KR20190088775A - Themoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising: a first copolymer comprising a conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer derived unit, an aromatic vinyl-based monomer derived unit, and a vinyl cyan-based monomer derived unit; a second copolymer comprising the alkyl (meth)acrylate-based monomer derived unit, the aromatic vinyl-based monomer derived unit, and the vinyl cyan-based monomer derived unit; and a compound represented by chemical formula 1. A molded article manufactured by the thermoplastic resin composition according to the present invention is excellent in transparency, flame retardancy, processability, and mechanical properties.

Description

[0001] THERMOPLASTIC RESIN COMPOSITION [0002]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition having excellent transparency, impact resistance, flame retardancy and processability.

Recently, as the industry has advanced and actively promoted product differentiation, many changes have occurred in product design. As a result, color diversity and transparent design are attracting much attention. Changes in design require changes in materials, and research on the development of transparent materials is actively underway.

On the other hand, the transparent ABS graft copolymer is prepared by adding alkyl (meth) acrylate to the shell to control the refractive index of the core and the cell, thereby producing a graft copolymer having excellent transparency. And transparent ABS copolymer has excellent processability and mechanical properties and can be applied to electric and electronic fields, office automation equipment, miscellaneous goods, and construction materials.

However, the transparent ABS graft copolymer is vulnerable to fire because of its high flammability, despite its excellent transparency, processability and mechanical properties. To overcome this problem, it is necessary to use an excessive amount of flame retardant in the transparent ABS graft copolymer. However, excessive use of a flame retardant may cause deterioration of mechanical properties. In general, a halogen-based flame retardant used as a flame retardant is not environmentally friendly and thus is not used.

Accordingly, studies have been continuing to produce environmentally friendly transparent thermoplastic resin compositions while realizing excellent flame retardance, impact strength and fluidity using a transparent ABS copolymer.

KR2012-0088090A

An object of the present invention is to provide an environmentally friendly thermoplastic resin composition while realizing excellent transparency, flame retardancy, processability and mechanical properties.

In order to solve the above-mentioned problems, the present invention relates to a first copolymer comprising a conjugated diene polymer, a unit derived from an alkyl (meth) acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; A second copolymer comprising an alkyl (meth) acrylate monomer-derived unit, an aromatic vinyl monomer-derived unit, and a vinylcyanide monomer-derived unit; And a compound represented by the following formula (1): < EMI ID = 1.0 >

≪ Formula 1 >

In Formula 1,

이고,R is

ego,

L is a direct bond or a C ₁ to C ₁₀ alkylene group,

R ₁ is an acryl group or a methacryl group.

Further, the present invention relates to a thermoplastic resin composition which is produced from the thermoplastic resin composition and has an impact strength (1/4 ") of 10 kgf · cm / cm or more based on ASTM D-256 and a flame retardancy based on UL94 HB of 130 seconds or more A thermoplastic resin molded article is provided.

The molded article produced from the thermoplastic resin composition according to the present invention is excellent in transparency, flame retardancy, processability and mechanical properties. Further, since the thermoplastic resin composition according to the present invention does not contain a halogen-based flame retardant, an environmentally friendly molded article can be produced.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

In the present invention, the average particle diameter can be defined as the particle diameter corresponding to 50% or more of the volume accumulation amount in the particle diameter distribution curve of the particles.

 In the present invention, the average particle diameter and the particle diameter distribution of the conjugated diene polymer can be measured by dissolving a predetermined amount of the first copolymer in a solvent and then using a dynamic laser light skating method using Nicomp 370HPL. Specifically, 0.5 g of the first copolymer is dissolved in 100 ml of methyl ethyl ketone, and then the measurement can be performed using a Coulter counter (trade name: LS230, manufactured by Beckman Coulter, Inc.).

In the present invention, the weight average molecular weight can be measured relative to a standard polystyrene (PS) sample through gel permeation chromatography (waters breeze) using THF (tetrahydrofuran) as an eluent.

A thermoplastic resin composition according to an embodiment of the present invention includes a first copolymer including a conjugated diene polymer, a unit derived from an alkyl (meth) acrylate monomer, a unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer; A second copolymer comprising an alkyl (meth) acrylate monomer-derived unit, an aromatic vinyl monomer-derived unit, and a vinylcyanide monomer-derived unit; And compounds represented by the following formula (1): < EMI ID =

≪ Formula 1 >

In Formula 1,

이고,R is

ego,

L is a direct bond or a C ₁ to C ₁₀ alkylene group,

R ₁ is an acryl group or a methacryl group.

