KR20150069888A - Low gloss thermoplastic resin composition having excellent weather-ability, and low gloss sheet and composite article therefrom - Google Patents

Abstract

The present invention relates to a styrene-based thermoplastic resin composition with weatherability and low gloss, a low gloss weatherable sheet using the same, and a manufacturing method thereof. According to the present invention, a low gloss weatherable product comprises: a low gloss styrene-based resin composed of (a) 20-50 parts by weight of an ASA graft copolymer, (b) 40-70 parts by weight of a SAN copolymer, (c) 0.1-20 parts by weight of a polyamide-based thermoplastic resin, and (d) 0.1-20 parts by weight of a crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer; and 0.1-5 parts by weight of a copolymer comprising a maleic anhydride-based compound with respect to 100 parts by weight of the low gloss styrene-based resin.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-gloss thermoplastic resin composition having excellent weather resistance, a low-gloss sheet and a composite using the same,

The present invention relates to a low gloss thermoplastic resin composition having excellent weather resistance and a low gloss sheet and a composite using the same. More particularly, the present invention relates to a low gloss styrene thermoplastic composition excellent in uniformity of low gloss and excellent in weatherability and impact resistance, Complexes and their preparation.

An ASA resin in which an acrylic rubber-like polymer graft-polymerized with styrene and an acrylonitrile monomer is dispersed in a styrene-acrylonitrile copolymer resin matrix has been widely applied in the exterior materials field.

In recent years, there has been an increasing demand for uncolored low-gloss ASA resins in order to meet the demand for sensitive resin deviating from an artificial plastic feeling and to prevent environmental pollution caused by painting.

Korean Patent No. 1240322 issued to Cheil Industries Co., Ltd. discloses a low gloss thermoplastic resin composition which is excellent in weather resistance and which is composed of an acrylic graft copolymer resin having a rubber particle size of 0.3 to 0.8 micrometer and an aromatic vinyl-cyanide vinyl copolymer Weather-resistant low-brightness resin.

Korean Patent No. 1056314 issued to LG Chemical Co., Ltd. discloses a thermoplastic resin composition comprising 30 to 70 parts by weight of an ASA copolymer; 5 to 20 parts by weight of a heat-resistant copolymer; 0.1 to 10 parts by weight of an acrylonitrile copolymer for a low-gloss filler; And 10 to 35 parts by weight of a SAN copolymer.

However, these conventional techniques are excellent in weatherability and low gloss, but are likely to cause low gloss non-uniformity on the surface. Further, in the case of extrusion molding in the form of a sheet, gloss can be expressed by a press roll for pressing the sheet.

Accordingly, there is a continuing need for a weather resistant resin having excellent low gloss and low gloss uniformity at the time of forming a sheet and a sheet molding method using the same.

A problem to be solved by the present invention is to provide a novel weatherable low-gloss thermoplastic resin composition capable of exhibiting uniform low gloss.

Another object of the present invention is to provide a low-gloss weather-resistant sheet comprising a novel weather-resistant low-gloss thermoplastic resin composition capable of exhibiting uniform low gloss and a method for producing the same.

Another object to be solved by the present invention is to provide a composite in which a low-gloss weather-resistant resin is formed on the surface.

The low-gloss styrene-based resin according to the present invention

(a) an ASA graft copolymer,

(b) a SAN copolymer,

(c) a polyamide-based thermoplastic resin,

(d) Crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer,

(e) a maleic anhydride-based compound.

The low gloss styrene resin composition according to the present invention comprises

(a) 20 to 50 parts by weight of an ASA graft copolymer,

(b) 40 to 70 parts by weight of a SAN copolymer, and

(c) 0.1 to 20 parts by weight of a polyamide-based thermoplastic resin, and

(d) 0.1 to 20 parts by weight of a crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer and 0.1 to 5 parts by weight of a copolymer containing 100 parts by weight of the low-gloss styrene- .

The low gloss sheet according to the present invention comprises (a) an ASA graft copolymer, (b) a SAN copolymer,

a weather-resistant styrene-based thermoplastic resin comprising a copolymer comprising (c) a polyamide-based thermoplastic resin, (d) a crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer, and (e) a maleic anhydride- The thermoplastic resin is extruded at a temperature lower than the melting temperature of the polyamide-based resin, preferably at 180 to 220 ° C. Although not limited in theory, the polyamide thermoplastic resin is extruded in a state in which the polyamide thermoplastic resin is not completely melted during the extrusion process of the low-gloss resin, so that low glossiness is strongly exhibited.

