KR20240055272A - Thermoplastic resin composition, method for preparing the thermoplastic resin composition and molding products thereof - Google Patents

Abstract

This disclosure relates to a thermoplastic resin composition, a manufacturing method thereof, and a molded article containing the same, and more specifically, (A) an alkyl acrylate containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm - an aromatic vinyl compound - vinyl cyan 100 parts by weight of a base resin containing 21 to 79% by weight of a compound graft copolymer and 21 to 79% by weight of (B) (meth)acrylic acid alkyl ester polymer; and (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250°C or higher, and an alkyl acrylate coverage (X) value calculated by Formula 1 above is 65% by weight or more. It relates to a resin composition, a manufacturing method thereof, and a molded article containing the same.
According to the present invention, there is an effect of providing a thermoplastic resin composition having excellent mechanical properties such as impact strength, tensile strength, hardness, processability, and weather resistance, as well as excellent transparency and low light characteristics, a method of manufacturing the same, and a molded article containing the same.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded product containing the same {THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THE THERMOPLASTIC RESIN COMPOSITION AND MOLDING PRODUCTS THEREOF}

The present invention relates to a thermoplastic resin composition, a manufacturing method thereof, and a molded article containing the same, and more specifically, to a thermoplastic resin composition having excellent mechanical properties such as impact strength, tensile strength, and hardness, processability, and weather resistance, as well as transparency and low-light characteristics. , its manufacturing method, and molded articles containing it.

Acrylonitrile-butadiene-styrene resin (hereinafter referred to as 'ABS resin'), which is based on conjugated diene rubber, has excellent processability, mechanical properties, and appearance characteristics and is used in parts for electrical and electronic products, automobiles, small toys, and furniture. It is widely used as a building material, etc. However, because ABS resin is based on butadiene rubber containing chemically unstable unsaturated bonds, the rubber polymer is easily aged by ultraviolet rays and has very poor weather resistance, making it unsuitable as an outdoor material.

In order to overcome the problems of ABS resin as described above, an acrylic copolymer, represented by acrylate-styrene-acrylonitrile graft copolymer (hereinafter referred to as 'ASA resin'), which does not have ethylenically unsaturated bonds, is used. . ASA resin has excellent physical properties such as processability, impact resistance, chemical resistance, and weather resistance, and is used in a variety of applications such as construction materials, interior and exterior materials for vehicles such as automobiles and motorcycles, electrical and electronic products, as well as ships, leisure products, construction materials, and gardening products. It is widely used in various fields, and its demand is rapidly increasing.

In addition, the demand for low-gloss ASA resin with a luxurious appearance is gradually increasing so that it can move away from the artificial plastic feel and meet the demands and levels of emotional quality of customers.

Recently, one of the applications for which low-gloss ASA resin is mainly applied is hidden display. When the LED is off, the LED is hidden and invisible, but when the LED is on, the LED light is clearly visible, and there is a display on top of the LED. A material that is transparent and scatters light is required so that it can emit light softly.

Accordingly, there is a need to develop a material that gives ASA resin excellent weather resistance, transparency, and low-light characteristics to hide the LED when the LED is off and to clearly show the LED light when the LED is on.

Korean Patent Publication No. 2009-0095764

In order to solve the problems of the prior art as described above, the purpose of the present invention is to provide a thermoplastic resin composition that has excellent mechanical properties such as impact strength, tensile strength, and hardness, processability, and weather resistance, as well as transparency and low-light characteristics.

Additionally, the purpose of this description is to provide a method for producing the above thermoplastic resin composition.

Additionally, the purpose of this description is to provide a molded article manufactured from the above thermoplastic resin composition.

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

In order to achieve the above object, the present substrate contains (A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinylcyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and (B) ) 100 parts by weight of a base resin containing 21 to 79% by weight of (meth)acrylic acid alkyl ester polymer; and (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250°C or higher, and an alkyl acrylate coverage (X) value calculated by the following formula (1) of 65% by weight or more. A resin composition is provided.

[Equation 1]

X = {(G-Y)/Y}

(In Equation 1 above, G represents the gel content (% by weight) relative to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel relative to the total weight of the thermoplastic resin composition.)

In addition, this substrate includes (A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and (B) (meth)acrylic acid. 100 parts by weight of a base resin containing 21 to 79% by weight of an alkyl ester polymer; and (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250° C. or higher, wherein the (A) graft copolymer has a grafting rate of 60% or more calculated by Equation 3 below. A thermoplastic resin composition can be provided.

[Equation 3]

Grafting rate (%) = [Weight of grafted monomer (g) / Rubber weight (g)]

(In Equation 3, the weight (g) of the grafted monomer is the weight (g) of the insoluble material (gel) minus the rubber weight (g) after dissolving the graft copolymer in acetone and centrifuging, Rubber weight (g) is the weight (g) of the theoretically added rubber component in the graft copolymer powder.)

In addition, this substrate includes (A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and (B) (meth)acrylic acid. 100 parts by weight of a base resin containing 21 to 79% by weight of an alkyl ester polymer; and (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250°C or higher; and a film with a thickness of 0.15 T at 60° using a gloss meter according to ASTM D2457. A thermoplastic resin composition can be provided, characterized in that the measured glossiness is 50 or less.

The (A) graft copolymer preferably contains 25 to 50% by weight of alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, based on the total weight thereof; and 50 to 75% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer.

The (B) (meth)acrylic acid alkyl ester polymer is preferably (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid. It may include at least one member selected from the group consisting of decyl ester, and lauryl (meth)acrylic acid.

The (B) (meth)acrylic acid alkyl ester polymer preferably has a weight average molecular weight of 50,000 to 150,000 g/mol.

The (C) crystalline polymer having a melting temperature (Tm) of 250° C. or higher is preferably polyhexamethylene adipamide (PA 66), polytetramethylene adipamide (PA 46), or polyhexamethylene sebasamide (PA). 610), polydodecanolactam (PA 12), polyamide 6/6T, polyamide 6/66, and syndiotactic polystyrene resin.

The thermoplastic resin composition may preferably have a total light transmittance of 75% or more as measured with a film with a thickness of 0.15 T according to ASTM D1003.

The thermoplastic resin composition is preferably manufactured into a sheet with a thickness of 0.15 mm using a T-die extruder, then cut into a length of 100 cm, and then the thickness of the portion excluding 2 to 3 cm from both ends is 10. The thickness deviation calculated as the difference between the maximum and minimum thickness by measuring more than one place may be less than 0.07 mm.

The thermoplastic resin composition may preferably include one or more selected from the group consisting of lubricants, antioxidants, ultraviolet stabilizers, and pigments.

In addition, this substrate includes (A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and (B) (meth)acrylic acid. 100 parts by weight of a base resin containing 21 to 79% by weight of an alkyl ester polymer; and (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250°C or higher; kneading and extruding under conditions of 200 to 300°C and 100 to 500 rpm, calculated using the following formula (1): A method for producing a thermoplastic resin composition is provided, wherein the alkyl acrylate coverage (X) value is 65% by weight or more.

[Equation 1]

X = {(G-Y)/Y}

(In Equation 1, G represents the gel content (% by weight) relative to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel relative to the total weight of the thermoplastic resin composition.)

In addition, this substrate includes (A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and (B) (meth)acrylic acid. 100 parts by weight of a base resin containing 21 to 79% by weight of an alkyl ester polymer; and (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250°C or higher, comprising kneading and extruding under conditions of 200 to 300°C and 100 to 500 rpm, wherein (A) Graf The copolymer can provide a method for producing a thermoplastic resin composition, characterized in that the grafting rate calculated by Equation 3 below is 60% or more.

[Equation 3]

Grafting rate (%) = [Weight of grafted monomer (g) / Rubber weight (g)]

(In Equation 3, the weight (g) of the grafted monomer is the weight (g) of the insoluble material (gel) minus the rubber weight (g) after dissolving the graft copolymer in acetone and centrifuging, Rubber weight (g) is the weight (g) of the theoretically added rubber component in the graft copolymer powder.)

