WO2020046013A1 - Molded product having fabric texture - Google Patents

Abstract

A molded product according to the present invention is a molded product having a structure in which colored particles are dispersed in thermoplastic resin, wherein the colored particles have an average particle size of about 250-3,200 µm as measured by a particle size analyzer, and are included in an amount of about 0.05-5 parts by weight with respect to about 100 parts by weight of the thermoplastic resin, a three-dimensional pattern is formed on at least one surface of the molded product, and the three-dimensional pattern has a 10-point average roughness (Rz) of about 50-500 µm and a number of different brightness values of about 30-60. The molded product has excellent impact resistance, excellent heat resistance, and the like, and has an appearance similar to actual fabric.

Description

Molded article with fabric texture

The present invention relates to a molded article having a fabric texture and a method of manufacturing the same. More specifically, the present invention relates to a molded article having excellent impact resistance and heat resistance and the like and having a similar appearance to an actual fabric, and a method of manufacturing the same.

The thermoplastic resin composition has a specific gravity lower than that of glass and metal, and is excellent in physical properties such as formability and impact resistance, and is useful for housings, interior / exterior materials, and interior / exterior materials for electric / electronic products. As the thermoplastic resin composition is widely used as an exterior material, there is an increasing demand for exterior materials, in particular, fabric texture, which can satisfy consumers who require a high-quality appearance.

Existing fabric texture materials include blending actual fabrics with thermoplastics, simply applying general pattern corrosion to thermoplastics, or in-mold, attach, or print pattern films of fabric textures. .

However, such a manufacturing method has disadvantages such as lowering physical properties of the thermoplastic resin, increasing costs due to the use of an adhesive, applying a film, and the like, increasing process steps, and reducing environmental friendliness.

Therefore, there is a need for development of a molded article having an appearance similar to that of a real fabric without deteriorating physical properties such as impact resistance and heat resistance.

Background art of the present invention is disclosed in the Republic of Korea Patent Publication No. 10-2015-0103541.

An object of the present invention is to provide a molded article excellent in impact resistance and heat resistance, and has a similar appearance to the actual fabric.

Another object of the present invention is to provide a method for producing the molded article.

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

1. One aspect of the present invention relates to a molded article. The molded article is a molded article having a structure in which colored particles are dispersed in a thermoplastic resin, and the colored particle has an average particle size of about 250 to about 3,200 μm measured by a particle size analyzer, and about 0.05 to about about 100 parts by weight of the thermoplastic resin. 5 parts by weight, wherein a three-dimensional pattern is formed on at least one surface of the molded article, and the three-dimensional pattern has a ten-point average roughness Rz of about 50 to about 500 μm, and the 3 mm × 3 mm width portion of the three-dimensional pattern is 600 Scanned at dpi resolution, converted into an image represented by 4900 pixels, and measured for each pixel's brightness (L ^* ) value based on CIE 1976 / CIE LAB chrominance. And from about 30 to about 60 numbers.

2. In one embodiment, the thermoplastic resin may include at least one of a polycarbonate resin and a rubber-modified aromatic vinyl copolymer resin.

3. In the above 1 or 2 embodiment, the rubber-modified aromatic vinyl copolymer resin is a rubber-modified vinyl graft copolymer graft copolymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer in a rubbery polymer About 10 to about 100 weight percent; And about 0 to about 90 wt% of an aromatic vinyl copolymer resin in which an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer are copolymerized.

4. In the embodiments 1 to 3, the colored particles may have a difference in brightness value from the thermoplastic resin of about 20 to about 99.

5. In the above 1 to 4 embodiments, the colored particles may include one or more of cellulose and carbon fibers.

6. In the above 1 to 5 embodiments, the aspect ratio of the colored particles may be about 0.015 to about 0.08.

7. In the above embodiments 1 to 6, the molded article, the thermoplastic resin is a diene rubber-modified aromatic vinyl copolymer resin, the notched Izod impact strength of the 1/4 "specimen thickness measured according to ASTM D256 Notch of 1/4 "thickness specimen measured according to ASTM D256, when the thermoplastic resin is a combination of polycarbonate resin and diene rubber modified aromatic vinyl copolymer resin, which may be from 9 to about 50 kgfcm / cm Izod impact strength may be about 15 to about 50 kgf · cm / cm, when the thermoplastic resin is a combination of polycarbonate resin and (meth) acrylate rubber modified aromatic vinyl copolymer resin, measured according to ASTM D256 Notched Izod impact strength of a 1/4 "specimen may be about 9 to about 50 kgfcm / cm.