In the low-gloss composite according to the present invention, the low-gloss weather-resistant sheet according to the present invention is attached to the surface of a window or a window frame to impart low gloss and weatherability to the attached member. Hereinafter, the present invention will be described in more detail.

(a) an ASA graft copolymer

The ASA graft copolymer of the present invention comprises a crosslinked alkyl acrylate core, and a graft shell. The ASA graft copolymer can be prepared by graft-polymerizing a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound for forming a shell on an acrylic rubber. Preferably, the ASA graft copolymer is a copolymer obtained by grafting 40 to 90 parts by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer to 10 to 60 parts by weight of an acrylic rubber. The ASA graft copolymer resin may be polymerized by a conventional method known in the art. For example, emulsion polymerization, suspension polymerization and the like may be employed, and emulsion graft polymerization may be preferably used , And the aromatic vinyl compound-cyanide vinyl compound preferably has a graft rate of 30 to 80%.

The alkyl acrylate core for producing the ASA graft copolymer is selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Butyl methacrylate, etc. These may be used alone or in combination of two or more. Of these, butyl acrylate is preferable.

In the practice of the present invention, the rubber can have a diameter in the range of 1,000 to 5,000 Å, preferably in the range of 2,000 to 4,000 Å, and more preferably in the range of 3,500 to 4,000 Å.

The aromatic vinyl compound-cyanide vinyl compound copolymer grafted on the acrylic rubber may be a copolymer of 60 to 80 parts by weight of an aromatic vinyl compound and 20 to 40 parts by weight of a vinyl cyanide compound.

Examples of the aromatic vinyl compound include styrene,? -Methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and vinyltoluene. These aromatic vinyl compounds may be used singly or in combination of two or more. The vinyl cyanide compound may be acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like, and these compounds may be used alone or in combination. The ASA graft copolymer is preferably 10 to 50 parts by weight of the total resin composition. In the present invention, 35 to 45 parts by weight is more preferable in order to obtain a balance of impact resistance, low light properties and fluidity.

(b) SAN copolymer

The SAN copolymer of the present invention is obtained by mixing 10 to 60 parts by weight of a vinyl cyanide compound with 50 to 90 parts by weight of an aromatic vinyl compound and subjecting it to a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, ≪ / RTI > The aromatic vinyl compound used in the aromatic vinyl copolymer resin may be styrene, alphamethylstyrene, para-methylstyrene, etc., but is not limited thereto. These may be used alone or as a mixture of two or more. Of these, styrene is preferable.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like can be used, but the present invention is not limited thereto. These may be used alone or as a mixture of two or more. Of these, acrylonitrile is preferable.

The SAN copolymer is preferably 40 to 70 parts by weight of the total composition. In the present invention, 45 to 55 parts by weight is more preferable in order to obtain excellent physical properties such as fluidity and impact resistance.

In the practice of the present invention, the SAN polymer preferably has a weight average molecular weight of 80,000 to 150,000.

(c) a polyamide-based thermoplastic resin

The polyamide-based thermoplastic resin of the present invention means a thermoplastic polymer containing an amide bond, and is used as a matting agent in the present invention. Examples of the polyamide-based thermoplastic resin include a homopolymer, a copolymer polyamide and a polyamide blend of polyamide. The homopolymer of the polyamide may be a polymerization product of an aminocarboxylic acid such as 6-aminohexanoic acid, 7-aminoheptanoic acid, 12-aminodecanoic acid, or p-aminocyclohexylcarboxylic acid; Dodecamethylenediamine, metaxylenediamine, para-xylenediamine, hexamethylenediamine, 2,2,4,4-trimethylhexamethylenediamine, 1,3-bisaminomethylcyclohexane, bis-p-amino Diamines such as cyclohexylmethane; Polymerization products of dicarboxylic acids such as adipic acid, sebacic acid, sh vereric acid, pivalent acid, isophthalic acid terephthalic acid and 2,6-naphthalenedicarboxylic acid; Polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polymetaxylene / para-xylene adipamide, polymetaxylene / Xylene / paraxenesuberamide, polymethoxylene / paraxene azelamide, and the like.

The copolymer polyamide is a copolymer having an amide exchange reaction of two or more selected from the above-mentioned polyamide homopolymers, and examples thereof include lactams such as caprolactam and lauryl lactam; Aminocarboxylic acids such as 6-aminohexanoic acid, 7-aminoheptanoic acid, 12-aminododecanoic acid and p-aminocyclohexylcarboxylic acid; Metaxylenediamine, para

Diamines such as xylenediamine, hexamethylenediamine, 2,2,4 / 2,4,4-trimethylhexamethylenediamine, 1,3-bisaminomethylcyclohexane and bis-p-aminocyclohexylmethane; And dicarboxylic acids such as adipic acid, sebacic acid, schaperic acid, pivalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid.

