KR20220126210A - Thermoplastic resin composition and exterior building materials comprising the resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition and an exterior material thereof and provides a thermoplastic resin composition which has equivalent or better mechanical properties and processability compared to a conventional ASA resin, has excellent natural coloring quality with even and low gloss and uniform refractive index control, and can reduce appearance defects with excellent PVC co-extrusion processability and a molded article thereof.

Description

Thermoplastic resin composition and its exterior material

The present invention relates to a thermoplastic resin composition and its exterior material, and more particularly, mechanical properties and processability, etc., compared to conventional ASA-based resins, are equal to or higher than those of conventional ASA-based resins, and have excellent natural coloring quality due to even and low gloss and uniform refractive index control. It relates to a low-gloss thermoplastic resin composition capable of reducing appearance defects due to excellent extrusion processability and an exterior material thereof.

The acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as 'ASA resin') has weather resistance, aging resistance, chemical resistance, rigidity, impact resistance, and processability. It is widely used in the field.

In the field of exterior materials, customer preference for molded products with excellent matte effect and natural colorability is increasing, but development of matte ASA resin that can satisfy this is insufficient.

Conventionally, a crystalline resin such as syndiotactic polystyrene (hereinafter referred to as 'sPS') was added to the ASA resin or an ABS resin having a particle size of several microns (㎛) was used to realize a low gloss ASA resin, In the case of sPS, the colorability was lowered, and in the case of an ABS resin having a large particle size, there were difficulties such as greatly lowering the weather resistance.

As a noteworthy point, when molding as a siding material or a decking board material, it is provided through co-extrusion with PVC resin. It is necessary to provide natural colorability and heat resistance while realizing an appearance without appearance.

Conventionally, an amorphous polymer such as polymethyl methacrylate (hereinafter referred to as 'PMMA') was added to improve the colorability, but the impact was lowered. There is still a limit to being able to identify a trade-off.

Korean Patent Publication No. 2019-0114898

In order to solve the problems of the prior art as described above, the present invention provides an even and low gloss and a uniform refractive index while maintaining the same or higher mechanical properties, weather resistance, and workability compared to the conventional ASA resin, thereby providing excellent natural coloring quality as well as An object of the present invention is to provide a low-gloss thermoplastic resin composition capable of reducing appearance defects due to excellent PVC co-extrusion processability.

Another object of the present invention is to provide a molded article prepared from the above thermoplastic resin composition.

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

In order to achieve the above object, the present invention

A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle diameter of 0.33 to 0.5 μm, and A-2) an alkyl acrylate rubber having an average particle diameter of 0.05 to 0.2 μm. 10 to 50 wt% of the total weight of the total weight of the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising;

B-1) 0 to 30 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 67 to 75 wt% of an aromatic vinyl compound and 25 to 33 wt% of a vinyl cyan compound;

B-2) 20 to 70 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 70 to 75 wt% of an aromatic vinyl compound and 25 to 30 wt% of a vinyl cyan compound; and

C) containing 0.5 to 10% by weight of a polyamide resin having a melting temperature (Tm) of 250° C. or higher,

The A-1) graft copolymer and A-2) the graft copolymer provide a thermoplastic resin composition, characterized in that each of the color development coverage values (X) calculated by the following Equation 1 is 20% or more.

[Equation 1]

X = {A/S} * 100

(In Equation 1, S is the content (wt%) of the soluble material (sol) after dissolving the graft copolymer in acetone and centrifuging, and A is the graft copolymer dissolved in acetone and centrifuged. Shows the content (wt%) of the vinyl cyanide compound in the molten material (sol) after.)

A-1) the graft copolymer and A-2) the combined content of the graft copolymer, and B-1) the aromatic vinyl compound-vinyl cyan compound copolymer and B-2) the aromatic vinyl compound-vinyl cyan compound copolymer The weight ratio ((A-1+A-2): (B-1+B-2)) of the sum of the contents may be 1:0.5 to 1:2.

The thermoplastic resin composition may have a black-and-white color index (Color Strength, N) of 100 or more calculated by Equations 3 and 5 below.

[Equation 3]

Monochrome color development index (N) = ∑ (absorption value of sample)/∑ (absorption value of standard sample) ∑ (absorption value of standard sample) ∑

(In Equation 3, the absorption value of the sample is the calculated absorption value of the solid sample calculated by the Kubelka-Munk equation represented by Equation 5 below, and ∑ is the integral value in the spectrum over the entire 400 to 700 nm region)

[Equation 5]

Calculated absorption value of solid sample = (1-R) ² / 2R

(In Equation 5, R is X-lite Color-eye 7000A and uses the reflection coefficient value measured according to the method of CIE Lab.)

The thermoplastic resin composition may have a color strength (C) of 110 or more calculated by Equations 4 and 5 below.

[Equation 4]

Color development index (C) = λmax (absorption value of sample) / λmax (absorption value of standard sample) X 100

(In Equation 4, the absorption value is the solid sample absorption value calculated by the Kubelka-Munk equation represented by Equation 5, and λmax is the highest absorption wavelength over the entire spectrum)

A weight ratio (A-1:A-2) of the A-1) graft copolymer to the A-2) graft copolymer may be 1:0.54 to 1:1.50.

The A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer contains 30 to 60% by weight of an acrylate rubber having an average particle diameter of 0.33 to 0.5 μm, 20 to 50% by weight of an aromatic vinyl compound, and 10 to 50% by weight of a vinyl cyanide compound. 30 to 60% by weight of acrylate rubber having an average particle diameter of 0.05 to 0.2 μm, and 20 to 20 to aromatic vinyl compound, wherein the A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 30 wt% It may be composed of 50% by weight and 10 to 30% by weight of the vinyl cyanide compound.

The B-1) aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 100,000 to 150,000 g/mol, and the B-2) aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of greater than 150,000 g/mol. It may be 200,000 g/mol or less.

Based on the total weight of the thermoplastic resin composition, the B-1) aromatic vinyl compound-vinyl cyan compound copolymer is included in an amount of 10 to 30 wt %, and the B-2) aromatic vinyl compound-vinyl cyan compound copolymer is 30% by weight. to 60% by weight.

A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, and B-2) aromatic vinyl compound-vinyl cyan compound copolymer The thermoplastic resin composition, characterized in that the color coverage value (Xa1 + Xa2 + Xb1 + Xb2) calculated by the following Equation 6-1 of the thermoplastic resin composition is 20 to 33%.

[Equation 6-1]

Xa1 + Xa2 + Xb1 + Xb2 = {(Aa1/Sa1) + (Aa2/Sa2) + (Ab1/Sb1) + (Ab2/Sb2)} * 100

(In Equation 6-1, Sa1, Sa2, Sb1, and Sb2 are A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer; B-2) The content (or weight %) of the soluble substance (sol) after each of the aromatic vinyl compound-vinyl cyan compound copolymer is dissolved in acetone and centrifuged, and Aa1, Aa2, Ab1, Ab2 are A-1 ) Graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, and B-2) aromatic vinyl compound-vinyl cyan compound copolymer were respectively dissolved in acetone and centrifuged It indicates the content (or weight %) of the vinyl cyanide compound in the molten material (sol) after fusion.)