8. In the above embodiments 1 to 7, wherein the molded article, the thermoplastic resin is a diene rubber-modified aromatic vinyl copolymer resin, load 18.56 kgf / cm ² , temperature increase rate 120 ℃ / hr in accordance with ASTM D648 When the heat deflection temperature (HDT) measured at can be about 82 to about 125 ℃, and the thermoplastic resin is a combination of a polycarbonate resin and a diene rubber modified aromatic vinyl copolymer resin, the load according to ASTM D648 18.56 kgf / cm ² , the heat deflection temperature (HDT) measured under conditions of a temperature increase rate of 120 ° C./hr may be about 108 to about 125 ° C., and the thermoplastic resin is a polycarbonate resin and a (meth) acrylate rubber-modified aromatic vinyl-based air In the case of the combination resin, the heat deflection temperature (HDT) measured under conditions of a load of 18.56 kgf / cm ² and a heating rate of 120 ° C./hr based on ASTM D648 may be about 82 to about 125 ° C.

9. Another aspect of the present invention relates to a method for producing the molded article. The manufacturing method includes the step of injecting a thermoplastic resin composition in an injection molding machine applying a mold capable of realizing a three-dimensional pattern having a ten-point average roughness Rz of about 50 to about 500 ㎛ on at least one surface, wherein the thermoplastic resin composition is a thermoplastic resin About 100 parts by weight, and about 0.05 to about 5 parts by weight of colored particles having an average particle size of about 250 to about 3,200 μm as measured by a particle size analyzer.

10. In the 9th embodiment, the injection may be performed at an injection temperature of about 200 to about 320 ℃, mold temperature about 40 to about 80 ℃.

The present invention is excellent in impact resistance and heat resistance, and has the effect of the invention to provide a molded article having a similar appearance to an actual fabric and a manufacturing method thereof.

Hereinafter, the present invention will be described in detail.

The molded article according to the present invention implements a fabric texture, and is a molded article having a structure in which colored particles are dispersed in a thermoplastic resin, formed from a thermoplastic resin composition, and a three-dimensional pattern is formed on at least one surface.

In the present specification, "a to b" indicating a numerical range is defined as "≥a and <b".

Thermoplastic resin composition according to an embodiment of the present invention (A) a thermoplastic resin; And (B) colored particles.

(A) thermoplastic resin

The thermoplastic resin of the present invention may be a thermoplastic resin used in conventional thermoplastic resin compositions. For example, polycarbonate resin and / or rubber-modified aromatic vinyl copolymer resin can be used. Specifically, a combination of polycarbonate resin or polycarbonate resin and rubber-modified aromatic vinyl copolymer resin can be used.

(a) polycarbonate resin

As the polycarbonate resin according to an embodiment of the present invention, a polycarbonate resin used in a conventional thermoplastic resin composition may be used. For example, an aromatic polycarbonate resin produced by reacting diphenols (aromatic diol compounds) with carbonate precursors such as phosgene, halogen formate, and carbonic acid diester can be used.

In an embodiment, the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1 , 1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) Propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, and the like, but are not limited thereto. . For example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4- Hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclohexane can be used, specifically, bisphenol- 2, 2-bis (4-hydroxyphenyl) propane called A can be used.

In embodiments, the carbonate precursor is dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate , Carbonyl chloride (phosphene), diphosgene, triphosgene, carbonyl bromide, bishaloformate, and the like. These can be used individually or in mixture of 2 or more types.

In embodiments, the polycarbonate resin may be a branched chain, for example, from about 0.05 to about 2 mole% of a trivalent or more polyfunctional compound, specifically, based on the total diphenols used for polymerization. It may also be prepared by adding a compound having a trivalent or more phenol group.

In an embodiment, the polycarbonate resin may be used in the form of a homo polycarbonate resin, a copolycarbonate resin or a blend thereof. In addition, the polycarbonate resin may be partially or entirely replaced by an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, for example, a bifunctional carboxylic acid.

In embodiments, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 200,000 g / mol, for example, about 15,000 to about 40,000 g / mol. In the above range, the thermoplastic resin composition may be excellent in impact resistance, rigidity, heat resistance, and the like.