In the present invention, 0.1 to 20 parts by weight of the polyamide-based thermoplastic resin is preferably used. In the present invention, 1 to 10 parts by weight is more preferable in order to obtain physical properties such as fluidity, impact resistance and low gloss.

In the present invention, the polyamide resin may be blended at a constant weight ratio. In this case, the content of one polyamide resin is preferably less than 20 parts by weight based on the other polyamide resin. At this time, if it exceeds 20 parts by weight, the amide exchange reaction during blending becomes insufficient, phase separation of the two resins occurs and the mechanical properties are deteriorated, which is not preferable.

In the present invention, the polyamide-based thermoplastic resin is commercially available and can be used. Preferably, the polyamide-based thermoplastic resin has a melting point of 230 ° C or higher, preferably 240 ° C or higher, more preferably 250 ° C or higher.

In the present invention, the relative viscosity of the polyamide-based thermoplastic resin is preferably 2.0 to 4.0 ml / g (sulfuric acid 96% solution). And more preferably 2.5 to 3.5 ml / g.

(d) Crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer

The crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer is used as a matting agent, and examples of the aromatic vinyl compound include side chain alkyl substituted styrene such as styrene,? -Ethyl styrene and? -Methyl styrene; alkyl substituted styrenes such as p-methylstyrene, o-t-butylstyrene; Bromostyrene, chlorostyrene, trichlorostyrene, and the like. These may be used alone or in combination of two or more. Of these, styrene is most preferable.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, etc. may be used alone or in combination. As the crosslinking agent, divinylbenzene, trivinylbenzene, trialkylisocyanurate may be used. Further, a methacrylate monomer having two or more polymerizable double bonds such as allyl methacrylate and ethylene glycol dimethacrylate may be used.

The degree of crosslinking of the cross-linked aromatic vinyl compound-cyanide vinyl compound copolymer (D) as a whole is 30 to 90%, preferably 30 to 70%, more preferably 40 to 65%. If the degree of crosslinking is less than 30% or more than 70%, it may not serve to reduce the gloss of the thermoplastic resin, or fine gel may be generated during processing, thereby causing a problem of appearance defects.

The crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer (D) is preferably used in an amount of 0.1 to 20 parts by weight based on the total composition. In the present invention, 1 to 10 parts by weight is more preferable in order to obtain physical properties such as fluidity, impact resistance and low gloss.

The crosslinked vinyl compound-cyanide vinyl compound copolymer resin can be purchased commercially and used, for example, from Hannotec Korea, and AM-10 grade can be used in the preferred embodiment.

(e) a copolymer comprising a maleic anhydride-based compound

The copolymer comprising a maleic anhydride-based compound may be prepared by mixing maleic anhydride, N-substituted maleate, or a mixture thereof with an aromatic vinyl compound and subjecting the copolymer to bulk polymerization, solution polymerization, emulsion polymerization, . In the present invention, it is used as a compatibilizing agent in order to enhance the miscibility between the styrene resin and the polyamide resin.

The copolymer containing the maleic anhydride-based compound is a copolymer of 40 to 60 parts by weight of maleic anhydride, N-substituted maleate or a mixture thereof and 40 to 60 parts by weight of an aromatic vinyl compound. In the above range, excellent physical properties such as heat resistance and fluidity can be imparted. The aromatic vinyl compound used in the copolymer (E) containing the maleic anhydride-based compound may be styrene, alphamethylstyrene, paramethylstyrene, etc., but is not limited thereto. These may be used alone or as a mixture of two or more. Of these, styrene is preferable. The copolymer (E) comprising the maleic anhydride-based compound is used in an amount of 0.1 to 5 parts by weight based on the total weight of the low gloss styrene resin. When the content is less than 0.1 parts by weight, miscibility is deteriorated. When the content is more than 5 parts by weight, it is not preferable because of low fluidity and increased manufacturing cost.

(g) Others

The resin composition of the present invention may further contain usual additives in addition to the above components. Additives such as dyes, pigments, antimicrobial agents, lubricants, heat stabilizers, antioxidants, mold release agents, light stabilizers, inorganic additives, ultraviolet absorbers, ultraviolet light blocking agents, flame retardants, fillers, nucleating agents, antistatic agents, foaming agents and plasticizers These may be added alone or in admixture of two or more. If the amount of the additive is less than 0.01 parts by weight, discoloration and kneading property may occur during processing due to insufficient thermal stability. When the amount of the additive exceeds 3 parts by weight, gas due to pyrolysis and volatilization of the additive may be generated. And the like.