Furthermore, the pigment or dye (D) may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

The weight ratio (D:C) of the (D) pigment or dye and (C) the polyamide resin may be greater than 1:1 to 1:10 or less.

In addition, the present invention provides A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle diameter of 0.33 to 0.5 μm, and A-2) an average particle diameter of 0.05 to 0.2 μm. 10 to 50 wt% of the total weight of the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including alkyl acrylate rubber;

B-1) 0 to 30 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 67 to 75 wt% of an aromatic vinyl compound and 25 to 33 wt% of a vinyl cyan compound;

B-2) 20 to 70 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 70 to 75 wt% of an aromatic vinyl compound and 25 to 30 wt% of a vinyl cyan compound; and

C) It provides a thermoplastic resin composition comprising 0.5 to 10% by weight of a polyamide resin having a melting temperature (Tm) of 250° C. or higher.

In addition, the present invention provides an exterior material comprising the above-described thermoplastic resin composition.

The facing material may be a siding material, a roofing material or a decking board material.

According to the present invention, a low-gloss thermoplastic that has excellent mechanical properties and processability compared to conventional ASA resins, and has excellent natural coloring quality due to even and low gloss and uniform refractive index control, as well as excellent PVC co-extrusion processability to reduce appearance defects. There is an effect of providing a resin composition and a molded article thereof.

Therefore, the thermoplastic resin composition and molded article according to the present invention can be widely used in the field of siding material, roofing material, or decking board material requiring the same. Specifically, it can be applied as a sliding door or window material.

Hereinafter, the thermoplastic resin composition of the present invention and its packaging material will be described in detail.

The present inventors blend an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, an aromatic vinyl compound-vinyl cyan compound copolymer and a polyamide resin containing an acrylate-based rubber having a predetermined average particle diameter in a predetermined ratio, , when the color development coverage value of the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is adjusted within a predetermined range, mechanical properties and processability are not reduced compared to the conventional ASA resin composition, while the ASA resin and polyamide It was confirmed that the compatibility between the resins was improved, the color development was excellent, and the improved gloss and colorability were provided, and based on this, further research was devoted to complete the present invention.

The thermoplastic resin composition of the present invention includes A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle diameter of 0.33 to 0.5 μm, and A-2) an average particle diameter of 0.05 to 0.2 10 to 50 wt% of the total weight of the total weight of the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing the alkyl acrylate rubber having a thickness of μm; B-1) 0 to 30 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 67 to 75 wt% of an aromatic vinyl compound and 25 to 33 wt% of a vinyl cyan compound; B-2) 20 to 70 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 70 to 75 wt% of an aromatic vinyl compound and 25 to 30 wt% of a vinyl cyan compound; and C) 0.5 to 10% by weight of a polyamide resin having a melting temperature (Tm) of 250° C. or higher.

In this case, a low-gloss thermoplastic resin that has excellent mechanical properties and processability compared to conventional ASA-based resins, and has excellent natural coloring quality due to even and low gloss and uniform refractive index control, as well as excellent PVC co-extrusion processability to reduce appearance defects. It is advantageous to provide a composition and a molded article thereof.

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

A-1) An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.33 to 0.5 μm

The acrylate rubber of the A-1) graft copolymer preferably has an average particle diameter of 0.33 to 0.5 μm, more preferably 0.38 to 0.5 μm, and still more preferably 0.4 to 0.5 μm, Within this range, it has good weather resistance and excellent mechanical properties such as fluidity, tensile strength and impact strength.

In this description, the average particle diameter can be measured using a dynamic light scattering method, and in detail, the intensity value in Gaussian mode using Nicomp 380 equipment (product name, manufacturer: PSS). can be measured with At this time, as a specific measurement example, the sample is prepared by diluting 0.1 g of Latex (TS 35-50wt%) 1,000-5,000 times with distilled water, and the measurement method is auto-dilution and measured with a flow cell, and the measurement mode is dynamic light scattering ( Dynamic light scattering) method/Intensity 300KHz/Intensity-weight Gaussian Analysis can be used, and the setting value can be measured with a temperature of 23°C, a measurement wavelength of 632.8nm, and a channel width of 10μsec.

In addition, in the present description, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, specifically, an average particle diameter of scattering intensity.

The A-1) graft copolymer is, for example, 50 to 90% by weight, preferably 50 to 80% by weight, more preferably 50 to 90% by weight based on the total weight of the A-1) and A-2) graft copolymers. 70% by weight, and has excellent effects in weather resistance, fluidity, tensile strength and impact strength within this range.

The A-1) graft copolymer comprises, for example, 40 to 60 wt% of the acrylate rubber, 20 to 45 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyanide compound, preferably the acryl 40 to 60% by weight of the late rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, more preferably 45 to 55% by weight of the acrylate rubber, 30 to 30% by weight of the aromatic vinyl compound 40% by weight and 10 to 20% by weight of the vinyl cyanide compound, there is an excellent effect in weather resistance, fluidity, tensile strength and impact strength within this range.

In the present description, a polymer including a certain compound means a polymer polymerized including the compound, and a unit in the polymerized polymer is derived from the compound.

In the present description, the acrylate may be, for example, at least one selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in the alkyl group, preferably an alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, more preferably butyl acrylate or ethylhexyl acrylate.

In the present description, the aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-tert-butylstyrene, and is preferably styrene.

In the present description, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, and is preferably acrylonitrile.

The A-1) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, chemical resistance, weather resistance, fluidity, tensile strength and impact strength are excellent.

The emulsion polymerization is not particularly limited if the emulsion graft polymerization method is commonly carried out in the art to which the present invention belongs.

The A-1) graft copolymer preferably has a color development power coverage value (X) calculated by the following formula (1) of 20% or more, preferably 20-30%, more preferably 25-30%, and , within this range, mechanical properties such as impact strength, tensile strength, and flexural strength, gloss and colorability are excellent, and color development and hiding power are excellent.

[Equation 1]

X = {A/S} * 100

(In Equation 1, S is the content (wt%) of the soluble material (sol) after dissolving the graft copolymer in acetone and centrifuging, and A is the graft copolymer dissolved in acetone and centrifuged. Shows the content (wt%) of the vinyl cyanide compound in the molten material (sol) after.)

In Equation 1, the content (wt%) of the vinyl cyanide compound in the molten material (sol) after dissolving the graft copolymer in acetone and centrifugation is the vinyl cyanide in the molten powder collected in the process of obtaining the gel content. The compound content (based on 100 wt% of the graft copolymer added) is indicated. Here, the gel content represents the content of insoluble matter based on 100% by weight of the total graft copolymer.