In addition, this substrate includes (A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and (B) (meth)acrylic acid. 100 parts by weight of a base resin containing 21 to 79% by weight of an alkyl ester polymer; And (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250 ℃ or higher; kneading and extruding under conditions of 200 to 300 ℃ and 100 to 500 rpm to prepare a thermoplastic resin composition. The thermoplastic resin composition prepared includes a gloss meter of 50 or less as measured at 60° using a film with a thickness of 0.15 T using a gloss meter according to ASTM D2457. Manufacturing methods can be provided.

Additionally, the present substrate provides a molded article comprising the thermoplastic resin composition.

The molded product may preferably be a hidden display.

According to the present invention, there is an effect of providing a thermoplastic resin composition having excellent mechanical properties such as impact strength, tensile strength, hardness, processability, and weather resistance, as well as excellent transparency and low light characteristics, a method of manufacturing the same, and a molded article containing the same.

In addition, the molded article containing the thermoplastic resin composition of the present invention has excellent transparency and low-light characteristics, has LED hiding characteristics when the LED is off, and has an excellent effect of clearly showing the LED light when the LED is on, providing high quality. It can be provided as a material for hidden displays.

Hereinafter, the thermoplastic resin composition of the present invention, its manufacturing method, and molded articles containing the same will be described in detail.

The present inventors were researching a transparent material for a hidden display that has LED hiding properties when the LED is off, but allows the LED light to be clearly visible when the LED is on, and discovered an alkyl acrylate having a predetermined average particle size. -A crystalline polymer having a melting temperature (Tm) of 250°C or higher is included in a predetermined amount in a base resin containing an aromatic vinyl compound-vinylcyan compound graft copolymer and (meth)acrylic acid alkyl ester polymer in a predetermined content ratio, and It was confirmed that when the alkyl acrylate coverage value in the thermoplastic resin composition is adjusted within a predetermined range, mechanical properties such as impact strength, tensile strength, and hardness, fluidity, weather resistance, and transparency are excellent, and low-light characteristics are improved. Based on this, further research is conducted. We worked hard to complete this invention.

A detailed look at the thermoplastic resin composition according to the present invention is as follows.

The thermoplastic resin composition of the present invention includes (A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinylcyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and (B) (meth ) 100 parts by weight of a base resin containing 21 to 79% by weight of acrylic acid alkyl ester polymer; and (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250°C or higher, and the alkyl acrylate coverage (X) value calculated by the following formula (1) is 65% by weight or more. In this case, mechanical properties such as impact strength, tensile strength, and hardness, processability, and weather resistance are excellent, while transparency and low-light characteristics are excellent. When the LED is turned off, the LED is hidden, and when the LED is turned on, the LED light is clearly visible. It has the advantage of making it look more attractive.

[Equation 1]

X = {(G-Y)/Y}

(In Equation 1 above, G represents the gel content (% by weight) relative to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel relative to the total weight of the thermoplastic resin composition.)

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail by composition.

(A) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer

The (A) graft copolymer is, for example, 21 to 79% by weight, preferably 30 to 75% by weight, more preferably 40 to 65% by weight, even more preferably 45 to 55% by weight, based on the total weight of the base resin. It may be in weight percent, and within this range, it has excellent mechanical properties such as impact strength, tensile strength, and hardness, as well as processability and weather resistance.

The (A) graft copolymer may preferably include an alkyl acrylate rubber (core) and an aromatic vinyl compound-vinyl cyan compound copolymer (shell) surrounding the same.

The alkyl acrylate rubber may preferably include an alkyl acrylate rubber having an average particle diameter of 50 to 120 nm, more preferably 60 to 120 nm, and even more preferably 80 to 110 nm, and the final particle size within this range. Excellent impact strength, tensile strength, gloss, and low-glow characteristics can be imparted to the manufactured thermoplastic resin composition.

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

For example, the (A) graft copolymer contains 25 to 50% by weight, preferably 30 to 50% by weight, more preferably 35 to 50% by weight of alkyl acrylate rubber based on the total weight thereof; and 50 to 75% by weight, preferably 50 to 70% by weight, and more preferably 50 to 65% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer surrounding the same. Impact strength and tensile strength within this range may be included. It has the advantage of excellent mechanical properties such as strength and hardness, as well as excellent transparency and fluidity.

For example, the alkyl acrylate rubber may further include an aromatic vinyl compound, in which case the mechanical properties are more excellent. For example, the content of the aromatic vinyl compound contained in the rubber may be 0.1 to 25% by weight, preferably 2 to 23% by weight, and more preferably 5 to 20% by weight, based on a total of 100% by weight of the acrylate rubber. , Within this range, excellent mechanical properties, gloss, and transparency are achieved without deterioration of physical properties.

The alkyl acrylate rubber can be manufactured, for example, by emulsion polymerization of alkyl acrylate. As a specific example, it can be manufactured by emulsion polymerization by mixing alkyl acrylate, emulsifier, initiator, grafting agent, crosslinking agent, electrolyte and solvent, In this case, the grafting efficiency is excellent, resulting in excellent mechanical properties such as impact strength and tensile strength.

For example, the aromatic vinyl compound-vinyl cyanide compound copolymer (shell) may have a weight average molecular weight of 40,000 to 120,000 g/mol, preferably 50,000 to 110,000 g/mol, and more preferably 60,000 to 110,000 g/mol. , within this range, it has excellent processability without reducing impact strength and has the effect of reducing the occurrence of whitening during bending processing.

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

For example, the aromatic vinyl compound-vinyl cyan compound copolymer (shell) may further include an alkyl acrylate, and in this case, mechanical properties such as impact strength and tensile strength, fluidity, and physical property balance are excellent.

For example, the aromatic vinyl compound-vinyl cyan compound copolymer (shell) contains 55 to 85 wt% of aromatic vinyl compound, 10 to 30 wt% of vinyl cyan compound, and 0.1 to 20 wt% of alkyl acrylate based on a total of 100 wt%. It consists of 60 to 80% by weight of an aromatic vinyl compound, 13 to 26% by weight of a vinyl cyan compound, and 3 to 20% by weight of an alkyl acrylate, and more preferably 65 to 78% by weight of an aromatic vinyl compound. By weight, it may contain 15 to 22% by weight of vinyl cyan compound and 5 to 17% by weight of alkyl acrylate, and within this range, more excellent impact resistance and weather resistance are achieved.

For example, the alkyl acrylate rubber may include seeds, and preferably may include rubber seeds.

For example, the seed contains 1 to 20 wt%, preferably 2 to 15 wt%, of at least one monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, and alkyl acrylates, based on 100 wt% of the (A) graft copolymer. It can be manufactured by polymerizing % by weight, more preferably 3 to 10% by weight, and within this range, excellent impact strength, weather resistance, physical property balance, etc. are achieved.

Preferably, the seeds include monomers containing an aromatic vinyl compound and an alkyl acrylate, 0.01 to 3 parts by weight of a crosslinker, 0.01 to 3 parts by weight of an initiator, and 0.01 parts by weight of an emulsifier based on 100 parts by weight of the units constituting the copolymer (A). It can be manufactured by polymerization containing from 5 parts by weight, and within the above range, a polymer of uniform size can be manufactured within a short time, and physical properties such as weather resistance and impact strength can be further improved.

More preferably, the seeds include monomers containing an aromatic vinyl compound and an alkyl acrylate, 0.1 to 1 part by weight of a crosslinking agent, 0.01 to 1 part by weight of an initiator, and an emulsifier based on 100 parts by weight of the units constituting the copolymer (A). It can be manufactured by polymerization containing 0.1 to 3.0 parts by weight, and within the above range, a polymer of uniform size can be manufactured within a short time, and physical properties such as weather resistance and impact strength can be further improved.

For example, the (A) graft copolymer containing the seed may include 1 to 20% by weight of the seed, 25 to 50% by weight of the rubber core, and 40 to 70% by weight of the shell, based on the total weight, and preferably It may contain 2 to 15% by weight of rubber seeds, 30 to 45% by weight of rubber core, and 45 to 65% by weight of shell, in which case it has an excellent balance of mechanical properties, weather resistance, fluidity, gloss, transparency, and non-whitening properties. It works.