Hereinafter, the components of the thermoplastic resin composition according to one embodiment of the present invention will be described in detail.

1. First copolymer

The first copolymer includes a unit derived from a conjugated diene polymer, an alkyl (meth) acrylate monomer, an aromatic vinyl monomer, and a vinyl cyan monomer.

The first copolymer can impart excellent transparency, chemical resistance, and impact resistance to the thermoplastic resin composition.

The conjugated diene polymer is obtained by polymerizing a conjugated diene polymer modified by graft polymerizing an alkyl (meth) acrylate monomer, an aromatic vinyl monomer and a vinyl cyan monomer to a conjugated diene polymer produced by polymerization of a conjugated diene monomer .

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

The conjugated diene-based polymer may have an average particle diameter of 0.1 to 0.5 mu m, 0.2 to 0.4 mu m, or 0.25 to 0.35 mu m, and preferably 0.25 to 0.35 mu m. When the above-mentioned range is satisfied, the impact resistance of the first copolymer can be further improved.

The conjugated diene polymer may be contained in an amount of 40 to 65% by weight, 45 to 60% by weight or 50 to 55% by weight based on the total weight of the first copolymer, and 50 to 55% by weight thereof desirable. When the above-mentioned range is satisfied, the impact resistance of the first copolymer can be further improved.

The unit derived from the alkyl (meth) acrylate monomer is at least one monomer selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl Lauryl (meth) acrylate, and among these, a unit derived from methyl methacrylate is preferable.

The unit derived from the alkyl (meth) acrylate monomer may be contained in an amount of 20 to 45% by weight, 25 to 40% by weight or 30 to 35% by weight based on the total weight of the first copolymer, By weight. When the above-mentioned range is satisfied, the transparency, rigidity and scratch resistance of the first copolymer can be further improved.

The aromatic vinyl-based monomer-derived unit may be at least one derived unit selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, and p-methylstyrene, and styrene-derived units are preferred.

The aromatic vinyl monomer-derived unit may be contained in an amount of 5 to 25% by weight, 7 to 20% by weight or 10 to 15% by weight based on the total weight of the first copolymer, and 10 to 15% by weight thereof . When the above-mentioned range is satisfied, the rigidity and processability of the first copolymer can be improved.

The unit derived from the vinyl cyan monomer may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenyl acrylonitrile and? -Chloroacrylonitrile, and the unit derived from acrylonitrile Unit is preferable.

The unit derived from the vinyl cyan monomer may be contained in an amount of 1 to 15% by weight, 1 to 10% by weight or 1 to 5% by weight based on the total weight of the first copolymer, and 1 to 5% by weight thereof . When the above range is satisfied, the chemical resistance, stiffness and impact resistance of the first copolymer can be further improved.

The shell of the first copolymer may have a weight average molecular weight of 70,000 to 300,000 g / mol, 80,000 to 150,000 g / mol or 90,000 to 130,000 g / mol, 90,000 to 130,000 g / mol being preferred. When the above-mentioned range is satisfied, there is an advantage that the mechanical properties are improved.

The shell of the first copolymer may include a unit derived from an alkyl (meth) acrylate monomer, an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit graft-polymerized to a conjugated diene polymer.

The first copolymer may be produced by subjecting an alkyl (meth) acrylate monomer, an aromatic vinyl monomer and a vinyl cyan monomer to at least one method selected from the group consisting of emulsion polymerization, suspension polymerization and bulk polymerization in the presence of a conjugated diene- , And it is preferable to produce by emulsion polymerization.

2. Second copolymer

The second copolymer includes an alkyl (meth) acrylate-based monomer-derived unit, an aromatic vinyl-based monomer-derived unit, and a vinylcyanide monomer-derived unit.

The second copolymer can impart high rigidity, scratch resistance, coloring property, and transparency to the thermoplastic resin composition.

The kind of the alkyl (meth) acrylate monomer-derived unit is as described in the description of the first copolymer.

The unit derived from the alkyl (meth) acrylate monomer may be 55 to 80% by weight, 60 to 75% by weight or 65 to 70% by weight based on the total weight of the second copolymer, and 65 to 70% desirable. When the above-mentioned range is satisfied, the rigidity and scratch resistance of the second copolymer can be further improved.