The content of the vinyl cyanide compound in the molten material (sol) may be measured using an NMR analyzer or FT-IR.

Specifically, the gel content is determined by adding 1 g of the graft copolymer to 60 ml of acetone, stirring it at room temperature for 12 hours, centrifuging it to collect insoluble fraction that is not dissolved in acetone, drying it for 12 hours, and measuring the weight, It is calculated by Equation 2 below. Specifically, 1 g of the graft copolymer was added to 60 ml of acetone and stirred at 210 rpm with a stirrer (Orbital Shaker, equipment name: Lab companion SKC-6075) at room temperature for 12 hours, and then centrifuged (Supra R30 of Hanil Science Company) The insoluble fraction that was not dissolved in acetone was collected by centrifugation at 0°C at 18000 rpm for 3 hours using a After drying, the weight can be measured.

[Equation 2]

Gel content (wt%) = [Weight of insoluble matter (gel) (g) / Weight of sample (g)] x 100

In the present description, the color development coverage value (X) is a parameter indicating the degree of dispersion of the ungrafted vinyl cyan compound in the graft copolymer and the vinyl cyan compound grafted to the alkyl acrylate rubber. As this value is higher, the vinyl cyan compound is evenly dispersed in an appropriate content, resulting in low gloss and excellent colorability and color development. However, if the color coverage value is too large, the hiding power may decrease, and thus the optimal compatibility may not be exhibited.

A-2) An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.05 to 0.2 μm

A-2) The acrylate rubber of the graft copolymer may preferably have an average particle diameter of 0.05 to 0.2 μm, more preferably 0.05 to 0.17 μm, still more preferably 0.1 to 0.17 μm, more preferably It is 0.1 to 0.15 μm, and excellent weather resistance, colorability, impact strength, color development and surface gloss properties can be imparted to the final product within this range.

The A-2) graft copolymer is, for example, 10 to 50% by weight, preferably 9 to 35% by weight, more preferably 12 to 50% by weight, based on the total weight of the A-1) and A-2) graft copolymers. It is 22 wt%, and it has excellent effects in weather resistance, fluidity, tensile strength and impact strength within this range.

The A-2) graft copolymer may include, for example, 40 to 60% by weight of the acrylate rubber, 20 to 45% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound, preferably the 40 to 60% by weight of the acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, more preferably 45 to 55% by weight of the acrylate rubber, 30% by weight of the aromatic vinyl compound to 50% by weight and 5 to 20% by weight of a vinyl cyan compound, more preferably 47 to 57% by weight of the acrylate rubber , 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound It has excellent effects in weather resistance, fluidity, tensile strength and impact strength within this range.

The A-2) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, it has excellent effects in weather resistance, fluidity, tensile strength and impact strength.

The emulsion polymerization is not particularly limited if the emulsion graft polymerization method is commonly carried out in the art to which the present invention belongs.

The A-2) graft copolymer preferably has a color development power coverage value (X) calculated by Equation 1 above 20%, preferably 20 to 30%, more preferably 25 to 30%, and , within this range, mechanical properties such as impact strength, tensile strength, and flexural strength, gloss and colorability are excellent, and color development and compatibility are excellent.

In the present description, the color development coverage value is a parameter indicating the content of the ungrafted vinyl cyan compound in the graft copolymer and the vinyl cyan compound grafted to the alkyl acrylate rubber. The higher this value, the more evenly the vinyl cyan compound is dispersed, so that the glossiness is low and the color development property is excellent. However, if the color development coverage value is too large, the hiding power may be lowered, and thus the optimal color development and hiding power may not be exhibited.

A-1) Blending of graft copolymer and A-2) graft copolymer

A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising acrylate rubber having an average particle diameter of 0.33 to 0.5 μm, and A-2) an acrylate rubber having an average particle diameter of 0.05 to 0.2 μm. In the case of a mixture of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, mechanical properties and processability are equal to or higher than that of conventional ASA-based resins, and the colorability characteristics are greatly improved, and there is an advantage of excellent quality reliability.

Weight ratio of the A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (A-1:A-2) may satisfy, for example, a weight ratio of 1:0.54 to 1:1.50, preferably 1:0.55 to 1:1.30, and more preferably 1:0.56 to 1:1.20, in this case workability, elongation, surface quality, and weather resistance And there is an excellent effect such as transparency.

B) Two kinds of aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights

In the present description, B) two kinds of aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights are, for example, the aromatic vinyl compound-vinyl cyan compound copolymer preferably B-1) having a weight average molecular weight of 100,000 to 150,000 g/mol of an aromatic vinyl compound-vinyl cyan compound copolymer; and B-2) an aromatic vinyl compound having a weight average molecular weight of greater than 150,000 g/mol to 200,000 g/mol or less-vinyl cyan compound copolymer; and at least one selected from the group consisting of, preferably B-2) Aromatic vinyl compound-vinyl cyan compound copolymer alone use; or B-1) aromatic vinyl compound-vinyl cyan compound copolymer and B-2) aromatic vinyl compound-vinyl cyan compound copolymer, and in this case, heat resistance, chemical resistance and impact strength, tensile strength, and processability are It has an excellent effect.

The B-1) aromatic vinyl compound-vinyl cyan compound copolymer is preferably 0 to 30 wt%, more preferably 0 to 25 wt%, still more preferably 0 to 20 wt%, based on the total weight of the thermoplastic resin composition. , Specific examples include 1 to 30% by weight, more specific examples include 10 to 25% by weight, and more specific examples include 15 to 20% by weight, and in this case, excellent heat resistance, chemical resistance and impact strength, tensile strength, and workability It works.

The B-2) aromatic vinyl compound-vinyl cyan compound copolymer is preferably 30 to 70 wt%, more preferably 30 to 60 wt%, still more preferably 35 to 60 wt%, based on the total weight of the thermoplastic resin composition In this case, heat resistance, chemical resistance, impact strength, tensile strength, and workability are excellent.

In the present description, unless otherwise defined, the weight average molecular weight may be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent. ) can be measured relative to a standard PS (standard polystyrene) sample. At this time, as a specific example of measurement, solvent: THF, column temperature: 40° C., flow rate: 0.3 ml/min, sample concentration: 20 mg/ml, injection amount: 5 μl, column model: 1xPLgel 10 μm MiniMix-B (250x4.6 mm) + 1xPLgel 10 μm MiniMix-B (250x4.6mm) + 1xPLgel 10 μm MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): It can be measured under OECD TG 118 conditions.

The B-1) and B-2) aromatic vinyl compound-vinyl cyan compound copolymer comprises, for example, 65 to 80 wt% of an aromatic vinyl compound and 20 to 35 wt% of a vinyl cyanide compound, preferably an aromatic vinyl compound. 67 to 80% by weight of the compound and 20 to 33% by weight of the vinyl cyan compound, more preferably 70 to 75% by weight of the aromatic vinyl compound and 25 to 30% by weight of the vinyl cyan compound, within this range It has excellent chemical resistance, impact strength, tensile strength, and workability.