The (A) copolymer containing the rubber seed is, for example, selected from the group consisting of A-1) aromatic vinyl compounds, vinyl cyan compounds, and alkyl acrylates, based on 100 parts by weight of the units constituting the (A) copolymer. Preparing seeds by polymerizing a mixture containing 1 to 20 parts by weight of one or more compounds, 0.001 to 1 part by weight of an electrolyte, 0.01 to 3 parts by weight of a crosslinker, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier; A-2) A mixture comprising 25 to 55 parts by weight of an alkyl acrylate compound and optionally an aromatic vinyl compound, 0.01 to 1 part by weight of a crosslinker, 0.01 to 3 parts by weight of an initiator and 0.01 to 5 parts by weight of an emulsifier in the presence of the seeds. manufacturing a rubber core by polymerizing; and A-3) in the presence of the rubber core, 40 to 70 parts by weight of at least one compound from the group consisting of an aromatic vinyl compound and a vinyl cyan compound, 0.01 to 3 parts by weight of a crosslinker, 0.01 to 3 parts by weight of an initiator, and 0.1 to 2 parts by weight of an emulsifier. It may be prepared including the step of producing a graft shell by mixing 0.01 to 1 part by weight of an activator. In this case, there is an excellent balance of mechanical properties such as impact strength, tensile strength, hardness, weather resistance, fluidity, and transparency.

In the present disclosure, the alkyl acrylate compound may be, for example, an alkyl acrylate in which the alkyl group has 1 to 15 carbon atoms, and is preferably methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, or 2-ethylbutyl acrylate. , octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate, and lauryl acrylate, and preferably an alkyl group having 1 to 4 carbon atoms. It may be an alkyl acrylate containing, and more preferably, it may be butyl acrylate, ethylhexyl acrylate, or a mixture thereof.

Examples of aromatic vinyl compounds in the present disclosure include styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobostyrene, ρ - It may be one or more selected from the group consisting of bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyl toluene, vinyl xylene, fluorostyrene, and vinyl naphthalene, Preferably, it may be at least one selected from the group consisting of styrene and α-methyl styrene, more preferably styrene. In this case, it has appropriate fluidity, excellent processability, and excellent mechanical properties such as impact strength and tensile strength. there is.

The vinyl cyan compound of the present disclosure may be, for example, one or more selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and may preferably be acrylonitrile.

The (A) graft copolymer can be manufactured by, for example, emulsion polymerization, and in this case, it has excellent gloss and hardness.

The emulsion polymerization is not particularly limited as long as it is carried out by an emulsion polymerization method commonly performed in the technical field to which the present invention pertains. For example, it may be an emulsion graft polymerization method.

In this description, a polymer comprising a certain compound (monomer) refers to a polymer polymerized by including that compound (monomer), and the units in the polymerized polymer are derived from the compound.

For example, the (A) graft copolymer has a grafting ratio calculated by Equation 3 below of 60% or more, preferably 60 to 150%, more preferably 62 to 140%, even more preferably 65 to 130%, More preferably, it may be 65 to 100%, particularly preferably 65 to 80%, and within this range, there are advantages of excellent mechanical properties such as impact strength and tensile strength, as well as excellent hardness and processability.

[Equation 3]

Grafting rate (%) = [Weight of grafted monomer (g) / Weight of rubber (g)] * 100

(In Equation 3, the weight (g) of the grafted monomer is the weight of the insoluble material (gel) minus the rubber weight (g) after dissolving the graft copolymer in acetone and centrifuging, and the rubber weight (g) g) is the weight (g) of the theoretically added rubber component in the graft copolymer powder.)

The weight of the insoluble material (gel) was determined by adding (A) 0.5 g of graft copolymer dry powder to 50 ml of acetone, stirring at room temperature for 12 hours, centrifuging it, collecting only the insoluble matter that did not dissolve in acetone, and stirring for 12 hours. This is the weight measured after drying, and the rubber weight (g) is the weight (g) of the theoretical rubber component added into 0.5 g of (A) graft copolymer dry powder.

As a specific measurement example, the weight of the insoluble material (gel) was measured by adding 0.5 g of graft copolymer dry powder to 50 ml of acetone and then shaking it at 210 rpm with a shaker (Orbital Shaker, equipment name: Lab companion SKC-6075) at room temperature. This was stirred for 12 hours and then centrifuged for 3 hours at 18,000 rpm at 0°C using a centrifuge (Supra R30 from Hanil Science Co., Ltd.) to collect only the insoluble matter that did not dissolve in acetone and place in an oven ((Forced Convection Oven; Equipment name: Lab) Companion OF-12GW) was dried at 85°C for 12 hours using a forced circulation drying method and then measured.

(B) (meth)acrylic acid alkyl ester polymer

The (B) (meth)acrylic acid alkyl ester polymer is, for example, 21 to 79% by weight, preferably 25 to 70% by weight, more preferably 35 to 60% by weight, even more preferably, based on the total weight of the base resin. It may be 45 to 55% by weight, and within this range, mechanical properties are excellent while transparency and low-light characteristics are excellent, which has the advantage of hiding the LED when the LED is off and making the LED light clearly visible when the LED is on. There is.

Examples of the (B) (meth)acrylic acid alkyl ester polymer include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, and (meth)acrylic acid decyl. It may include one or more types selected from the group consisting of esters and (meth)acrylic acid lauryl esters, preferably alkyl methacrylate esters, alkyl acrylic acid esters, or a mixture thereof, more preferably It may be a polymethyl methacrylate resin, and more preferably, it may be a polymethyl methacrylate resin. In this case, it has the advantage of excellent mechanical properties, transparency, and low-light characteristics.

Unless otherwise specified in this description, “(meth)acrylic acid alkyl ester” means that both “acrylic acid alkyl ester” and “methacrylic acid alkyl ester” are possible.

The polymethyl methacrylate resin may include, for example, methyl methacrylate and methyl acrylate, and preferably contains 1 to 10% by weight of methyl acrylate, preferably 2 to 7% by weight. There is an advantage that low light characteristics, transparency, fluidity, and mechanical properties are improved within this range.

For example, the polymer (B) may have a weight average molecular weight of 50,000 to 150,000 g/mol, preferably 50,000 to 130,000 g/mol, more preferably 60,000 to 110,000 g/mol, and even more preferably It may be 70,000 to 90,000 g/mol, and has the advantage of excellent fluidity, transparency, and low-light characteristics while maintaining mechanical properties within this range.

For example, the (B) (meth)acrylic acid alkyl ester polymer may have a glass transition temperature of 80 to 130°C, preferably 90 to 120°C, and has the advantage of excellent heat resistance within this range.

In this material, the glass transition temperature can be measured using Differential Scanning Calorimetry (DSC) according to ASTM D3418, and as a specific example, TA Instrument's Q100 DSC (Differential Scanning Calorimetry) can be used to measure the temperature at 10°C/min. It can be measured by the temperature increase rate.

The (B) (meth)acrylic acid alkyl ester polymer may be prepared, for example, by suspension polymerization, and the suspension polymerization is not particularly limited as long as it is a suspension polymerization commonly performed in the technical field to which the present invention pertains.

(C) Crystalline polymer with a melting temperature (Tm) of 250 ℃ or higher

The (C) crystalline polymer preferably has a melting temperature (Tm) of 255°C or higher, more preferably 260°C or higher, and even more preferably 260 to 300°C, and the mechanical properties are maintained within this range. It has excellent transparency, low-light characteristics, and processability, and has the advantage of hiding the LED when the LED is off and making the LED light clearly visible when the LED is on.

In the present disclosure, the melting temperature (Tm) can be measured by a measurement method commonly used in the technical field to which the present invention pertains, specifically a Differential Scanning Calorimeter (DSC), device name: DSC 2500, manufacturer. : It can be measured using a TA instrument. Here, using DSC, the temperature is maintained at 330°C for 5 minutes, then the temperature is lowered to 0°C at a rate of 10°C/min, then the temperature is raised to 10°C/min, and the endothermic peak at the time of melting is referred to.