The kind of the aromatic vinyl-based monomer-derived unit is as described in the description of the first copolymer.

The aromatic vinyl monomer-derived unit may be from 15 to 40% by weight, from 20 to 35% by weight, or from 25 to 30% by weight, and preferably from 25 to 30% by weight, based on the total weight of the second copolymer. When the above-mentioned range is satisfied, the rigidity and processability of the second copolymer can be improved.

The kind of the unit derived from the vinyl cyan monomer is as described in the description of the first copolymer.

The unit derived from the vinyl cyan monomer may be 3 to 20% by weight, 4 to 15% by weight or 5 to 10% by weight, and preferably 5 to 10% by weight, based on the total weight of the second copolymer. When the above range is satisfied, the chemical resistance, stiffness and impact resistance of the second copolymer can be improved.

The weight average molecular weight of the second copolymer may be 70,000 to 180,000 g / mol, 80,000 to 150,000 g / mol, or 90,000 to 130,000 g / mol, 90,000 to 130,000 g / mol being preferred. When the above-mentioned range is satisfied, there is an advantage of excellent processability and mechanical properties.

The second copolymer may be prepared by polymerization by one or more methods selected from the group consisting of emulsion polymerization, suspension polymerization and bulk polymerization, and it is preferable that the second copolymer is produced by bulk polymerization.

The weight ratio of the first and second copolymers may be from 10:90 to 50:50, from 20:80 to 40:60 or from 25:75 to 35:65, and from 25:75 to 35:65 . When the above-mentioned range is satisfied, there is an advantage that the mechanical properties are excellent.

3. A compound represented by the formula (1)

The compound represented by the following formula (1) can impart excellent flame retardancy, processability and impact resistance to the thermoplastic resin composition:

A thermoplastic resin composition comprising a compound represented by the following formula (1):

≪ Formula 1 >

In Formula 1,

이고,R is

ego,

L is a direct bond or a C ₁ to C ₁₀ alkylene group,

R ₁ is an acryl group or a methacryl group.

Since R of the compound represented by the formula (1) is an acrylic group or a methacryl group, it is excellent in compatibility with the first and second copolymers and can impart excellent mechanical properties and transparency to the thermoplastic resin composition.

In Formula 1, L may be a C ₁ to C ₄ alkylene group, and in Formula 1, R ₁ is preferably a methacryl group.

인 것이 보다 바람직하다.Wherein R is

Is more preferable.

When the above-mentioned R is satisfied, the compatibility with the first and second copolymers is improved while the flame retardancy, workability and impact resistance of the thermoplastic resin composition are improved, and mechanical properties and transparency can be further improved.

If R is an alkyl group or hydrogen, compatibility with the first and second copolymers may be deteriorated and the mechanical properties of the thermoplastic resin composition may be deteriorated.

The compound represented by Formula 1 is harmless to the human body and environmentally friendly, unlike the halogen-based flame retardant containing halogen which is a carcinogen. In addition, unlike the organic halogen-based flame retardant, it can provide excellent flame retardancy even when only a small amount is used, and can impart excellent mechanical properties to the thermoplastic resin composition.

The compound represented by Formula 1 may have a weight average molecular weight of 800 to 2,000 g / mol or 1,200 to 1,600 g / mol, and preferably 1,200 to 1,600 g / mol. When the above-mentioned conditions are satisfied, the mechanical properties of the thermoplastic resin composition can be improved.

The compound represented by Formula 1 may have a viscosity of 10 to 25 poise or 15 to 20 poise at 25 ° C, and preferably 15 to 25 poise. When the above-mentioned viscosity is satisfied, the processability of the thermoplastic resin composition can be improved.

The compound represented by Formula 1 may have excellent stability in tetrahydrofuran, chloroform, acetone, acetone nitrile, and ethanol.

The compound represented by Formula 1 may be a colorless liquid.

The compound represented by Formula 1 may be contained in an amount of 0.1 to 1 part by weight or 0.5 to 0.7 part by weight based on 100 parts by weight of the sum of the first copolymer and the second copolymer, . When the above-mentioned range is satisfied, the flame retardancy and the impact strength can be further improved, and the increase in the manufacturing cost can be minimized.