The aromatic vinyl polymers B-1) and B-2) may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and in this case, heat resistance and fluidity are excellent.

The suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are not particularly limited in the case of solution polymerization and bulk polymerization methods commonly performed in the art to which the present invention pertains, respectively.

In this description, in addition to the above-described B-1) and B-2) aromatic vinyl compound-vinyl cyan compound copolymer, it is desirable to exclude the use of a heat-resistant styrene-based resin or methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer for colorability and It is preferable that the hiding power can be maintained while sufficiently realizing the color development characteristic, but the present invention is not limited thereto.

A-1) graft copolymer, A-2) graft copolymer, and B) two types of aromatic vinyl compound-vinyl cyan compound copolymer having different weight average molecular weights

The thermoplastic resin composition preferably contains 10 to 50 wt% of the total amount of A-1) the graft copolymer and A-2) the graft copolymer, and B) two aromatic vinyl compounds having different weight average molecular weights-vinyl cyan 50 to 90 wt% of the compound copolymer, more preferably 20 to 50 wt% of the total amount of A-1) graft copolymer and A-2) graft copolymer, and B) weight average molecular weight 50 to 80 wt % of two different aromatic vinyl compounds-vinyl cyan compound copolymers, and more preferably 30 to 50 weight percent in total of A-1) graft copolymer and A-2) graft copolymer % and B) 50 to 70% by weight of two aromatic vinyl compounds-vinyl cyan compound copolymers having different weight average molecular weights, and more preferably A-1) graft copolymer and A-2) graft 30 to 45% by weight of the total copolymer and B) 55 to 70% by weight of two aromatic vinyl compounds having different weight average molecular weight-vinyl cyan compound copolymers, most preferably A-1) graft copolymer 30 to 40 wt% of the total amount of the coalescence and A-2) graft copolymer and B) 60 to 70 wt% of two aromatic vinyl compounds-vinyl cyan compound copolymers having different weight average molecular weights, within this range It has the effect of giving the impression that the surface appearance of the co-extruded product is improved by improving the mechanical properties and processability, but has excellent weather resistance, low gloss, and improved colorability.

A-1) the graft copolymer and A-2) the combined content of the graft copolymer, and B-1) the aromatic vinyl compound-vinyl cyan compound copolymer and B-2) the aromatic vinyl compound-vinyl cyan compound copolymer When the weight ratio ((A-1+A-2): (B-1+B-2)) of the combined content is 1:0.5 to 1:2, the gloss is low, and the colorability and color development characteristics are improved. The surface appearance of the extruded product has a beautiful effect.

A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, and B-2) aromatic vinyl compound-vinyl cyan compound copolymer When the color development power coverage value (X) calculated by the following Equation 6 of the thermoplastic resin composition is 20 to 33%, preferably 25 to 30%, the colorability and color development properties are improved, so that the surface appearance of the co-extruded product is beautiful. have.

[Equation 6]

(In Equation 6, Sa1, Sa2, Sb1, and Sb2 are A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, B- 2) The content (or weight %) of the soluble material (sol) after each of the aromatic vinyl compound-vinyl cyan compound copolymer is dissolved in acetone and centrifuged, and Aa1, Aa2, Ab1, Ab2 are A-1) graph After dissolving each of the copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, and B-2) aromatic vinyl compound-vinyl cyan compound copolymer in acetone and centrifuging Indicates the content (or weight %) of the vinyl cyanide compound in the molten substance (sol).)

polyamide

The polyamide resin of the present base is preferably 0.5 to 10% by weight, more preferably 1 to 10% by weight, still more preferably 3 to 8% by weight, most preferably 5 to 7% by weight based on the thermoplastic resin composition There is an advantage of providing a thermoplastic resin composition having excellent weather resistance, low gloss, and excellent surface appearance by improving viscoelastic properties while maintaining the same or higher mechanical properties and processability within this range.

The polyamide resin preferably has a melting temperature (Tm) of 250° C. or higher, and a specific example is 250 to 280° C., preferably 250 to 270° C., and has particularly low gloss within this range, has an even surface gloss, and has a surface roughness. It has the advantage of giving an emotionally soft feeling due to its low value.

In the present disclosure, the melting temperature (Tm, Melting Temperature) may be measured by a measurement method commonly used in the technical field to which the present invention belongs, and specifically, it may be measured by a Dynamic Scanning Calorimeter (DSC) method. .

The polyamide resin preferably has a relative viscosity (96% sulfuric acid solution) of 2.5 or less, a specific example of 2.0 to 2.5, and a preferred example of 2.2 to 2.5, and within this range, mechanical properties and processability are maintained at the same level or higher, but weather resistance There is an advantage of providing a thermoplastic resin composition having an excellent, low gloss, an even surface gloss, and a low surface roughness value, which gives an emotionally soft feeling.

In the present description, % means % by weight unless otherwise defined.

In the present description, the relative viscosity can be measured with a Ubbelohde viscometer by the ISO 307 sulfuric acid method. Specifically, a solution prepared by dissolving 1 g of a sample to be measured in 100 ml of an aqueous solution of sulfuric acid having a concentration of 96% by weight is measured with a Brookfield rotational viscometer (Brookfield). rotational viscometer) can be used to measure at 20°C.

In the present substrate, if the polyamide resin satisfies the melting temperature according to the present invention, the type is not particularly limited, and specific examples include polyamide 6, polyamide 66 (PA 6.6), polyamide 46, polyamide ll, polyamide 12 , Polyamide 610, Polyamide 612, Polyamide 6/66, Polyamide 6/612, Polyamide MXD6, Polyamide 6/MXD6, Polyamide 66/MXD6, Polyamide 6T, Polyamide 6I, Polyamide 6/6T , polyamide 6/6I, polyamide 66/6T, polyamide 66/6I, polyamide 6/6T/6I, polyamide 66/6T/6I, polyamide 9T, polyamide 9I, polyamide 6/9T, poly At least one selected from the group consisting of amide 6/9I, polyamide 66/9T, polyamide 6/12/9T, polyamide 66/12/9T, polyamide 6/12/9I and polyamide 66/12/6I and preferably at least one selected from the group consisting of polyamide 6, polyamide 12 and polyamide 66.

The method for preparing the polyamide resin is not particularly limited as long as it is a polymerization method commonly carried out in the art to which the present invention belongs, and may be commercially purchased and used if it meets the definition of polyamide according to the present invention.