The (C) crystalline polymer is, for example, 3 to 12 parts by weight, preferably 4 to 11 parts by weight, more preferably 5 to 10 parts by weight, even more preferably 5 to 7 parts by weight, based on 100 parts by weight of the base resin. It can be parts by weight, and the mechanical properties are maintained within this range, while having excellent transparency, low-light characteristics and processability, and having the advantage of hiding the LED when the LED is off and making the LED light clearly visible when the LED is on. there is.

The (C) crystalline polymer is, for example, polyhexamethylene adipamide (PA 66), polytetramethylene adipamide (PA 46), polyhexamethylene sebasamide (PA 610), and polydodecanolactam (PA 12). ), polyamide 6/6T, polyamide 6/66, and syndiotactic polystyrene resin. Preferably, it may be polyamide 66, syndiotactic polystyrene resin, or a mixture thereof. , More preferably, it may be polyamide 66, and in this case, the mechanical properties are maintained while maintaining excellent transparency, low-light characteristics, and processability, and when the LED is off, it has LED hiding properties and when the LED is on, it emits LED light. It has the advantage of making it visible clearly.

The syndiotactic polystyrene resin has a syndiotactic structure, that is, a three-dimensional structure in which side phenyl groups or substituted phenyl groups are alternately located in opposite directions to the main chain formed by carbon-carbon bonds.

For example, the syndiotactic polystyrene-based resin may be syndiotactic polystyrene, a derivative of syndiotactic polystyrene, or a mixture thereof.

The syndiotactic polystyrene includes, for example, diand polystyrene with a stereoregularity of 85% or more, pentad (racemipentad) polystyrene with a stereoregularity of 35% or more, polyhalogenated styrene, polyalkoxystyrene, polyalkyl styrene, poly It may be one or more types selected from the group consisting of ester-styrene and copolymers containing these as main components, and in this case, the mechanical properties are maintained while maintaining excellent transparency, low-light characteristics, and processability, and when the LED is off, the LED has hiding properties and When the LED is turned on, there is an advantage in that the LED light is clearly visible.

In this description, the degree of stereoregularity is not particularly limited as long as it is used by a measurement method commonly used in the technical field to which the present invention pertains, and as a specific example, it can be measured by ¹³ C-NMR method.

Derivatives of the syndiotactic polystyrene include, for example, syndiotactic polyhalogenated styrene, syndiotactic polyalkoxy styrene, syndiotactic polyalkyl styrene, syndiotactic polybenzoate styrene, syndiotactic polystyrene maleic anhydride (sPS-MAH) , carboxyl terminated-syndiotactic polystyrene (sPSCOOH), maleic anhydride-syndiotactic polystyrene (sPS-MAH), maleic acid-syndiotactic polystyrene (sPS-MA), fumaric acid-syndiotactic polystyrene (sPS-FA) ), glycidyl methacrylate-syndiotactic polystyrene (sPS-GMA), and copolymers containing these as main components. In this case, transparency and low-light characteristics are maintained while mechanical properties are maintained. It has excellent LED hiding characteristics and excellent processability.

The syndiotactic polystyrene-based resin may be, for example, syndiotactic polystyrene having a stereoregularity of 90% or more, preferably 97% or more, more preferably 99% or more, as measured by ¹³ C-NMR method, Within this range, excellent low-light characteristics and hardness can be provided.

In addition, the syndiotactic polystyrene-based resin preferably has a melting temperature of 250 to 300°C, more preferably 260 to 280°C, and within this range, mechanical properties are maintained while transparency, low-light characteristics and processability are maintained. It is excellent and has the advantage of hiding the LED when the LED is off and making the LED light clearly visible when the LED is on.

Thermoplastic resin composition

The thermoplastic resin composition preferably has an alkyl acrylate coverage value (X) calculated by Equation 1 below of 65% by weight or more, preferably 67 to 150% by weight, more preferably 70 to 140% by weight, , Within this range, it has excellent mechanical properties such as impact strength, tensile strength, and hardness, processability, and weather resistance, and has excellent transparency and low-light characteristics, hiding the LED when the LED is off and emitting LED light when the LED is on. It has the advantage of making it visible clearly.

[Equation 1]

X = {(G-Y)/Y}

(In Equation 1 above, G represents the gel content (% by weight) relative to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel relative to the total weight of the thermoplastic resin composition.)

In Equation 1, the content of alkyl acrylate in the gel of the thermoplastic resin composition represents the content of alkyl acrylate in the insoluble matter collected in the process of calculating the gel content described above (based on 100% by weight of the total thermoplastic resin added). Here, the gel content represents the content of insoluble matter based on 100% by weight of the total thermoplastic resin.

The content of the alkyl acrylate is measured using an NMR analyzer or FT-IR.

In this description, NMR analysis means analysis by ¹ H NMR, unless otherwise specified.

In this description, NMR analysis can be measured using methods commonly performed in the art, and specific measurement examples are as follows.

- Equipment name: Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy Probe

- Measurement conditions: 1H NMR (zg30): ns=32, d1=5s, TCE-d2, at room temp.

In this description, FT-IR analysis can be measured using methods commonly performed in the technical field, and specific measurement examples are as follows.

- Equipment name: Agilent Cary 660

- Measurement conditions: ATR mode

The gel content was determined by adding 1 g of the thermoplastic resin composition to 30 ml of acetone, stirring at room temperature for 12 hours, centrifuging it, collecting only the insoluble matter that did not dissolve in acetone, drying it for 12 hours, and measuring the weight, using Equation 2 below: Calculated as As a specific measurement example, the gel content was measured by adding 1 g of the thermoplastic resin composition to 30 ml of acetone, stirring at 210 rpm for 12 hours at room temperature with a shaker (Orbital Shaker, equipment name: Lab companion SKC-6075), and centrifuging the mixture. Using (Hanil Science Co., Ltd.'s Supra R30), centrifuge at 18,000 rpm for 3 hours at 0℃ to collect only the insoluble matter that has not dissolved in acetone, and then place in an oven (Forced Convection Oven; equipment name: Lab companion OF-12GW) at 85℃. The weight can be measured after drying using forced circulation drying method for 12 hours.

[Equation 2]

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

In the present disclosure, the alkyl acrylate coverage value is a parameter that measures the degree of dispersion of the aromatic vinyl compound-vinylcyan compound polymer grafted onto the alkyl acrylate rubber in the thermoplastic resin composition. The higher this value is, the more the aromatic vinyl compound-vinyl cyan compound polymer is evenly grafted onto the alkyl acrylate rubber, forming a form that evenly surrounds the rubber, resulting in high glossiness and excellent tensile strength, colorability, and transparency. In addition, the higher the alkyl acrylate coverage value, the narrower the distance between rubber particles, which reduces voids due to cracks occurring inside the thermoplastic resin composition, thereby reducing the whitening phenomenon, resulting in better transparency.

The difference between the alkyl acrylate coverage value and the grafting rate is that the alkyl acrylate coverage value measures the degree of dispersion of the aromatic vinyl compound-vinylcyan compound polymer grafted to the alkyl acrylate in the thermoplastic resin composition, and the grafting rate is a measure of the degree of dispersion of the aromatic vinyl compound-vinylcyan compound polymer grafted to the alkyl acrylate in the thermoplastic resin composition. In the rate-aromatic vinyl compound-vinyl cyan compound graft copolymer, the degree of grafting of the aromatic vinyl compound-vinyl cyan compound polymer to the alkyl acrylate was calculated.

In addition, the alkyl acrylate coverage value is quantitatively calculated from the alkyl acrylate content actually present in the thermoplastic resin composition using an NMR analyzer or FT-IR, and the graft rate is calculated from the content of the rubber component added during polymerization. .

For example, the thermoplastic resin composition has a flow index (220°C, 10 kg) measured according to ASTM D1238 of 7.5 g/10min or more, more preferably 10 g/10min or more, even more preferably 12 g/10min or more, More preferably, it may be 15 g/10min or more, and particularly preferably 15 to 34 g/10min. Within this range, excellent balance of physical properties and excellent film processability are achieved.