(b) rubber-modified aromatic vinyl copolymer resin

Rubber modified aromatic vinyl copolymer resin according to an embodiment of the present invention is a thermoplastic resin having excellent balance of physical properties such as impact resistance, fluidity, heat resistance, etc., which can be used in various applications such as building interior / exterior materials, automotive interior / exterior materials .

In one embodiment, the rubber-modified aromatic vinyl copolymer resin is a rubber-modified vinyl-based graft copolymer (b1) in which a rubber copolymer is copolymerized with an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer. About 100% by weight; And about 0 wt% to about 90 wt% of the (b2) aromatic vinyl copolymer resin copolymerized with the aromatic vinyl monomer and the monomer copolymerizable with the aromatic vinyl monomer. That is, the rubber-modified aromatic vinyl copolymer resin of the present invention is a rubber-modified vinyl-based graft copolymer (b1) alone or a rubber-modified vinyl-based graft copolymer (b1) and an aromatic vinyl-based copolymer resin ( in the form of a mixture of b2).

In an embodiment, the rubber-modified vinyl graft copolymer (b1) may be polymerized by adding an aromatic vinyl monomer, a monomer copolymerizable with the aromatic vinyl monomer, and the like to a rubbery polymer, and the aromatic vinyl copolymer resin (b2) can superpose | polymerize by adding an aromatic vinylic monomer, the monomer copolymerizable with the said aromatic vinylic monomer, etc. The polymerization may be carried out by a known polymerization method such as emulsion polymerization, suspension polymerization, block polymerization. In the case of the bulk polymerization, the rubber-modified vinyl-based graft copolymer (b1) is produced by only one step reaction process without separately preparing the rubber-modified vinyl-based graft copolymer (b1) and the aromatic vinyl-based copolymer resin (b2). The rubber-modified aromatic vinyl copolymer resin in a form dispersed in the aromatic vinyl copolymer resin (b2) which is a matrix can be prepared.

In an embodiment, the rubber (rubber polymer) content in the final rubber modified aromatic vinyl copolymer resin component may be 5 to 50% by weight, and the rubbery polymer has an average particle size (Z-average) measured by a particle size analyzer of about 0.2 to about 15 μm, for example about 0.3 to about 10 μm. Impact resistance and the like in the above range can be excellent, it is possible to obtain a thermoplastic resin composition that can implement a three-dimensional texture. Here, the average particle size (Z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state. Specifically, the rubber polymer latex is filtered through a mesh to remove coagulum generated during the polymerization of the rubber polymer, and 0.5 g of latex and 30 ml of distilled water are poured into a 1,000 ml flask and filled with distilled water to prepare a sample. 10 ml of the sample is transferred to a quartz cell, and the average particle size (Z-average) of the rubbery polymer may be measured by a light scattering particle size analyzer (nano-zs).

Hereinafter, the rubber-modified vinyl graft copolymer (b1) and the aromatic vinyl copolymer resin (b2) will be described in more detail.

(b1) Rubber modified vinyl graft copolymer

The rubber-modified vinyl graft copolymer may be obtained by graft copolymerization of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer to a rubbery polymer, and, if necessary, further includes a monomer which gives workability and heat resistance. You can.

Specific examples of the rubbery polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), saturated rubbers hydrogenated to the diene rubber, isoprene rubber, Alkyl (meth) acrylate rubbers, copolymers of alkyl (meth) acrylates having 2 to 10 carbon atoms and styrene, ethylene-propylene-diene monomer terpolymers (EPDM), and the like. These can be applied individually or in mixture of 2 or more types. For example, a diene rubber, a (meth) acrylate rubber, etc. can be used, Specifically, a butadiene rubber, a butyl acrylate rubber, etc. can be used.

In an embodiment, the amount of rubbery polymer is about 5 to about 65 weight percent, such as about 10 to about 60 weight percent, specifically about 20 to about 50 weight percent of the total weight of the rubber-modified vinyl-based graft copolymer (b1) Weight percent. In the above range, mechanical properties such as impact resistance of the rubber-modified aromatic vinyl copolymer resin may be excellent.