Thermoplastic resin composition

The thermoplastic resin composition of the present disclosure ((A-1)+(A-2)+(B-1)+(B-2)+(C)) is, for example, an inorganic pigment based on 100 parts by weight of the total amount of the thermoplastic resin composition. 0.1 to 5 parts by weight, preferably 0.1 to 2 parts by weight, more preferably 0.1 to 1 parts by weight, even more preferably 0.3 to 0.6 parts by weight, within this range, the effect of excellent weather resistance and hiding power there is

The inorganic pigment may be, for example, at least one selected from the group consisting of a metal compound such as Ti, Pb, Fe, Cr, and carbon black, and the metal compound is preferably a metal oxide or a metal hydroxide. For example, TiO ₂ , zinc oxide (Zinc Oxide) as a white inorganic pigment; Carbon black, graphite as black inorganic pigments; Red inorganic pigments such as IOR, Cadmium Red, Red Lead (Pb3O4); Chrome Yellow, Zinc Chromate, Cadmium Y.; And the green inorganic pigment may be at least one selected from the group consisting of Chrome Green and Zinc Green, and the most preferred inorganic pigment may be TiO ₂ which is a white inorganic pigment.

In the present invention, the weight ratio (D:C) of the (D) pigment or dye to the (C) polyamide resin is, for example, more than 1:1 to 1:10 or less, preferably 1:2 to 1:10. , a specific example of 1:5 to 1:10, in which case there is an advantage suitable for siding, roofing and decking board materials.

The thermoplastic resin composition preferably has a softening point of 90° C. or more, more preferably 90.5° C. or more, as measured by a load of 18.5 kg/cm ² with an HDT Tester 6M-2K (made by Toyoseiki) device in accordance with ASTM D648. Specific examples may be 91 to 93 ℃, there is an excellent effect, such as heat resistance properties, co-extrusion properties within this range.

The thermoplastic resin composition has, for example, an Izod impact strength (1/8 inch) of 5 kg cm / cm or more, preferably 6 kg cm / cm or more, according to ASTM 256, and a specific example is 6 to 13 kg cm / cm. There are advantages to being suitable for siding, roofing and decking board materials within this range.

The thermoplastic resin composition is a film produced by processing the pellets extruded at 280 ° C. under the conditions of barrel temperature 150 ° C., 190 ° C., 190 ° C., 190 ° C. and die part temperature 200 ° C., 200 ° C., 200 ° C. The gloss value measured at 60 ° with a gloss meter is 5.0 to 11.0, preferably 5.5 to 10.0, and may be 5.5 to 9.0 as a specific example, and there is an advantage suitable for siding, roofing and decking board materials within this range.

The thermoplastic resin composition has an L value of 90 or more, preferably 91 or more, measured based on the method of CIE Lab with Hunter Lab as an example, and may be 91 to 93 as a specific example, and siding within this range , has the advantage of being suitable for roofing and decking board materials.

The thermoplastic resin composition has a b value of 8 or more, preferably 8.1 or more, as measured by the method of CIE Lab with Hunter Lab as an example, and may be 8.1 to 10 as a specific example, and siding within this range , has the advantage of being suitable for roofing and decking board materials.

The thermoplastic resin composition has a correlation (G/C) of 0.5 to 1.1, preferably 0.8 to 1.1, between gloss (G) measured at 60° with a gloss meter and chromaticity b value (C) measured by CIE Lab. , there is an advantage suitable for siding, roofing and decking board materials when it satisfies 0.8 to 1.0 as a specific example.

In the present description, the color development index is a parameter indicating the coloring power or color yield of a dye or a pigment, and is expressed as an absorption ratio between a standard sample and a sample sample to directly indicate the absorption of the dye and pigment.

The method for measuring the color development index is known in the art, and for example, there are a λ maxima color strength method, an Apparent color strength method, an Integrated color strength method, etc., and the Apparent color strength method is mainly used for measuring achromatic colors including white and black. , λ maxima color strength method is mainly used for chromatic color measurement.

The thermoplastic resin composition may have a black-and-white color development index (Color Strength, C/S) of 100 or more, preferably 100 to 130, and specifically 100 to 116 calculated by Equation 3 below, as shown in Equations 4 and 5 The calculated color strength index (C/S) may be 110 or more, preferably 113 to 130, and specifically 114 to 119. Within these ranges there is the advantage of providing achromatic or chromatic color power suitable for siding, roofing and decking board materials.

[Equation 3]

Monochrome color development index (N) = ∑ (absorption value of sample)/∑ (absorption value of standard sample) ∑ (absorption value of standard sample) ∑

(In Equation 3, the absorption value is the solid sample absorption value calculated by the Kubelka-Munk equation represented by the following Equation 5, and ∑ is the spectral integral value of the entire region of 400 to 700 nm.)

[Equation 4]

Color color index (C) = λmax (absorption value of sample)/λmax (absorption value of standard sample) X 100

(In Equation 4, the absorption value is the solid sample absorption value calculated by the Kubelka-Munk equation represented by Equation 5 below, and λmax is the highest absorption wavelength over the entire spectrum)

[Equation 5]

Calculated absorption value of solid sample = (1-R) ² / 2R

(In Equation 5, R is X-lite Color-eye 7000A and uses the reflection coefficient value measured according to the method of CIE Lab.)

As can be seen from Equation 5, absorption and scattering of color cannot be measured directly, but are given as a relational expression between reflection, absorption, and scattering.

In addition, in Equation 4, ∑ is defined as referring to a spectral integral value in the entire region of 400 to 700 nm.

In addition, in the present description, R (reflection coefficient value) of Equation 5 is, specifically, X-lite Color-eye 7000A, based on the method of CIE Lab, from UV D65 light source to SCI method at Degree Observer 10°, LAV Apertuyre , LAV LENS, CIE GANZ 82 whiteness, YI ASTM E313-73 (D1965) conditions. The L value and b value were measured by obtaining the values in the Reflectance Mode according to the CIE Lab method based on the Munsell System. L is expressed as a number from 0 to 100, and the closer to 0, the more black, and the closer to 100, the more white. The a value represents the Red-Green value, and the b value represents the Yellow-Boue value. For the C/S value, the value automatically calculated based on the formula by the software of Propalett Paint/Plastics Formulation Platinum 5.2.5.1. of GretagMacbeth LLC was used as it is. To obtain reproducible experimental values, the average values of three samples were obtained. The color development (C/S) shows a value greater than 100 when the standard is 100 and the colorability is good.

In the present description, the black-and-white color development index value (N) is a parameter indicating the degree of color development for black or white pigments and dyes. As this value is higher, there is an effect of exhibiting the same level of colorability with a small amount of pigment.

In the present description, the color development index value (C) is a parameter indicating the degree of color development with respect to pigments and dyes of chromatic colors, including grays, except for black and white. As this value is higher, there is an effect of exhibiting the same level of colorability with a small amount of pigment.