In this description, the flow index can be measured according to ASTM D1238 by setting the weight of 10 kg at 220 ℃ and the standard time of 10 minutes. More specifically, the specimen was heated to a temperature of 220°C using GOETTFERT's melting index measuring equipment, placed in the cylinder of a melt indexer, and melted for 10 minutes by applying a load of 10 kg with a piston. It can be obtained by measuring the weight (g) of the resin produced.

For example, the thermoplastic resin composition has an Izod impact strength (1/4" specimen thickness, room temperature) measured according to ASTM D256 of 2.3 kgf·cm/cm or more, more preferably 2.8 kgf·cm/cm or more, even more preferably Preferably, it may be 3.5 kgf·cm/cm or more, more preferably 3.5 to 7 kgf·cm/cm, and within this range, excellent balance of physical properties is achieved while providing excellent mechanical properties and film processability.

In the present disclosure, room temperature may be a point within the range of 20 ± 5°C.

For example, the thermoplastic resin composition has a tensile strength of 280 kgf/cm ² or more, preferably 400 kgf/cm ² or more, more preferably measured at a crosshead speed of 50 mm/min and a specimen thickness of 3.2 mm according to ASTM D638. May be 400 to 600 kgf/cm ² , and within this range, excellent balance of physical properties is achieved while providing excellent mechanical properties and film processability.

For example, the thermoplastic resin composition has a hardness (R-scale) of 70 or more, preferably 75 or more, more preferably 80 or more, even more preferably 85 or more, as measured by an injection specimen according to ASTM D785. It may be 85 to 95, and within this range, there is an excellent balance of physical properties and excellent mechanical properties and scratch resistance.

The thermoplastic resin composition preferably has a gloss of 50 or less, preferably 40 or less, as measured at 60° as a film with a thickness of 0.15 T using a gloss meter according to ASTM D2457. It may be 30 or less, more preferably 20 or less, even more preferably 15 or less, and especially preferably 1 to 15. Within this range, the physical property balance is excellent and transparency and low-light effect are excellent, so that when the LED is turned off, the has the advantage of hiding the LED and making the LED light clearly visible when the LED is turned on.

The lower the gloss, the more low-gloss characteristics are expressed, and the higher the gloss, the more glossy characteristics are expressed.

For example, the thermoplastic resin composition may have a total light transmittance of 75% or more, preferably 80% or more, more preferably 80 to 100%, as measured with a film with a thickness of 0.15 T according to ASTM D1003, and within this range. It has an excellent balance of physical properties while exhibiting both low-light characteristics and transparency, which has the advantage of hiding the LED when the LED is off and making the LED light clearly visible when the LED is on.

The higher the total light transmittance, the more transparent and excellent the coloring properties are.

The thermoplastic resin composition is, for example, manufactured into a sheet with a thickness of 0.15 mm using a T-die extruder, cut into a length of 100 cm, and then cut into 10 places excluding 2 to 3 cm from both ends. The thickness deviation calculated as the difference between the maximum thickness and the minimum thickness measured above may be 0.07 mm or less, preferably 0.05 mm or less, more preferably 0.03 mm or less, and even more preferably 0.001 to 0.03 mm, and is within this range. It has excellent physical property balance and excellent film processability.

In this substrate, the thickness can be measured with Mitutoyo's ABSOLUTE ID-C1012BS.

For example, the thermoplastic resin composition may include one or more selected from the group consisting of lubricants, antioxidants, ultraviolet stabilizers, and pigments.

The lubricant may preferably be one or more selected from the group consisting of aliphatic amide-based lubricants, fatty acid ester-based lubricants, and olefin-based waxes.

The aliphatic amide-based lubricant preferably consists of stearamide, oleamide, erucamide, ethylene bis stearamide, and ethylene bis oleamide. It may be one or more types selected from the group.

The fatty acid ester-based lubricant is preferably one selected from the group consisting of alcohol or fatty acid ester of polyhydric alcohol, hydrogenated oil, butyl stearate, monoglyceride stearate, pentaerythritol tetrastearate, stearyl stearate, ester wax, and alkyl phosphate ester. There may be more than one species.

The olefin wax may preferably be polyethylene wax.

For example, the lubricant may be included in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the base resin, and within this range, an excellent balance of physical properties is achieved. there is.

The antioxidant may preferably include a primary antioxidant and a secondary antioxidant.

The primary antioxidant may be, for example, a phenol-based antioxidant, and is preferably 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate. , 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 1,6-hexanediolbis-[3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis-[3-(3,5-di-t-butyl-4-hydroxyphenyl) ) propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocylate Anurate, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl] Isocyanurate, tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate, 2,2'-methylenebis(4-methyl-6-t-butylphenol)tere Phthalate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2- {β-(3-t-butyl-4-hydroxy-5-methyl-phenyl)pripionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 2, 2-bis[4-(2-3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)ethoxyphenyl]propane, and β-(3,5-di-t-butyl-4- It may be one or more selected from the group consisting of hydroxyphenyl)propionic acid stearyl ester, and more preferably octadecyl 3-(3,5-ditertiary-butyl-4-hydroxyphenyl)propanoate (octadecyl 3-). (3,5-ditert-butyl-4-hydroxyphenyl)propanoate; IR1076).

The secondary antioxidant may be, for example, a phosphorus-based antioxidant, and is preferably bis(dialkylphenyl)pentaerythritol diphosphite ester, phosphite ester, trioctyl phosphite, trilauryl phosphite, and tridecyl phosphite. , (octyl)diphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearyl Pentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxy-phenyl)butane diphosphite, tetra(C12-C15 mixed alkyl)- 4,4'-Isopropylidenediphenyl diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-t-bunylphenol)diphosphite, tris(mono- and di- Mixed nonylphenyl)phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, phenyl(4,4'-isopropylidenediphenol)pentaerythritol diphosphite, distearylpentaerythritol depot Spite, tris[4,4'-isopropylidenebis(2-t-butylphenol)] phosphite, di(isodecyl)phenyl phosphite, 4,4'-isopropylidenebis(2-t-butylphenol) ) Bis(nonylphenyl) phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, 2-[{2,4,8,10-tetra-t-butyldibenz[d ,f][1.3.2]-dioxa-phosphepin-6-yl}oxy]-N,N-bis[2-[{2,4,8,10-tetra-t-butyl-dibenz[d ,f][1.3.2]-dioxaphosphepin-6-yl}oxy]ethyl]-ethanamine, and 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy ]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepine, and more preferably tris (2 , 4-di-tert-butylphenyl) phosphite (Tris(2,4-di-tert-butylphenyl) phosphite; IF168).

For example, the antioxidant may be included in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the base resin. Within this range, it may be contained in an amount of 0.01 to 5 parts by weight, based on 100 parts by weight of the base resin. It prevents oxidation and has excellent mechanical properties.

For example, the UV stabilizer may be one or more selected from the group consisting of HALS series UV stabilizers and benzotriazole series UV stabilizers, and preferably may be a mixture of HALS series UV stabilizers and benzotriazole series UV stabilizers.

The HALS series UV stabilizer is preferably bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate. ; UV 770), bis[N-methyl-2,2,6,6-tetramethyl-4-piperidinyl]sebacate (bis-[N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) ] sebacate) and succinic acid dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine (succinic acid dimethyl-1-(2-hydroxyethyl)-4-hydroxy -2,2,6,6-tetramethylpiperidine; Tinuvin 622), and more preferably bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate. (bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; UV 770).