In embodiments, the rubbery polymer may have an average particle size (Z-average) as measured by a particle size analyzer of about 250 to about 3,000 nm, for example about 350 to about 2,000 nm. Impact resistance and the like in the above range can be excellent, it is possible to obtain a thermoplastic resin composition that can implement a three-dimensional texture. Here, the average particle size (Z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state. Specifically, the rubber polymer latex is filtered through a mesh to remove coagulum generated during the polymerization of the rubber polymer, and 0.5 g of latex and 30 ml of distilled water are poured into a 1,000 ml flask and filled with distilled water to prepare a sample. 10 ml of the sample is transferred to a quartz cell, and the average particle size (Z-average) of the rubbery polymer may be measured by a light scattering particle size analyzer (nano-zs).

The aromatic vinyl monomer may be graft copolymerized to the rubbery copolymer, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene , Monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene and the like can be used, but is not limited thereto. These can be applied individually or in mixture of 2 or more types. The content of the aromatic vinyl monomer is about 15 to about 94% by weight, for example about 20 to about 80% by weight, specifically about 30 to about 60% by weight, based on the total weight of the rubber-modified vinyl graft copolymer (b1) Can be. It is possible to obtain a rubber-modified aromatic vinyl copolymer resin having excellent mechanical properties in the above range.

As the monomer copolymerizable with the aromatic vinyl monomer, for example, vinyl cyanide compounds such as acrylonitrile, unsaturated nitrile compounds such as ethacrylonitrile, methacrylonitrile, and the like can be used. It can mix and use the above. The content of the monomer copolymerizable with the aromatic vinyl monomer is about 1 to about 50% by weight, for example about 5 to about 45% by weight, specifically about 10 to about 30% by weight of the total weight of the rubber-modified vinyl graft copolymer May be%. It is possible to obtain a rubber-modified aromatic vinyl copolymer resin having excellent mechanical properties in the above range.

Examples of the monomer for imparting processability and heat resistance may include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, and the like. These can be applied individually or in mixture of 2 or more types. The content of the monomer for imparting processability and heat resistance may be about 0 to about 15 wt%, for example, about 0.1 to about 10 wt% of the total weight of the rubber-modified vinyl graft copolymer. In the above range, workability and heat resistance can be imparted without deterioration of other physical properties.

In one embodiment, the rubber-modified vinyl graft copolymer is a copolymer in which a styrene monomer, an aromatic vinyl compound, and an acrylonitrile monomer, a vinyl cyanide compound, are grafted to a butadiene rubber polymer, and a butyl acryl. The acrylate-styrene-acrylonitrile graft copolymer (g-ASA) etc. which are a copolymer in which the styrene monomer which is an aromatic vinyl type compound, and the acrylonitrile monomer which is a vinyl cyanide compound are grafted to the rate type rubbery polymer can be illustrated. have.

(b2) aromatic vinyl copolymer resin

The aromatic vinyl copolymer resin may be prepared using a monomer mixture excluding rubber (rubber polymer) among the components of the rubber-modified vinyl graft copolymer (b1), and the ratio of monomer may vary depending on compatibility and the like. have. For example, the aromatic vinyl copolymer resin can be obtained by copolymerizing a monomer copolymerizable with the aromatic vinyl monomer and the aromatic vinyl monomer.

Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene and dibromo. Styrene, vinyl naphthalene, etc. may be used, but is not limited thereto. These can be applied individually or in mixture of 2 or more types.

As the monomer copolymerizable with the aromatic vinyl monomer, for example, vinyl cyanide compounds such as acrylonitrile, unsaturated nitrile compounds such as ethacrylonitrile, methacrylonitrile, and the like can be used. It can mix and use 2 or more types.

The aromatic vinyl copolymer resin may further include a monomer to impart the processability and heat resistance, if necessary. Examples of the monomer for imparting processability and heat resistance may include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, and the like. These can be applied individually or in mixture of 2 or more types.

In the aromatic vinyl copolymer resin, the content of the aromatic vinyl monomer is about 50 to about 95% by weight, for example about 60 to about 90% by weight, specifically about 70 of the total weight of the aromatic vinyl copolymer resin. To about 80 weight percent. It is possible to obtain a good balance of physical properties of the impact strength and mechanical properties in the above range.