The thermoplastic resin composition optionally includes a lubricant, a pigment, a heat stabilizer, a light stabilizer, a dye, a colorant, a mold release agent, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, a flame retardant, an anti-drip agent, an anti-friction agent, and 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 parts by weight, based on 100 parts by weight of the thermoplastic resin composition (A-1) to (C) in total, at least one selected from the group consisting of abrasion resistance agents It may be further included in parts by weight, and within this range, there is an advantage in that necessary physical properties are well implemented without reducing the original properties of the thermoplastic resin composition of the present invention.

The thermoplastic resin composition may have a color development power coverage value (X) calculated by Equation 4 or more, preferably 20 to 30%, more preferably 25 to 30%, and impact strength within this range, It has excellent mechanical properties such as tensile strength and flexural strength, glossiness and colorability, and has excellent color development and hiding power.

In the present base material, the higher the value of the color development power coverage (Y), the more evenly the vinyl cyan compound is dispersed, so that the glossiness is low and the colorability and color development property are excellent.

The method for producing the thermoplastic resin composition of the present invention is preferably A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle diameter of 0.33 to 0.5 μm, and A-2 ) 10 to 50 wt% of the total weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle diameter of 0.05 to 0.2 μm; B-1) 0 to 30 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 67 to 75 wt% of an aromatic vinyl compound and 25 to 33 wt% of a vinyl cyan compound; B-2) 20 to 70 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 70 to 75 wt% of an aromatic vinyl compound and 25 to 30 wt% of a vinyl cyan compound; and C) 0.5 to 10 wt% of a polyamide resin having a melting temperature (Tm) of 250 ° C. or higher, wherein the A-1) graft copolymer and A-2) the graft copolymer are calculated by the following Equation 1 After mixing so that the color development coverage value (X) is 20% or more, it is characterized in that it comprises the step of preparing pellets using an extrusion kneader under the conditions of 220 to 280 ° C. In this case, mechanical properties compared to conventional ASA-based resins There is an advantage of providing a thermoplastic resin composition having excellent weather resistance, low gloss, even surface gloss, and excellent colorability and color development while maintaining processability and the like at the same or higher level.

The method for producing the thermoplastic resin composition shares all the technical characteristics of the aforementioned thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.

The step of preparing the pellets using the extrusion kneader is preferably under 220 to 290 ℃, more preferably under 250 to 290 ℃, even more preferably under 270 to 290 ℃ may be carried out, and in this case, the temperature means the temperature set in the cylinder.

The extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the art to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.

< Exterior material >

The exterior material of the present substrate is characterized in that it contains the thermoplastic resin composition of the present substrate, and in this case, mechanical properties and processability are equal to or higher than that of the conventional ASA resin, and the advantage is excellent in appearance quality due to low gloss and improved colorability and color development. have.

The exterior material may be, for example, a co-extrusion extrusion molding product or an injection molding product, preferably a siding material, a decking board material, a roofing material, and more preferably a sliding door or window can

The exterior material is preferably co-extrusion or injection of the thermoplastic resin composition of the present base at a molding temperature of 190 to 250 ℃, preferably 190 to 230 ℃, more preferably 190 to 220 ℃ It can be prepared including There is an advantage in that the matte effect is well expressed in the product within this range.

The co-extrusion may be, for example, co-extrusion with a PVC resin. As a specific example, PVC may have a thickness of 0.5 to 3.0 mm, and the thermoplastic resin composition of the present disclosure may have a thin film thickness of 0.05 to 0.5T. When the thickness of the thermoplastic resin composition of the present base is thin, the hiding power is decreased, and the pigment content such as TiO ₂ may be increased.

In describing the thermoplastic resin composition of the present disclosure, its manufacturing method and the exterior material, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation. do.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.

[Example]

Materials used in Examples 1 to 4 and Comparative Examples 1 to 5 below are as follows.

A-1) Large-diameter graft copolymer of emulsion polymerization (Rubber: 50 wt% of butyl acrylate polymer having an average particle diameter of 500 nm, 35 wt% of styrene, 15 wt% of acrylnitrile)

A-2) Small-diameter graft copolymer of emulsion polymerization method (Rubber: 50 wt% of butyl acrylate polymer having an average particle diameter of 130 nm, 37 wt% of styrene, 13 wt% of acrylnitrile)

A-3) Small-diameter graft copolymer of emulsion polymerization (Rubber: 50 wt% of butyl acrylate polymer having an average particle diameter of 130 nm, 32.5 wt% of styrene, 17.5 wt% of acrylnitrile)

B-1) Bulk polymerization type weight average molecular weight 100,000 to 150,000 g/mol SAN resin (90HR, styrene 73% by weight, acrylonitrile 27% by weight)

B-2) SAN resin (97HC, styrene 70% by weight, acrylonitrile 30% by weight) of weight average molecular weight exceeding 150,000 g/mol to 200,000 g/mol or less in bulk polymerization method

B-3) SAN resin (65 wt% of styrene, 35 wt% of acrylonitrile) with a weight average molecular weight of greater than 150,000 g/mol and less than or equal to 200,000 g/mol of bulk polymerization

C-1) Melting temperature (Tm) of 261 ℃ PA 6.6

C-2) Melting temperature (Tm) PA 6 at 221 ℃

(D-1) heat-resistant SAN resin (weight average molecular weight of 80,000 to 100,000 g/mol in bulk polymerization, 71 wt% of methyl-substituted styrene, 29 wt% of acrylonitrile, product name 200UH);

(D-2) Polymethacrylate resin (IF850 from LGMMA)

(D-3) sPS surface control agent (product name: Polyone, brand name: QT-20MN).

Examples 1 to 4 and Comparative Examples 1 to 5

Each of the components and contents described in Table 1 below were prepared into pellets using an extrusion kneader (twin screw extruder) of 28 pie, L/D 36 standard under 280 °C.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 A-1) 19 23 28 22 - - 35 25 23 A-2) 15 13 16 26 - - 20 13 18 A-3) - - - - 42 48 - - - B-1) 20 - 24 20 - - - 41 8 B-2) 40 58 32 32 - - - - 36 B-3) - - - - 58 52 - - - C-1) 6 6 4 4 6 4 - 6 15 C-2) - - One One - One - - - D-1) - - - - - - - 15 - D-2) - - - - - - 40 - - D-3) - - - - - - 5 - - TiO ₂ 0.6 0.6 0.5 0.5 0.6 0.5 0.5 0.6 0.6

(In the table, TiO ₂ content is A-1), A-2), A-3), B-1), B-2), B-3), C-1), C-2), D -1), D-2), and D-3) are in parts by weight based on a total of 100 parts by weight.)