The benzotriazole-based UV stabilizer is preferably 2-(2'-Hydroxy-5'-t-octylphenyl)-benzotriazole (2-(2'-Hydroxy-5'-t-octylphenyl)-benzotriazole; Cyasorb UV-541), 2-(2'-Hydroxy-5'-methylphenyl)benzotriazole; TinUVin-P), 2-(2'- Hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chloro-benzotriazole (2-(2'-Hydroxy-3'-tert.butyl-5'-methylphenyl)-5-chloro- benzotriazole; Tinuvuvin-326), 2-(2'-hydroxy-3',5'-ditertiary-butylphenyl)-5-chloro-benzotriazole (2-(2'-Hydroxy-3',5'-ditert.butylphenyl)-5-chloro-benzotriazole; Tinuvin-327), 2-(2'-hydroxy-3,5-ditert-amylphenyl)benzotriazole (2-(2'-Hydroxy-3, 5-di-tert.amylphenyl) benzotriazole; Tinuvin-328), 2-(2'-hydroxy-3',5'-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole (2- (2'-hydroxy-3',5'-di(1,1-imethylbenzyl)phenyl]-2H-benzotriazole; Tinuvin-234), 2-(2'-hydroxy-3',5'-di-t -Butylphenyl)benzotriazole (2-(2'hydroxy-3',5'-di-t-butylphenyl)benzotriazole; Tinuvin-320), and 2-(2H-benzotriazol-2-yl)-4 -(1,1,3,3-tetramethylbutyl)phenol (2-(2H-benzotrizol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol; UV329) There may be one or more types, more preferably 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (2-(2H-benzotrizol-2- yl)-4-(1,1,3,3-tetramethylbutyl)phenol; UV 329) .

For example, the UV stabilizer may be included in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the base resin. Within this range, the mechanical properties and weather resistance are maintained. It has excellent effects.

It is preferable to use the pigment that has excellent heat resistance, weather resistance, and chemical resistance, does not contain heavy metal compounds, and does not seep into various solvents. Examples of the pigment include black pigment, white pigment, yellow pigment, red pigment, and blue pigment.

The black pigment may include, for example, carbon black. The carbon black of the present invention is not limited as long as it is carbon black that can be commonly used in the relevant technical field. The carbon black may preferably be one or more types selected from the group consisting of ketjen black, acetylene black, furnace black, and channel black.

For example, the pigment may be included in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the base resin, and within this range, the mechanical properties and glossiness are maintained. It has the effect of having an excellent and beautiful appearance.

The thermoplastic resin composition optionally contains at least one selected from the group consisting of dyes, colorants, antistatic agents, antibacterial agents, processing aids, metal deactivators, flame retardants, suppressants, anti-dripping agents, anti-friction agents, and anti-wear agents as necessary. It may be further included in an amount of 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 part by weight based on 100 parts by weight of the resin, and within this range, the original physical properties of the thermoplastic resin composition of the present base are maintained. It has the effect of realizing the necessary physical properties well without deteriorating it.

Method for producing thermoplastic resin composition

The method for producing the thermoplastic resin composition of the present invention is (A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and ( B) 100 parts by weight of a base resin containing 21 to 79% by weight of (meth)acrylic acid alkyl ester polymer; and (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250°C or higher; kneading and extruding under conditions of 200 to 300°C and 100 to 500 rpm, calculated using the following formula (1): It is characterized in that the alkyl acrylate coverage (X) value is 65% by weight or more. In this case, it has excellent mechanical properties such as impact strength, tensile strength, and hardness, as well as processability and weather resistance, and has excellent transparency and low-light characteristics, so it has excellent LED hiding properties and has the effect of clearly showing the LED light.

[Equation 1]

X = {(G-Y)/Y}

(In Equation 1 above, G represents the gel content (% by weight) relative to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel relative to the total weight of the thermoplastic resin composition.)

The method for producing the thermoplastic resin composition shares all technical features of the thermoplastic resin composition described above. Therefore, description of the overlapping parts will be omitted.

The kneading and extrusion can preferably be carried out using an extrusion kneader at 200 to 300°C, more preferably 210 to 260°C, and even more preferably 220 to 250°C, and stable extrusion is possible within this range. The mixing effect is excellent. At this time, the temperature is the temperature set in the cylinder.

For example, the kneading and extrusion may be performed under conditions where the screw rotation speed is 100 to 500 rpm, preferably 150 to 450 rpm, and more preferably 200 to 400 rpm. In this case, the throughput per unit time is appropriate, so that the process efficiency is high. It has excellent effects.

The thermoplastic resin composition obtained through the extrusion can be manufactured into pellets using an Illero pelletizer.

The extrusion kneader is not particularly limited as long as it is an extrusion kneader commonly used in the technical field to which the present invention pertains, and may preferably be a twin-screw extrusion kneader.

molded product

The molded article of this base is characterized in that it contains the thermoplastic resin composition, and in this case, it has excellent mechanical properties such as impact strength, tensile strength, and hardness, transparency, low-light characteristics, processability, and weather resistance, and when the LED is off, the LED It has the advantage of hiding characteristics and making the LED light clearly visible when the LED is turned on.

The molded article may preferably be a film or a sheet, and in this case, it has excellent mechanical properties and scratch resistance, as well as transparency and low-light characteristics, providing LED hiding properties when the LED is off and LED light when the LED is on. It has the advantage of making it clearly visible.

For example, the molded product is applied to a hidden display and has the advantage of hiding the LED when the LED is off and making the LED light clearly visible when the LED is on.

The method for manufacturing the molded article preferably includes (A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinylcyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and (B) 100 parts by weight of a base resin containing 21 to 79% by weight of (meth)acrylic acid alkyl ester polymer; and (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250°C or higher; kneading and extruding under conditions of 200 to 300°C and 100 to 500 rpm to produce an extrudate; and manufacturing the molded product by molding the extrudate, wherein the alkyl acrylate coverage (X) value of the extrudate calculated by the following formula (1) is 65% by weight or more. In this case, it has excellent mechanical properties such as impact strength, tensile strength, and hardness, as well as processability and weather resistance, as well as excellent transparency and low-light characteristics, hiding the LED when the LED is off and clearly emitting the LED light when the LED is on. There is an advantage in making it visible.

[Equation 1]

X = {(G-Y)/Y}

(In Equation 1 above, G represents the gel content (% by weight) relative to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel relative to the total weight of the thermoplastic resin composition.)

The extrudate may be in the form of a pellet or plate, for example.

In this description, the plate shape is not particularly limited as long as it is generally defined as a plate shape in the technical field to which the present invention pertains, and may include, for example, a flat shape, a sheet shape, a film shape, etc.

In describing the thermoplastic resin composition, its manufacturing method, and molded article of the present disclosure, it is stated that other conditions and equipment not explicitly described can be appropriately selected within the range commonly practiced in the industry and are not particularly limited. do.

Below, preferred examples are presented to aid understanding of the present description. However, the following examples are merely illustrative of the present description, and it is clear to those skilled in the art that various changes and modifications are possible within the scope and technical spirit of the present description. It is natural that such variations and modifications fall within the scope of the attached patent claims.

[Example]

The materials used in the following examples and comparative examples are as follows.

* (A-1) Graft copolymer: ASA graft copolymer with an average particle diameter of 90 to 110 nm of alkyl acrylate rubber manufactured by emulsion polymerization (core: butylacrylate 38 % by weight and styrene 7 Weight percent, shell: 4 wt% butylacrylate, 40 wt% styrene and 11 wt% acrylonitrile. Weight %, grafting rate 70 %)

* (A-2) Graft copolymer: ASA graft copolymer with an average particle diameter of 90 to 110 nm of alkyl acrylate rubber manufactured by emulsion polymerization (core: butylacrylate 34 % by weight, styrene 11 Weight %, shell: butylacrylate 4 weight %, styrene 40 % by weight and acrylonitrile 11 % by weight, grafting rate 75 %)

* (A-3) Graft copolymer: ASA graft copolymer with an average particle diameter of 100-130 nm of alkyl acrylate rubber manufactured by emulsion polymerization (core: butylacrylate 48 Weight %, styrene 2 weight %, shell: butylacrylate 2 Weight %, styrene 37 % by weight and acrylonitrile 11 % by weight, grafting rate 45 %)

* (A-4) Graft copolymer: ASA graft copolymer with an average particle size of 90-110 nm of alkyl acrylate rubber manufactured by emulsion polymerization (core: 45% by weight of butylacrylate, 5% by weight of styrene, shell) : Butylacrylate 15% by weight, styrene 25% by weight, and acrylonitrile 10% by weight, grafting rate 60%)