According to another embodiment of the present invention, when the impact strength (1/4 ") of the thermoplastic resin composition according to one embodiment of the present invention is 10 kgf · cm / cm or more based on ASTM D-256 , And a flame retardancy based on UL94 HB of not less than 130 seconds can be provided. A thermoplastic resin composition having excellent impact resistance and flame retardancy, preferably a transparent thermoplastic resin composition, can be provided by satisfying the above conditions .

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

≪ Preparation of first copolymer >

Manufacturing example  One

35 parts by weight of methyl methacrylate, 12 parts by weight of styrene, 3 parts by weight of acrylonitrile, 0.5 parts by weight of an alkenyl C ₁₆ -C ₁₈ succinic acid, potassium salt 0.5 (weight average molecular weight: 0.5) as a butadiene polymer latex having an average particle diameter of 0.3 μm, 0.5 part by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.04 part by weight of cumene hydroperoxide as an initiator, 0.048 part by weight of sodium formaldehyde sulfoxylate as an activator, 0.012 part by weight of sodium ethylenediamine tetraacetate, 0.001 parts by weight of iron and 100 parts by weight of ion-exchanged water was polymerized at 75 DEG C for 5 hours at a constant rate continuously. Then, the temperature was raised to 80 DEG C, aged for 1 hour, and polymerization was terminated. The polymerization conversion was 98.8% and the solid solid content was 0.1%.

≪ Preparation of Second Copolymer >

Manufacturing example  2

A mixture containing 70 parts by weight of methyl methacrylate, 25 parts by weight of styrene, 5 parts by weight of acrylonitrile, 30 parts by weight of toluene as a solvent, and 0.15 part by weight of t-dodecyl mercaptan as a molecular weight modifier was stirred for 4 hours And the polymerization was carried out while maintaining the reaction temperature at 148 ° C.

The polymerized liquid discharged from the reaction vessel was heated in a preheating tank, volatile unreacted monomers were volatilized in a volatilization tank, and a temperature of 210 ° C was maintained. Thus, a pellet-shaped copolymer was prepared using a polymer transfer pump extrusion machine.

The polymerization conversion was 78%, the TSC (total solid content) was 58%, and the weight average molecular weight was 100,000 g / mol.

≪ Production of thermoplastic resin &

Example  1 to Example  5

, 상품명: MA0735, 제조사: Hybrid Plastics Inc.), 활제 및 산화방지제를 하기 표 1에 기재된 함량으로 혼합하고, 220℃로 설정된 이축 압출기에 투입하여 펠렛 형태의 열가소성 수지 조성물을 제조하였다.The copolymer of Preparation Example 1 as the first copolymer, the copolymer of Preparation Example 2 as the second copolymer, the methacryl POSS cage mixture (R:

, Trade name: MA0735, manufactured by Hybrid Plastics Inc.), a lubricant and an antioxidant were mixed in the amounts shown in Table 1, and the mixture was fed into a twin-screw extruder set at 220 ° C to prepare a thermoplastic resin composition in the form of a pellet.

division The first copolymer
(Parts by weight) The second copolymer
(Parts by weight) The compound represented by the formula (1)
(Parts by weight) Lubricant
(Parts by weight) Antioxidant
(Parts by weight) Example 1 30 70 0.1 0.3 0.2 Example 2 30 70 0.3 0.3 0.2 Example 3 30 70 0.5 0.3 0.2 Example 4 30 70 0.7 0.3 0.2 Example 5 30 70 0.9 0.3 0.2

Comparative Example  One

Was prepared in the same manner as in Example 1, except that the compound represented by the formula (1) was not added.

Comparative Example  2

20 parts by weight of a copolymer of Preparation Example 1 as a first copolymer, 80 parts by weight of a copolymer of Preparation Example 2 as a second copolymer, 0.3 part by weight of a lubricant and 0.2 part by weight of an antioxidant were mixed and melt kneaded in a twin- To prepare a thermoplastic resin composition in the form of a pellet.

Comparative Example  3

Except that 10 parts by weight of BTAC-245 (trade name: Woojin Polymer) as a bromine-based flame retardant instead of the compound represented by the general formula (1) was added.

Comparative Example  4

Octamethyl substituted (CAS Number 17865-85-9, manufactured by Hybrid Plastics Inc.) was used instead of the compound represented by the formula (1).