(f) Production of resin

Each component of the low gloss styrenic thermoplastic resin composition of the present invention can be prepared by kneading by a twin screw extruder. At this time, the processing temperature at the time of extrusion is such that the polyamide-based resin which is a matting agent can be melted and the upper limit of the temperature is 15 ° C higher than the melting point of the polyamide-based resin used so as to prevent the styrene- And more preferably, the upper limit is set at a temperature 10 ° C higher than the melting point of the polyamide-based resin to be used.

The low-gloss styrenic resin composition prepared by the above-mentioned method preferably has a degree of gloss of 20 to 70, preferably 20 to 50, at 75 DEG when measured by a gloss meter according to ASTM D523.

(g) Extrusion of low gloss sheet

The low gloss styrenic thermoplastic resin according to the present invention is preferably extruded at a temperature lower than the melting point of the polyamide based resin so as to offset the increase in gloss caused by roll pressing upon extrusion of the sheet, It is preferable that the maximum temperature of the extruder used for the extrusion is processed at a temperature lower than the melting point of the polyamide based resin by at least 30 캜, preferably at 190 캜 to 210 캜.

The low-gloss sheet may be extruded into a single layer and fused or bonded to a member such as a window or a window frame that needs weather resistance and low gloss.

The low-gloss sheet may be co-extruded together with an ABS resin, an ASA resin, an AES resin or the like to coat the surface with a low-gloss weather-resistant sheet. Preferably, the low-gloss sheet is applied to the surface layer at 10 to 15% .

The low-gloss resin according to the present invention has low gloss, excellent low-gloss uniformity, and is manufactured into a low-gloss sheet through an extrusion process. The low light Tex sheet is extruded together with resins that do not exhibit low gloss and weatherability through coextrusion, for example, ABS to provide composite members that exhibit low gloss and weatherability in a small amount.

Examples of the present invention in which a styrene-based resin containing a polyamide-based thermoplastic resin (C) and a crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer (D) as a matting agent are used as a base resin are shown in (C) and ) Is a graph showing that the low gloss characteristics of the sheet composition according to the processing temperature is superior to the comparative example using a styrene resin which does not contain two types of matting agents at the same time.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It should be noted, however, that the following examples are intended to illustrate the invention and are not to be construed as limiting the scope of the invention in any way.

The specifications of each component used in the following examples and comparative examples are as follows.

The resin (A) ASA graft copolymer used was an acrylic rubber-containing resin having an average size of 3500 to 4000 Å and a rubbery content of 50.0%. Styrene and acrylonitrile were added to the crosslinked butyl acrylate rubber at a weight ratio of 7: 3 (Grafting rate of 55%), and the synthesis and grafting of rubber were emulsion-polymerized by polymerization and then coagulated and dried.

(B) The SAN copolymer was a resin having a styrene monomer content of 68 parts by weight, acrylonitrile of 32 parts by weight, and a weight average molecular weight of 120,000.

(C) The polyamide thermoplastic resin used as a matting agent was a resin having a melting temperature of 265 DEG C and a relative sulfuric acid viscosity (sulfuric acid 96% solution) of 2.5 to 3.5 ml / g.

 (D) The cross-linked aromatic vinyl compound-cyanide vinyl compound copolymer used as a matting agent was AM-10 (manufactured by Hanano Corporation).

(E) MS-NB (manufactured by DENKA) was used as a copolymer containing a maleic anhydride-based compound used as a compatibilizer.

(F) The lubricant was SUNLUBE ethylene bis-stearamide (manufactured by Pure Chemical).

(G) Antioxidant SN 147BF (manufactured by Songwon Industrial Co., Ltd.) was used. Here, the lubricant and the antioxidant were used in a weight ratio of 2.5: 0.5.

The preparation examples were added in the amounts shown in Table 1 below and then extruded by a twin screw extruder of SM Platek Co., Ltd., having a diameter of 30 mm under conditions of an extrusion temperature of 250 to 270 DEG C, a screw rotation speed of 100 RPM and a feed rate of 12 kg / Lt; / RTI > The pellets thus prepared were injected under the conditions of a molding temperature of 180 to 280 DEG C and a mold temperature of 40 to 80 DEG C by an injection molding machine, and the pellets were measured by the following property evaluation method.