* (A-5) Graft copolymer: ASA graft copolymer with an average particle diameter of 280-330 nm of alkyl acrylate rubber manufactured by emulsion polymerization (core: 43% by weight of butylacrylate, 17% by weight of styrene, shell) : Butylacrylate 4% by weight, styrene 26% by weight and acrylonitrile 10% by weight, grafting rate 40%)

* (B-1) PMMA resin: polymethyl methacrylate resin (IF850 from LG MMA, weight average molecular weight 70,000~90,000 g/mol)

* (B-2) SAN resin: styrene-acrylonitrile copolymer containing 73% by weight of styrene and 27% by weight of acrylonitrile (90HR, LG Chemical, weight average molecular weight 120,000 ~ 180,000 g/mol)

* (C-1) PA66: Polyamide 66 with a melting temperature (Tm) of 260°C

* (C-2) Syndiotactic PS: Syndiotactic polystyrene resin with a melting temperature (Tm) of 265 ℃ (stereoregularity measured by ¹³ C-NMR method of 99% or more)

* (D) Additives:

- Lubricant: tallow stearic acid (ELOFAD TH100 from LG Household & Health Care) 0.5 parts by weight

- Antioxidant: Irganox 1076 (BASF) 0.5 parts by weight, Irgafos 168 (BASF) 0.5 parts by weight

- UV stabilizer: Tinuvin 770 (BASF) 1 part by weight, Sunsorb329 (Sun Fine Global) 1 part by weight

Examples 1 to 7 and Comparative Examples 1 to 8

The ingredients and contents shown in Tables 1 and 2 below were added to a twin-screw extruder along with a total of 3.5 parts by weight of additives, and melt-kneaded and extruded at 230°C and 150 rpm to prepare pellets. Flow index and alkyl acrylate coverage values were measured using the prepared pellets. Afterwards, specimens for measuring appearance and physical properties were produced by injection using an injection molding machine (VC 330/80 TECJ PRO from ENGEL) at 220°C and a screw speed of 100 to 200 rpm. In addition, the manufactured pellets were molded using a T-die extruder (Collins' Techline 20T, screw 20 mm, L/D=25) at a molding temperature of 230 ℃, a molding pressure of 200 kgf/cm ² , a roll temperature of 85 ℃, and roll rotation. A film with a thickness of 0.15 mm was produced at a speed of 3.5 m/min, and glossiness, total light transmittance, and film thickness deviation were measured.

[Test example]

The properties of the pellets or specimens prepared in Examples 1 to 7 and Comparative Examples 1 to 8 were measured by the following method, and the results are shown in Tables 1 to 2 below.

measurement method

* Alkyl acrylate coverage value (X value, weight %): Calculated using Equation 1 below.

[Equation 1]

X = {(G-Y)/Y}

(In Equation 1 above, G represents the gel content (% by weight) relative to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel relative to the total weight of the thermoplastic resin composition.)

Here, the content of alkyl acrylate in the gel was quantitatively measured using a ¹ NMR analyzer or FT-IR. Specific measurement conditions are as follows.

^One H NMR

- Equipment name: Bruker 600MHz NMR (AVANCE III HD) CPP BB (1H 19F tunable and broadband, with z-gradient) Prodigy Probe

- Measurement conditions: ₁ H NMR (zg30): ns=32, d1=5s, TCE-d2, at room temp.

FT-IR

- Equipment name: Agilent Cary 66

- Measurement conditions: ATR mode

* Gel content (%): 1 g of pellet extruded from the thermoplastic resin composition was added to 30 ml of acetone, then stirred at 210 rpm for 12 hours at room temperature with a shaker (Orbital Shaker, equipment name: Lab companion SKC-6075) and stirred for 12 hours at room temperature. Using a centrifuge (Supra R30 from Hanil Science Co., Ltd.), centrifuge at 18,000 rpm at 0℃ for 3 hours to collect only the insoluble matter that has not dissolved in acetone, and then place it in an oven (Forced Convection Oven; Equipment name: Lab companion OF-12GW). After being dried using a forced circulation drying method at 85°C for 12 hours, the weight was measured and calculated using Equation 2 below.

[Equation 2]

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

* Graft rate (%): 0.5 g of graft copolymer dry powder was added to 50 ml of acetone, stirred at room temperature for 12 hours, centrifuged, and only the insoluble matter that did not dissolve in acetone was collected, dried for 12 hours, and then weighed. So, it was calculated using Equation 3 below.

[Equation 3]

Grafting rate (%) = [Weight of grafted monomer (g) / Rubber weight (g)]

(In Equation 3, the weight (g) of the grafted monomer is the weight of the insoluble material (gel) minus the rubber weight (g) after dissolving the graft copolymer in acetone and centrifuging, and the rubber weight (g) g) is the weight (g) of the theoretically added rubber component in the graft copolymer powder.)

Specifically, the weight of the insoluble material (gel) was calculated by adding 0.5 g of graft copolymer dry powder to 50 ml of acetone and stirring for 12 hours at 210 rpm with a stirrer (Orbital Shaker, equipment name: Lab companion SKC-6075) at room temperature. This was centrifuged at 18,000 rpm at 0°C for 3 hours using a centrifuge (Supra R30 from Hanil Science Co., Ltd.) to collect only the insoluble matter that did not dissolve in acetone, and then placed in an oven (Forced Convection Oven; Equipment name: Lab companion OF-12GW). ) was dried using a forced circulation drying method at 85°C for 12 hours, and then the weight was measured.

* Flow index (g/10min): Measured at 220°C and 10 kg load for 10 minutes according to ASTM D1238.

* Izod impact strength (kgf·cm/cm): Measured according to ASTM D256 using injection specimens (1/4" thick) at room temperature.

* Tensile strength (kgf/cm ² ): Tensile strength was measured with an injection specimen (thickness 3.2 mm) under a crosshead speed of 50 mm/min according to ASTM D638.

* Hardness (R-scale): Measured using injection specimens according to ASTM D785.

* Film gloss: Measured at 60° with a film with a thickness of 0.15 T using a gloss meter VG7000 according to ASTM D2457.

* Film total light transmittance (Tt, %): Measured with a film with a thickness of 0.15 T according to ASTM D1003.

* Film thickness deviation (mm): Using a T-die extruder (Collins' Techline 20T, screw diameter 20 mm, L/D=25), molding temperature 230 ℃, screw speed 100 rpm, roll temperature 85 ℃, roll rotation After manufacturing a film with a thickness of 0.15 T under a speed of 3.5 m/min, the manufactured sheet was cut to a length of 100 cm, and then the thickness of the part excluding 2 to 3 cm from both ends was measured in at least 5 places to determine the maximum and minimum thickness. The thickness deviation was calculated from the difference in thickness and evaluated based on the following criteria.