The composition of the comparative example is summarized in Table 2 below.

division The first copolymer
(Parts by weight) The second copolymer
(Parts by weight) Brominated flame retardant
(Parts by weight) PSS-Octamethyl substituted (parts by weight) Lubricant
(Parts by weight) Antioxidant
(Parts by weight) Comparative Example 1 30 70 - - 0.3 0.2 Comparative Example 2 20 80 - - 0.3 0.2 Comparative Example 3 30 70 10 - 0.3 0.2 Comparative Example 4 30 70 - 0.5 0.3 0.2

Experimental Example  One

The physical properties of the thermoplastic resin compositions of Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3 below.

(1) Flowability (g / 10 min): Measured according to ASTM D1238.

Experimental Example  2

The thermoplastic resin compositions of Examples and Comparative Examples were injected to prepare specimens, and physical properties of the specimens were measured by the following methods. The results are shown in Table 3 below.

(2) Notched Izod Impact Strength (kgf · cm / cm): The notched Izod impact strength was measured according to ASTM D-256. Measurements were made using 1/4 "specimens.

(3) Flammability (seconds): Measured according to the UL94 HB (Horizontal Burning Test) test method.

division liquidity Impact strength Flammability Example 1 25 11 130 Example 2 25 12 138 Example 3 27 12 147 Example 4 27 14 151 Example 5 28 15 161 Comparative Example 1 25 9 120 Comparative Example 2 31 6 119 Comparative Example 3 28 7 210 Comparative Example 4 27 8 139

Referring to Table 3, in Examples 1 to 5, the flowability, impact strength and flame retardancy were superior to those of Comparative Example 1 and Comparative Example 2.

As the content of the compound represented by the general formula (1) was increased, it was confirmed that the flowability, impact strength and flame retardancy were further improved.

In Comparative Example 1 and Comparative Example 2 in which no flame retardant was used, not only the flame retardancy but also the impact strength were lowered.

In the case of Comparative Example 3, the use of the brominated flame retardant improves the flame retardancy, but the impact strength is lowered.

In the case of Comparative Example 4, since the compound represented by Chemical Formula 1 in which R is methyl was used, it was confirmed that the flame retardancy was excellent, but the compatibility with the first and second copolymers was poor and the mechanical properties were remarkably lowered.

Claims (10)

A first copolymer comprising a conjugated diene polymer, a unit derived from an alkyl (meth) acrylate monomer, an unit derived from an aromatic vinyl monomer, and a unit derived from a vinyl cyan monomer;
A second copolymer comprising an alkyl (meth) acrylate monomer-derived unit, an aromatic vinyl monomer-derived unit, and a vinylcyanide monomer-derived unit; And
A thermoplastic resin composition comprising a compound represented by the following formula (1):
≪ Formula 1 >

In Formula 1,
R is

ego,
L is a direct bond or a C ₁ to C ₁₀ alkylene group,
R ₁ is an acryl group or a methacryl group.
The method according to claim 1,
Wherein L in Formula 1 is an alkylene group of C ₁ to C ₄ .
The method according to claim 1,
In the general formula 1 R ₁ is a methacrylate group to the thermoplastic resin composition.
The method according to claim 1,
Wherein the compound represented by Formula 1 has a viscosity of 10 to 25 poise at 25 占 폚.
The method according to claim 1,
With respect to 100 parts by weight of the sum of the first copolymer and the second copolymer,
0.1 to 1 part by weight of the compound represented by the formula (1).
The method according to claim 1,
Wherein the weight ratio of the first copolymer and the second copolymer is from 10:90 to 50:50.
The method according to claim 1,
The first copolymer
Wherein, based on the total weight of the first copolymer,
40 to 65% by weight of the conjugated diene-based polymer;
20 to 45% by weight of the alkyl (meth) acrylate monomer-derived units;
5 to 25% by weight of the aromatic vinyl-based monomer unit; And
And 1 to 15% by weight of the vinyl-based monomer-derived unit.
The method according to claim 1,
The second copolymer
Based on the total weight of the second copolymer,
55 to 80% by weight of the unit derived from the alkyl (meth) acrylate monomer;
15 to 40% by weight of the aromatic vinyl-based monomer unit; And
And 3 to 20% by weight of the vinyl-based monomer-derived unit.
A thermoplastic resin composition which is produced from the thermoplastic resin composition according to any one of claims 1 to 8,
A thermoplastic resin molded article having an impact strength (1/4 ") of 10 kgf · cm / cm or more according to ASTM D-256.
The method of claim 9,
Wherein the thermoplastic resin molded article has a flame retardancy of 130 seconds or more based on UL94 HB.