properties of the additive without affecting the physical properties of the thermoplastic resin composition.

In another example, the additive is 0.1 to 2 parts by weight or 0.5 to 1.5 parts by weight of a lubricant; And 0.1 to 1.0 parts by weight or 0.1 to 0.5 parts by weight of the antioxidant, and within this range, there is an effect of expressing the inherent characteristics of the lubricant and antioxidant without affecting the physical properties of the thermoplastic resin composition.

For example, the thermoplastic resin composition may have a haze of less than 4.0%, less than 3.0%, or less than 2.5.

For example, the thermoplastic resin composition may have an impact strength (IMP) of 20 or more, or 21 or more.

For example, the thermoplastic resin composition may have a fluidity index (MI) of 12 or more, 13 or more, or 13 to 17, and has excellent processability within this range.

For example, the thermoplastic resin composition may have a chemical resistance measured as a time when a specimen is fixed to a 1.0% jig and then a 70% by weight isopropyl alcohol aqueous solution is applied, and a crack occurs for 10 minutes or more.

The method for preparing the thermoplastic resin composition of the present disclosure includes A) a thermoplastic graft resin in which a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group are graft-polymerized to a diene rubber. To 90% by weight; And B) 10 to 90% by weight of a thermoplastic resin copolymerized with a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group; in an extruder and melt-kneading at 220 to 240°C. It characterized in that it comprises the step of.

In another example, the method for preparing the thermoplastic resin composition is to mix the A) thermoplastic graft resin and B) the thermoplastic resin, then uniformly disperse and extrude using a single screw extruder, a twin screw extruder, or a Banbury mixer, and then Passing through a water bath, and cutting it to produce a pellet.

The thermoplastic resin composition pellet may be manufactured into an injection molded article using an injection machine, for example.

The molded article of the present disclosure is characterized in that it is manufactured from the thermoplastic resin composition of the present disclosure.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present description, but the following examples are only illustrative of the present description, and that various changes and modifications are possible within the scope of the present description and the scope of the technical idea will be apparent to those skilled in the art, It is natural that such modifications and modifications fall within the appended claims.

[Example]

< Manufacturing example >

Manufacturing example 1: thermoplastic Graft Suzy

As the diene rubber latex, a polybutadiene rubber latex having an average particle diameter of 300 nm, a refractive index of 1.516, and a gel content of 70% by weight was used.

100 parts by weight of ion-exchanged water to 50 parts by weight of the polybutadiene rubber latex (solid content), 1.0 parts by weight of sodium dodecylbenzenesulfonate as an emulsifier, 32 parts by weight of methyl methacrylate, 11 parts by weight of styrene, 7 parts by weight of acrylonitrile Parts, 0.3 parts by weight of tertiary dodecyl mercaptan, 0.048 parts by weight of sodium formaldehyde sulfoxylate, 0.012 parts by weight of sodium ethylenediaminetetraester, 0.001 parts by weight of ferrous sulfide and 0.04 parts by weight of cumene hydroperoxide at 75° C. It was reacted by continuous administration for 5 hours.

After the reaction, the temperature was raised to 80° C. and then aged for 1 hour and the reaction was terminated. Then, it was solidified with an aqueous calcium chloride solution and washed to obtain a powdery thermoplastic transparent resin. The polymerization conversion rate of the thermoplastic graft resin thus obtained was 99%, and the refractive index was 1.516.

Manufacturing example 2: thermoplastic Graft Suzy

Preparation Example 1 except that 29.0 parts by weight of methyl methacrylate, 12.0 parts by weight of styrene, and 7.0 parts by weight of acrylonitrile were used in Preparation Example 1, and 2.0 parts by weight of 3-[Tris(trimethyls iloxy)silyl]propyl methacrylate were added. A thermoplastic graft resin was obtained in the same process as. The polymerization conversion rate of the thermoplastic graft resin thus obtained was 98%, and the refractive index was 1.516.

Manufacturing example 3: thermoplastic Graft Suzy

Preparation Example 1 except that 26.6 parts by weight of methyl methacrylate, 13.0 parts by weight of styrene, and 7.0 parts by weight of acrylonitrile were used in Preparation Example 1, and 3.4 parts by weight of 3-[Tris(trimethyls iloxy)silyl]propyl methacrylate were added. A thermoplastic graft resin was obtained in the same process as. The polymerization conversion rate of the thermoplastic graft resin thus obtained was 97%, and the refractive index was 1.516.

Manufacturing example 4: thermoplastic Graft Suzy

Preparation Example 1 except that 24.2 parts by weight of methyl methacrylate, 14.0 parts by weight of styrene, and 7.0 parts by weight of acrylonitrile were used in Preparation Example 1, and 5.8 parts by weight of 3-[Tris(trimethyls iloxy)silyl]propyl methacrylate was added. A thermoplastic graft resin was obtained in the same process as. The polymerization conversion rate of the thermoplastic graft resin thus obtained was 97%, and the refractive index was 1.516.