The thickness was measured using Mitutoyo's ABSOLUTE ID-C1012BS.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 (A-1) ASA (% by weight) 30 50 50 50 70 50 (A-2) ASA (% by weight) 50 (A-3) ASA (% by weight) (B-1) PMMA (% by weight) 70 50 50 50 30 50 50 (B-2) SAN (% by weight) (C-1) PA66 (part by weight) 5 5 10 5 7 5 (C-2) Syndiotactic PS
(part by weight) 5 (A) ASA's
Graft rate (%) 70 70 70 70 70 70 75 thermoplastic resin
X value of the composition (% by weight) 90 90 90 90 90 90 120 Properties Flow index (g/10min) 29.1 16.4 15.8 13.0 7.6 16.1 16.8 Injection specimen impact strength
(kgf·cm/cm) 2.5 3.1 2.9 3.0 6.4 3 2.6 tensile strength
(kgf/ ^cm2 ) 556 425 429 431 303 427 430 Hardness 112 97 98 98 72 95 99 film Glossiness 25 20 22 6 12 16 22 Total light transmittance (%) 75 80 77 76 89 78 82 Thickness deviation (mm) 0.02 0.03 0.03 0.04 0.07 0.03 0.03

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 (A-1) ASA (% by weight) 10 90 50 50 50 (A-2) ASA (% by weight) (A-3) ASA (% by weight) 50 (A-4) ASA (% by weight) 50 (A-5) ASA (% by weight) 50 (B-1) PMMA (% by weight) 90 10 50 50 50 50 50 (B-2) SAN (% by weight) 50 (C-1) PA66 (part by weight) 5 5 One 15 5 5 5 5 (C-2) Syndiotactic PS (part by weight) (A) Grafting rate (%) of ASA 70 70 70 70 45 70 60 40 thermoplastic resin
X value of the composition (% by weight) 90 90 90 90 49 90 48 84 Properties Flow index (g/10min) 42.3 3.4 16.6 11.4 12.0 10.2 15.7 12.8 Injection specimen impact strength
(kgf·cm/cm) 1.9 7.8 3.4 3.2 4.6 3.5 2.5 24 tensile strength
(kgf/ ^cm2 ) 641 264 429 436 383 409 362 366 Hardness 134 55 98 99 90 88 87 80 film Glossiness 30 10 75 4 10 24 22 12 Total light transmittance (%) 73 89 90 66 69 58 68 43 Thickness deviation (mm) 0.09 0.1 0.03 0.09 0.03 0.03 0.05 0.08

As shown in Tables 1 to 2, Examples 1 to 7 prepared according to the present invention are superior in impact strength, tensile strength, hardness and flow index compared to Comparative Examples 1 to 8, which are outside the scope of the present invention, and have excellent film properties. The T-die processability is excellent due to the small thickness deviation, the glossiness of the film is low, and the total light transmittance of the film is high, so you can see the effect of hiding the LED when the LED is off and clearly showing the LED light when the LED is on. I was able to.

Specifically, Comparative Example 1, which included the base resin (A-1) graft copolymer below the range of the present invention, had an excessively high flow index, low impact strength, and very large film thickness deviation, and on the contrary, (A- 1) Comparative Example 2, in which the graft copolymer exceeded the scope of the present invention, had low flow index, tensile strength, and hardness, and very large variation in film thickness, resulting in poor T-die processability.

In addition, (C) Comparative Example 3, which included a crystalline polymer with a melting temperature (Tm) of 250°C or higher below the range of the present invention, had a high film gloss and did not exhibit low-light characteristics.

In addition, (C) Comparative Example 4 in which the crystalline polymer with a melting temperature (Tm) of 250°C or higher exceeds the range of the present invention, Comparative Example 5 in which the alkyl acrylate coverage value of the thermoplastic resin composition is below the range of the present invention, and ( Comparative Example 6, in which B-1) PMMA resin was changed to (B-2) SAN resin, had a low total light transmittance of the film, and in this case, a problem occurred in which the LED light was not clearly visible when applied to a hidden display. In particular, in Comparative Example 4, the film thickness variation was large and T-die processability was poor.

In addition, Comparative Example 7, in which the graft ratio of the (A-4) ASA graft copolymer was high but the alkyl acrylate coverage value of the thermoplastic resin composition was low, had a low total light transmittance of the film, and included in the (A-5) ASA graft copolymer In Comparative Example 8, in which the average particle diameter of the rubber exceeded 120 nm, light scattering was severe, the total light transmittance of the film was low, and the thickness deviation of the film was large, resulting in poor T-die processability.

In conclusion, according to the present invention, a base resin containing an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and a (meth)acrylic acid alkyl ester polymer containing rubber having a predetermined average particle size in a predetermined content ratio is used. A thermoplastic resin composition containing a predetermined amount of a crystalline polymer with a melting temperature (Tm) of 250°C or higher, and adjusting the alkyl acrylate coverage value in the thermoplastic resin composition to within a predetermined range, has mechanical properties such as impact strength, tensile strength, and hardness. It was confirmed that the material had excellent physical properties, processability, and weather resistance, as well as excellent transparency and low-light characteristics.

Claims (13)

(A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and (B) 21 to 79% by weight of (meth)acrylic acid alkyl ester polymer. 100 parts by weight of base resin containing 79% by weight; and
(C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250° C. or higher,
Characterized in that the alkyl acrylate coverage (X) value calculated by Formula 1 below is 65% by weight or more.
Thermoplastic resin composition.
[Equation 1]
X = {(GY)/Y}
(In Equation 1, G represents the gel content (% by weight) relative to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel relative to the total weight of the thermoplastic resin composition.)
According to paragraph 1,
The (A) graft copolymer includes 25 to 50% by weight of alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, based on the total weight thereof; And 50 to 75% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer;
Thermoplastic resin composition.
According to paragraph 1,
The (A) graft copolymer is characterized in that the grafting rate calculated by Equation 3 below is 60% or more.
Thermoplastic resin composition.
[Equation 3]
Grafting rate (%) = [Weight of grafted monomer (g) / Rubber weight (g)]
(In Equation 3, the weight (g) of the grafted monomer is the weight (g) of the insoluble material (gel) minus the rubber weight (g) after dissolving the graft copolymer in acetone and centrifuging, Rubber weight (g) is the weight (g) of the theoretically added rubber component in the graft copolymer powder.)
According to paragraph 1,
The (B) (meth)acrylic acid alkyl ester polymer includes (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester.
Thermoplastic resin composition.
According to paragraph 1,
The (B) (meth)acrylic acid alkyl ester polymer is characterized in that the weight average molecular weight is 50,000 to 150,000 g/mol.
Thermoplastic resin composition.
According to paragraph 1,
The (C) crystalline polymer having a melting temperature (Tm) of 250° C. or higher includes polyhexamethylene adipamide (PA 66), polytetramethylene adipamide (PA 46), polyhexamethylene sebasamide (PA 610), Characterized by at least one selected from the group consisting of polydodecanolactam (PA 12), polyamide 6/6T, polyamide 6/66, and syndiotactic polystyrene resin.
Thermoplastic resin composition.
According to paragraph 1,
The thermoplastic resin composition is a film with a thickness of 0.15 T using a gloss meter according to ASTM D2457, characterized in that the gloss measured at 60° is 50 or less.
Thermoplastic resin composition.
According to paragraph 1,
The thermoplastic resin composition is characterized in that it has a total light transmittance of 75% or more as measured with a film with a thickness of 0.15 T according to ASTM D1003.
Thermoplastic resin composition.
According to paragraph 1,
The thermoplastic resin composition is manufactured into a sheet with a thickness of 0.15 mm using a T-die extruder, cut into a length of 100 cm, and then the thickness of the portion excluding 2 to 3 cm from both ends is measured in at least 10 locations. Characterized in that the thickness deviation calculated as the difference between the maximum thickness and the minimum thickness is 0.07 mm or less.
Thermoplastic resin composition.
According to paragraph 1,
The thermoplastic resin composition is characterized in that it contains at least one selected from the group consisting of a lubricant, an antioxidant, an ultraviolet stabilizer, and a pigment.
Thermoplastic resin composition.
(A) 21 to 79% by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber with an average particle diameter of 50 to 120 nm, and (B) 21 to 79% by weight of (meth)acrylic acid alkyl ester polymer. 100 parts by weight of base resin containing 79% by weight; and (C) 3 to 12 parts by weight of a crystalline polymer having a melting temperature (Tm) of 250°C or higher, comprising kneading and extruding under conditions of 200 to 300°C and 100 to 500 rpm,
Characterized in that the alkyl acrylate coverage (X) value calculated by Formula 1 below is 65% by weight or more.
Method for producing a thermoplastic resin composition.
[Equation 1]
X = {(GY)/Y}
(In Equation 1, G represents the gel content (% by weight) relative to the total weight of the thermoplastic resin composition, and Y represents the content (% by weight) of alkyl acrylate in the gel relative to the total weight of the thermoplastic resin composition.)
Characterized by comprising the thermoplastic resin composition of any one of claims 1 to 10.
Molded product.
According to clause 12,
The molded product is characterized in that it is a hidden display.
Molded product.