In addition, the produced pellets were uniformly prepared into a film with a thickness of 0.15T through a film extruder, and film gloss was measured by the following method using this as a sample. At this time, the film extruder uses a single screw extruder for sheet molding (manufactured by Collin, E20T product, 20 pie, L/D:25), and the temperature conditions are 150, 200, 210, 210 ℃ of barrel temperature in order from the extruder inlet. And the die part temperature was set to 220, 220, 230 ℃. The pellets were sufficiently dried in an oven at 80° C. for 3 hours or more before input into the film extruder to remove the moisture influence, and then put into the inlet of the film extruder to uniformly produce a film with a thickness of 0.15T. The temperature of the used rear roller was set to 85°C using water as a medium, and the roller was configured so that only one side of the resin extruded through the T-die is in contact with the roller. Here, the RPM of the film extruder screw was fixed at 100 and the linear speed of the roll was adjusted so that the thickness of the sheet was 0.15T. Among the extruded sheet surfaces, film gloss and surface roughness (Ra), etc. were measured for the surface in contact with the first roll. For reference, when measuring with a surface that is not in contact with the first roll, a difference in surface roughness may occur.

Furthermore, the prepared pellets were injected at a molding temperature of 220° C. to prepare a specimen for measuring physical properties, and the impact strength was measured using this.

[Test Example]

The properties of the pellets, sheets and specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 5 were measured by the following method, and the results are shown in Table 2 below.

* Izod impact strength (kg.cm/cm): Measured by ASTM 256 method.

* Film Gloss: Measured at 60° with a gloss meter VG7000.

* Softening point (℃): In accordance with ASTM D648, HDT Tester 6M-2K (manufactured by Toyoseiki) was measured with a load of 18.5 kg/cm ² .

* Film Gloss: A sheet having a thickness of 0.15T prepared by processing at 190°C as described above was measured at 60° with a gloss meter VG7000.

* L value, b value, C/S value: It was measured according to the method of CIE Lab by Hunter Lab . Specifically, according to the method of CIE Lab with X-lite Color-eye 7000A, at Degree Observer 10° from UV D65 light source by SCI method, LAV Apertuyre, LAV LENS, CIE GANZ 82 whiteness, YI ASTM E313-73 (D1965) conditions were measured. The L value and b value were measured by obtaining the values in the Reflectance Mode according to the CIE Lab method based on the Munsell System. L is expressed as a number from 0 to 100, and the closer to 0, the more black, and the closer to 100, the more white. The a value represents the Red-Green value, and the b value represents the Yellow-Boue value. For the C/S value, the value automatically calculated based on the formula by the software of Propalett Paint/Plastics Formulation Platinum 5.2.5.1. of GretagMacbeth LLC was used as it is. To obtain reproducible experimental values, the average values of three samples were obtained. The color development (C/S) shows a value greater than 100 when the standard is 100 and the colorability is good.

*Color development (unit %): The calculation of color development was calculated by substituting Equation 3 for black and white, and Equation 4 for colors other than black and white.

[Equation 3]

Monochrome color development index (N) = ∑ (absorption value of sample) / ∑ (absorption value of standard sample) X 100

(In Equation 3, the absorption value is the solid sample absorption value calculated by the Kubelka-Munk equation represented by Equation 5 below, and ∑ is the spectral integral value of the entire region of 400 to 700 nm)

[Equation 4]

Color development index (C) = λmax (absorption value of sample) / λmax (absorption value of standard sample) X 100

(In Equation 4, the absorption value is the solid sample absorption value calculated by the Kubelka-Munk equation represented by Equation 5 below, and λmax is the highest absorption wavelength over the entire spectrum)

[Equation 5]

Calculated absorption value of solid sample = (1-R) ² / 2R

(In Equation 5, R is X-lite Color-eye 7000A and uses the reflection coefficient value measured according to the method of CIE Lab.)

* Color development index (unit %): The color development index was calculated by substituting it in Equation 6-1 below.

[Equation 6-1]

Xa1 + Xa2 + Xb1 + Xb2 = {(Aa1/Sa1) + (Aa2/Sa2) + (Ab1/Sb1) + (Ab2/Sb2)} * 100

(In Equation 6-1, Sa1, Sa2, Sb1, and Sb2 are A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer; B-2) Aromatic vinyl compound-vinyl cyan compound copolymer is each dissolved in acetone and centrifuged, followed by the content (% by weight) of the soluble substance (sol), Aa1, Aa2, Ab1, Ab2 is A-1) The graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, and B-2) aromatic vinyl compound-vinyl cyan compound copolymer were each dissolved in acetone and centrifuged. Shows the content (wt%) of the vinyl cyanide compound in the molten material (sol) after.)

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 impact strength
(1/8") 6.0 6.3 8.5 12.1 6.2 7.0 4.5 6.2 - softening point 92.8 92.4 93.8 90.8 96.1 91.9 84.2 93.7 - film gloss 7.1 7.6 5.9 8.1 6.3 12.2 11.1 3.9 - L value 93.18 92.64 93.41 91.27 90.48 90.29 94.92 93.06 - b value 8.27 8.25 7.84 8.13 10.62 10.42 4.83 8.46 - chromogenic
(C/S)
1.0 parts by weight Black - - 100 - - - 129.0 - - chromogenic
(C/S)
3.6 parts by weight Dark Gray - - - 117.9 - 100 - - - chromogenic
(C/S)
2.4 parts by weight Light gray 116.4 114.5 - - 100 - - - - chromogenic
(C/S)
0.6 parts by weight White - 115.4 - - - - - 100 107.1 color development index 28.7 29.6 28.6 28.5 34.8 35.1 28.3 27.5 29.0

As shown in Table 2 above, the thermoplastic resin compositions (see Examples 1 to 4) according to the present invention have mechanical properties such as impact strength, etc. compared to Comparative Examples 1 to 5 that do not include the composition according to the present invention, and furthermore, heat resistance such as softening point It can be seen that the L value, b value, and color development property are adjusted within an appropriate range to provide natural coloring quality while maintaining the same or higher properties while providing a natural matte as seen in film glossiness.

Specifically, the thermoplastic resin composition according to the present invention (see Examples 1 to 4) satisfies an impact strength of 5.5 or more, a softening point of 90 or more, a gloss of 10 or less, and a high degree of coloration. If the softening point is lower than this, bending may occur in the summer season and sunlight. If the gloss is higher than the suggested value, reflected light occurs and glare occurs, and it does not match the recent design trend. Even with a small amount of pigment, there is an effect of implementing the same level of color.

On the other hand, according to Comparative Examples 1 and 2, compared to Examples 1, 2, and 4, the L value is low and the color is dark, and the b value is high, so that the coloration degree is lowered. Specifically, it can be seen that the light gray color development of Examples 1 and 2 is superior to that of Comparative Example 1, and the dark gray color development of Example 4 is superior to that of Comparative Example 2. It can be seen that the color development property is superior to the direction in which the b value is increased by increasing the vinyl cyan compound content in order to similarly match the overall refractive index of the resin and increase the color development coverage (X). Therefore, it was confirmed that the color development property was excellent within the optimal range of the color development power coverage (X).

In addition, with respect to Comparative Example 3, it is known that the use of component (D-3) reduces color development, and when the component (D-2) is used to solve this problem, the colorability is improved but the impact is reduced. Therefore, it can be seen that (a) when the amount of the bimodal graft copolymer component is increased, the softening point is lowered.