Manufacturing example 5: thermoplastic Graft Suzy

Preparation Example 1 except that 19.7 parts by weight of methyl methacrylate, 16.0 parts by weight of styrene, and 7.0 parts by weight of acrylonitrile were used in Preparation Example 1, and 7.3 parts by weight of 3-[Tris(trimethyls iloxy)silyl]propyl methacrylate was added. A thermoplastic graft resin was obtained in the same process as. The polymerization conversion ratio of the thermoplastic graft resin thus obtained was 92%, and the refractive index was 1.520.

Manufacturing example 6: thermoplastic resin

A raw material in which 69 parts by weight of methyl methacrylate, 24 parts by weight of styrene, and 7 parts by weight of acrylonitrile were mixed with 30 parts by weight of toluene as a solvent and 0.15 parts by weight of tertiary dodecyl mercaptan as a molecular weight modifier, the average reaction time was 3 hours. It was continuously added to the reaction tank so that the reaction temperature was maintained at 148°C. Subsequently, the polymerization liquid discharged from the reaction tank was heated in a preheating tank, and unreacted monomers were volatilized in the volatilization tank. Then, by maintaining the temperature at 210 ℃ using a polymer transfer pump extruder to prepare a pellet-shaped copolymer. The refractive index of the thermoplastic resin thus prepared was 1.516.

Manufacturing example 7: thermoplastic resin

The same as in Preparation Example 6 except that 61 parts by weight of methyl methacrylate, 27 parts by weight of styrene, and 7 parts by weight of acrylonitrile were used in Preparation Example 6, and 5 parts by weight of 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate was added. A thermoplastic resin was prepared by the process. The refractive index of the thermoplastic resin thus prepared was 1.516.

Example 1 to 5 and Comparative example 1 to 4

The thermoplastic graft resin of Preparation Example 1-4 and the thermoplastic resin of Preparation Example 6-7 were mixed in the composition shown in the table below, and 1.0 part by weight of a lubricant and 0.2 part by weight of an antioxidant were added, and then twin-screw extrusion at a cylinder temperature of 230°C. It was prepared in the form of pellets using a kneader.

division Graft copolymer Thermoplastic resin Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 6 Manufacturing Example 7 Example 1 40 60 Example 2 40 60 Example 3 40 60 Example 4 50 50 Example 5 60 40 Comparative Example 1 40 60 Comparative Example 2 60 40 Comparative Example 3 40 60 Comparative Example 4 40 60

[Test Example]

After injecting the pellets prepared in Examples 1 to 4 and Comparative Examples 1 to 3 at an injection temperature of 230°C using an injection machine, the injected specimens were subjected to 25°C and 50±5% relative humidity for 12 hours. After aging, property evaluation was performed according to the following method, and the results are shown in Table 2 below.

1. Transparency: The haze value of the 3mm sheet was measured at room temperature using AS TM D-1003.

2. Impact strength (Notched Izod Impact S trength): Notched Izod impact strength was measured according to ASTM D-256. Measurement was made using a 1/4” specimen.

3. Melt Index: Flowability was measured according to ASTM D-1238. It was measured under the condition of 10 kg under 220 ℃ using the extruded pellets.

4. Chemical resistance: After fixing the tensile specimen of each sample to 1.0% Jig, 70% Is opropyl Alcohol Solution was applied on the sample, and the change was observed after 10 minutes.

5. Refractive index measurement: In order to determine the refractive index of each resin, the specimen was thinly cut to a thickness of 0.2 mm using a hot press, and then measured by irradiating 450 nm of light with an Abbe refractometer at 25°C.

6. Polymerization conversion rate: To measure the polymerization conversion rate, 1.5 g of the prepared latex was dried in a hot air dryer at 150° C. for 15 minutes, and then the weight was measured to obtain the total solid content (TSC), and the polymerization conversion rate can be calculated by Equation 1 below. .

[Equation 1]

division Transparency (haze, %) Impact strength (IMP) Liquidity Index (MI) Chemical resistance Example 1 2.2 21.5 15.0 No Change Example 2 2.1 22.2 15.4 No Change Example 3 2.3 23.0 16.0 No Change Example 4 2.5 26.5 13.9 No Change Example 5 2.5 27.0 11.8 No Change Comparative Example 1 2.0 20.1 13.5 Break Comparative Example 2 2.3 24.0 10.0 Break Comparative Example 3 2.1 20.7 14.0 Crack Comparative Example 4 2.2 21.0 13.8 Crack

As shown in Table 1, Examples 1 to 4 in which the (meth)acrylate compound containing a siloxane group according to the present description was applied to both the thermoplastic graft resin and the thermoplastic resin did not show any change in the chemical resistance evaluation, The resistance was excellent, and the flow also showed excellent properties.

On the other hand, in Comparative Examples 1 and 2, in which the (meth)acrylate compound containing a siloxane group was not applied to both the thermoplastic graft resin and the thermoplastic resin, the tensile specimen was broken in the chemical resistance evaluation, and only one resin contained a siloxane group (meth) ) In the case of Comparative Examples 3 and 4 to which the acrylate compound was applied, the chemical resistance was improved rather than the case where it was not used at all, but there was a problem that cracks occurred.