At the time of sheet processing, a sheet having a thickness of 0.5 mm was produced by using a Torque Rheometers uniaxial screw extruder and a T-die of HAAKE at a screw rotating speed of 80 RPM and a feed rate of 10 kg / hr . At this time, in order to develop the matte properties of the extruded sheet, it was processed at a temperature of 190 to 210 DEG C which is 30 DEG C or less than the melting temperature of the polyamide resin (C) used as the matting agent.

division Example Comparative Example One 2 3 4 5 One 2 3 A 45 45 45 45 45 45 45 45 B 51 49 47 45 41 48 52 45 C 3 5 7 7 7 7 - 7 D One One One 3 7 - 3 3 E One One One One One One One - F / G 3 3 3 3 3 3 3 3

Property evaluation method

(1) Impact strength: Measured according to ASTM D256. (Kgf / cm)

(2) Flow Index: Measured according to ASTM D1238. (g / 10 min, 220 캜, 10 kg)

(3) Extrusion sheet Gloss measurement: Measured according to ASTM D523.

(4) Weatherability: Evaluated according to SAE J2527 as? E.

? E =

division Example Comparative Example One 2 3 4 5 One 2 3 Impact Strength (1/8 ") 24 23 22 21 19 22 24 18 Flow index 6 6 5 5 5 5 6 5 Gloss (75 °) 45 43 40 32 29 47 76 34 Weatherability (ΔE) 2.5 2.5 2.4 2.6 2.6 2.4 2.6 2.6

The compositions of Examples 1 to 5 including the simultaneous use of the polyamide thermoplastic resin (C) and the crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer (D) as a matting agent were not simultaneously used It was confirmed that the compositions of Comparative Examples 1 and 2 including the case where the low glossiness was low and the low gloss characteristics were excellent.

Compared with the composition of Comparative Example 3 which did not contain the composition of Example 4 containing the compatibilizing agent (E), it was confirmed that the impact strength of the matting agent and the styrene-based resin was improved and the impact strength was increased.

Claims (10)

(a) 20 to 50 parts by weight of an ASA graft copolymer,
(b) 40 to 70 parts by weight of a SAN copolymer, and
(c) 0.1 to 20 parts by weight of a polyamide-based thermoplastic resin, and
(d) 0.1 to 20 parts by weight of a crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer; and
0.1 to 5 parts by weight of a copolymer containing a maleic anhydride-based compound per 100 parts by weight of the low-gloss styrene-based resin
Wherein the styrene-based thermoplastic resin composition is a weather-resistant low gloss styrene-based thermoplastic resin composition. The weather-resistant low gloss styrenic thermoplastic resin composition according to claim 1, wherein the ASA graft copolymer is an acrylic rubber-like polymer having an average size of 2000 to 4000 ANGSTROM as a core. The acrylic rubber polymer according to claim 2, wherein the acrylic rubber polymer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Methacrylate group, and a methacrylate group. The weather-resistant low gloss styrenic thermoplastic resin composition according to claim 1, wherein the polyamide-based thermoplastic resin is at least one selected from a homopolymer, a copolymer polyamide and a polyamide blend of polyamide. The weather-resistant low gloss styrenic thermoplastic resin composition according to claim 1, wherein the crosslinked aromatic vinyl compound-cyanide vinyl compound copolymer has a crosslinking degree of 30 to 70%. The weather-resistant low gloss styrenic thermoplastic resin composition according to claim 1, wherein the copolymer comprising maleic anhydride-based compounds is obtained by copolymerizing maleic anhydride, N-substituted maleate or a mixture thereof with an aromatic vinyl compound. The weather-resistant low gloss styrenic thermoplastic resin composition according to claim 1, further comprising a lubricant and an antioxidant. A weather-resistant low gloss sheet comprising a surface layer composed of the weather-resistant low gloss styrene thermoplastic resin composition according to any one of claims 1 to 7. The weathering low-gloss sheet according to claim 8, wherein the sheet is a single-layer sheet or a multi-layer sheet co-extruded together with another resin. (a) 20 to 50 parts by weight of an ASA graft copolymer, (b) 40 to 70 parts by weight of a SAN copolymer, (c) 0.1 to 20 parts by weight of a polyamide thermoplastic resin, and (d) 0.1 to 20 parts by weight of a cyanide-vinyl compound copolymer and 0.1 to 5 parts by weight of a copolymer comprising a low-gloss styrene-based resin and 100 parts by weight of the low-gloss styrene- Wherein the extruding is carried out at a temperature lower than the melting temperature of the amide-based thermoplastic resin by 30 占 폚 or more.

Images