In addition, according to Comparative Example 4, when the component (D-1) was used to improve the softening point compared to Example 2, the color development index calculated from Equation 1 was 15.4%, indicating that the color development property was lowered.

In addition, according to Comparative Example 5, it can be seen that when the component (C-1) is used in excess, the impact strength and the softening point are respectively lowered.

Furthermore, although the color development index was at a desired level of 29.1 or less, it can be confirmed that physical properties that are difficult to use for the purpose can be confirmed.

Considering these results, a resin composition containing a styrene-based resin and a polyamide-based resin satisfies the color development coverage and color development index characteristics, thereby maintaining the basic physical properties of the base resin used in molded products and providing a natural matte exterior material. Since compatibility can be improved while improving the quality of coloring and color development required as a molded article, it can be confirmed that it is suitable for a resin composition having excellent product reliability as an exterior material.

Claims (13)

A-1) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising an alkyl acrylate rubber having an average particle diameter of 0.33 to 0.5 μm, and A-2) an alkyl acrylate rubber having an average particle diameter of 0.05 to 0.2 μm. 10 to 50 wt% of the total weight of the total weight of the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising;
B-1) 0 to 30 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 67 to 75 wt% of an aromatic vinyl compound and 25 to 33 wt% of a vinyl cyan compound;
B-2) 20 to 70 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer comprising 70 to 75 wt% of an aromatic vinyl compound and 25 to 30 wt% of a vinyl cyan compound; and
C) containing 0.5 to 10% by weight of a polyamide resin having a melting temperature (Tm) of 250° C. or higher,
The thermoplastic resin composition, characterized in that the A-1) graft copolymer and A-2) the graft copolymer each have a color development coverage value (X) calculated by the following Equation (1) of 20% or more.
[Equation 1]
X = {A/S} * 100
(In Equation 1, S is the content (wt%) of the soluble material (sol) after dissolving the graft copolymer in acetone and centrifuging, and A is the graft copolymer dissolved in acetone and centrifuged. Shows the content (wt%) of the vinyl cyanide compound in the molten material (sol) after.) According to claim 1,
A-1) the graft copolymer and A-2) the combined content of the graft copolymer, and B-1) the aromatic vinyl compound-vinyl cyan compound copolymer and B-2) the aromatic vinyl compound-vinyl cyan compound copolymer The weight ratio of the sum of the contents ((A-1+A-2): (B-1+B-2)) is 1:0.5 to 1:2. According to claim 1,
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the black and white color index (Color Strength, N) calculated by the following Equations 3 and 5 is 100 or more.
[Equation 3]
Monochrome color development index (N) = ∑ (absorption value of sample) / ∑ (absorption value of standard sample) X 100
(In Equation 3, the absorption value is the solid sample absorption value calculated by the Kubelka-Munk equation represented by Equation 5 below, and ∑ is the spectral integral value of the entire region of 400 to 700 nm)
[Equation 5]
Calculated absorption value of solid sample = (1-R) ² / 2R
(In Equation 5, R is X-lite Color-eye 7000A and uses the reflection coefficient value measured according to the method of CIE Lab.) According to claim 1,
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the color development index (Color Strength, C) calculated by the following Equations 4 and 5 is 110 or more.
[Equation 4]
Color color index (C) = λmax (absorption value of sample) / λmax (absorption value of standard sample) X 100
(In Equation 4, the absorption value is the solid sample absorption value calculated by the Kubelka-Munk equation represented by Equation 5 below, and λmax is the highest absorption wavelength over the entire spectrum)
[Equation 5]
Calculated absorption value of solid sample = (1-R) ² / 2R
(In Equation 5, R is X-lite Color-eye 7000A and uses the reflection coefficient value measured according to the method of CIE Lab.) According to claim 1,
The weight ratio (A-1: A-2) of the A-1) graft copolymer and the A-2) graft copolymer is 1:0.54 to 1:1.50. According to claim 1,
The A-1) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer contains 30 to 60% by weight of an acrylate rubber having an average particle diameter of 0.33 to 0.5 μm, 20 to 50% by weight of an aromatic vinyl compound, and 10 to 50% by weight of a vinyl cyanide compound. 30 to 60% by weight of an acrylate rubber having an average particle diameter of 0.05 to 0.2 μm, and 20 to 60% by weight of an acrylate rubber, wherein the A-2) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 30 wt% A thermoplastic resin composition comprising 50% by weight and 10 to 30% by weight of a vinyl cyanide compound. According to claim 1,
The B-1) aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 100,000 to 150,000 g/mol, and the B-2) aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of greater than 150,000 g/mol. Thermoplastic resin composition, characterized in that 200,000 g / mol or less. The method of claim 1,
Based on the total weight of the thermoplastic resin composition, the B-1) aromatic vinyl compound-vinyl cyan compound copolymer is included in an amount of 10 to 30 wt %, and the B-2) aromatic vinyl compound-vinyl cyan compound copolymer is 30% by weight. Thermoplastic resin composition, characterized in that it is included in an amount of to 60% by weight. According to claim 1,
A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, and B-2) aromatic vinyl compound-vinyl cyan compound copolymer The thermoplastic resin composition, characterized in that the color coverage value (Xa1 + Xa2 + Xb1 + Xb2) calculated by the following Equation 6-1 of the thermoplastic resin composition is 20 to 33%.
[Equation 6-1]
Xa1 + Xa2 + Xb1 + Xb2 = {(Aa1/Sa1) + (Aa2/Sa2) + (Ab1/Sb1) + (Ab2/Sb2)} * 100
(In Equation 6-1, Sa1, Sa2, Sb1, and Sb2 are A-1) graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer; B-2) The content (or weight %) of the soluble substance (sol) after each of the aromatic vinyl compound-vinyl cyan compound copolymer is dissolved in acetone and centrifuged, and Aa1, Aa2, Ab1, Ab2 are A-1 ) Graft copolymer, A-2) graft copolymer, B-1) aromatic vinyl compound-vinyl cyan compound copolymer, and B-2) aromatic vinyl compound-vinyl cyan compound copolymer were respectively dissolved in acetone and centrifuged It indicates the content (or weight %) of the vinyl cyanide compound in the molten material (sol) after fusion.) According to claim 1,
It characterized in that it contains 0.1 to 5 parts by weight of a pigment or dye (D) based on 100 parts by weight of the thermoplastic resin composition.
Thermoplastic resin composition. 11. The method of claim 10,
The weight ratio (D:C) of the (D) pigment or dye and (C) the polyamide resin is greater than 1:1 to 1:10, characterized in that
Thermoplastic resin composition. A composition comprising the thermoplastic resin composition of any one of claims 1 to 11
exterior material. 13. The method of claim 12,
wherein the exterior material is a siding material, a roofing material or a decking board material
exterior material.