Reference example

40 parts by weight of the thermoplastic graft resin of Preparation Example 5 and 60 parts by weight of the thermoplastic resin of Preparation Example 7 were mixed, and 1.0 parts by weight of a lubricant and 0.2 parts by weight of an antioxidant were added to pellets using a twin-screw extrusion kneader at a cylinder temperature of 230°C. It was prepared in the form. After injecting the prepared pellets at an injection temperature of 230°C using an injection machine, the injected specimens were aged for 12 hours under conditions of 25°C and 50±5% relative humidity, and the transparency evaluated according to the above method (haze, %), impact strength (IMP), fluidity index (MI), and chemical resistance were 4.7, 23.5, 16.4, and "No Change", respectively. From these results, when 7 parts by weight or more of a (meth)acrylate compound containing a siloxane group is applied in the manufacture of a thermoplastic graft resin, the stability of the latex is somewhat deteriorated due to the low polymerization conversion rate, and coagulum is generated and the refractive index is affected. Seems to have an effect.

Claims (17)

A) 10 to 90% by weight of a thermoplastic graft resin in which a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group are graft-polymerized to a diene rubber; And
B) 10 to 90% by weight of a thermoplastic resin copolymerized with a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group; characterized in that it comprises
Thermoplastic resin composition. The method of claim 1,
The difference in refractive index between the A) thermoplastic graft resin and the B) thermoplastic resin is less than 0.004.
Thermoplastic resin composition. The method of claim 1,
The A) thermoplastic graft resin contains 10 to 50% by weight of a methacrylate compound, 5 to 30% by weight of an aromatic vinyl compound, 1 to 20% by weight of a vinyl cyan compound, and a siloxane group in 30 to 70% by weight of a diene rubber ( 0.5 to 20% by weight of the meth)acrylate compound is a graft polymerized thermoplastic graft resin, characterized in that
Thermoplastic resin composition. The method of claim 1,
The B) thermoplastic resin contains 30 to 85% by weight of a methacrylate compound, 10 to 45% by weight of an aromatic vinyl compound, 1 to 20% by weight of a vinyl cyan compound, and 0.5 to 20% by weight of a (meth)acrylate compound containing a siloxane group. Characterized in that it is a copolymerized thermoplastic resin
Thermoplastic resin composition. The method of claim 1,
The A) thermoplastic graft resin and the B) thermoplastic resin each have a refractive index of 1.510 or more to less than 1.520.
Thermoplastic resin composition. The method of claim 1,
The (meth)acrylate compound containing the siloxane group is characterized in that the compound represented by the following formula (1)
Thermoplastic resin composition.
[Formula 1]

(The R is bonding or alkylene having 1 to 10 carbon atoms, and R1 to R5 are independently hydrogen or an alkyl group having 1 to 10 carbon atoms, wherein n is an integer of 1 to 3, and m is 0 It is an integer of 2, and n+m is 3.) The method of claim 1,
The diene rubber is at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene. Characterized in that it is a polymerized rubber including
Thermoplastic resin composition. The method of claim 1,
The methacrylate compound is methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, methacrylic acid butyl ester, methacrylic acid hexyl ester, methacrylic acid 2-ethylhexyl ester, methacrylic acid decyl ester And methacrylic acid lauryl ester, characterized in that at least one selected from the group consisting of
Thermoplastic resin composition. The method of claim 1,
The aromatic vinyl compound is at least one selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, and trichlorostyrene. Characterized by
Thermoplastic resin composition. The method of claim 1,
The vinyl cyan compound is characterized in that at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile.
Thermoplastic resin composition. The method of claim 1,
The thermoplastic resin composition further comprises at least one selected from the group consisting of a heat stabilizer, a UV stabilizer, a lubricant, an antioxidant, a processing aid, a pigment and a colorant.
Thermoplastic resin composition. The method of claim 1,
The thermoplastic resin composition is characterized in that the transparency (haze) is less than 4.0%
Thermoplastic resin composition. The method of claim 1,
The thermoplastic resin composition is characterized in that the impact strength (IMP) is 20 or more
Thermoplastic resin composition. The method of claim 1,
The thermoplastic resin composition is characterized in that the fluidity index (MI) is 12 or more
Thermoplastic resin composition. The method of claim 1,
The thermoplastic resin composition is characterized in that the chemical resistance measured as a time when a specimen is fixed to a 1.0% jig and then a 70% by weight isopropyl alcohol aqueous solution is applied and a crack occurs is 10 minutes or more.
Thermoplastic resin composition. A) 10 to 90% by weight of a thermoplastic graft resin in which a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group are graft-polymerized to a diene rubber; And B) 10 to 90% by weight of a thermoplastic resin copolymerized with a methacrylate compound, an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylate compound containing a siloxane group; into an extruder and melt kneading at 220 to 240°C. Characterized in that it comprises the step of
Method for producing a thermoplastic resin composition. It characterized in that it is prepared from the thermoplastic resin composition of any one of claims 1 to 15
Molded products.