The content of the monomer copolymerizable with the aromatic vinyl monomer may be about 5 to about 50% by weight, for example about 10 to about 40% by weight, specifically about 20 to about 30% by weight, based on the total weight of the aromatic vinyl copolymer resin. Can be. It is possible to obtain a good balance of physical properties of the impact strength and mechanical properties in the above range.

In addition, the content of the monomer for imparting processability and heat resistance may be about 0 to about 30% by weight, for example about 0.1 to about 20% by weight of the total weight of the aromatic vinyl copolymer resin. In the above range, workability and heat resistance can be imparted without deterioration of other physical properties.

The weight average molecular weight of the aromatic vinyl copolymer resin may be about 50,000 to about 500,000 g / mol, but is not limited thereto.

Non-limiting examples of the rubber-modified aromatic vinyl copolymer resin of the present invention is a copolymer in which a styrene monomer as an aromatic vinyl compound and an acrylonitrile monomer as an unsaturated nitrile compound are grafted to a central butadiene rubber polymer (g Rubber modified vinyl graft copolymer (b1) single use form, such as -ABS), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile- ethylene propylene rubber-styrene copolymer resin (AES resin) ), And a mixture form of a rubber-modified vinyl graft copolymer (b1) and an aromatic vinyl copolymer resin (b2) such as acrylonitrile-acryl rubber-styrene copolymer resin (AAS resin). Here, the ABS resin is dispersed in styrene-acrylonitrile copolymer resin (SAN resin) as the rubber-modified vinyl graft copolymer (b1), g-ABS as the aromatic vinyl copolymer resin (b2). It may have been.

In an embodiment, when the thermoplastic resin is a combination of the polycarbonate resin (a) and the rubber-modified aromatic vinyl copolymer resin (b), the content of the polycarbonate resin (a) is 100% by weight of the total thermoplastic resin, About 5 to about 95% by weight, for example about 30 to about 70% by weight, and the content of the rubber-modified aromatic vinyl copolymer resin (b) is about 5 to about 95 in 100% by weight of the total thermoplastic resin. Weight percent, for example, about 30 to about 70 weight percent. In the above range, the impact resistance, heat resistance and the like of the thermoplastic resin composition may be excellent.

(B) colored particles

The colored particles of the present invention may be included in the thermoplastic resin composition to broadly improve the color spectrum so that a molded article having a three-dimensional pattern formed therefrom may realize a similar appearance to an actual fabric material. The colored particles may have the form of acicular (fibrous), have an average particle size of about 250 to about 3,200 ㎛, for example about 350 to about 3,000 ㎛ measured by a particle size analyzer, the cross-sectional diameter before processing About 10 to about 100 μm, for example about 15 to about 80 μm. If the average particle size of the colored particles is out of the range, the color spectrum (number of different brightness values) of the molded article is reduced, it may be difficult to implement the fabric texture.

In embodiments, the colored particles may have a difference in brightness (L ^* ) value from about 20 to about 99, for example, about 20 to about 80, based on the CIE 1976 / CIE LAB color difference. Within this range molded articles having a texture similar to the actual fabric material (particularly visual texture) can be obtained.

In an embodiment, the aspect ratio of the colored particles can be from about 0.015 to about 0.08, for example from about 0.018 to about 0.08. Here, the aspect ratio is the ratio of the longest axis diameter to the shortest axis diameter of the cross section of acicular (fibrous) colored particles. Within this range molded articles having a texture similar to the actual fabric material (particularly visual texture) can be obtained.

In embodiments, the colored particles may include cellulose, carbon fiber, combinations thereof, and the like.

In an embodiment, the colored particles may be included in an amount of about 0.05 to about 5 parts by weight, for example about 0.1 to about 3 parts by weight, based on about 100 parts by weight of the thermoplastic resin. When the content of the colored particles is less than about 0.05 parts by weight, there is a concern that the color spectrum, dispersibility, etc. of the thermoplastic resin composition and the molded article may be lowered. When the content of the colored particles exceeds about 5 parts by weight, the impact resistance and heat resistance of the thermoplastic resin composition and the molded article may be reduced. Etc. may fall.

In addition to the above components, the thermoplastic resin composition according to one embodiment of the present invention may further include an additive in a range that does not inhibit the effects of the present invention. The additives include, but are not limited to, flame retardants, antioxidants, anti drip agents, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, colorants, mixtures thereof, and the like.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of pellets mixed with the components and melt-extruded at about 200 to about 280 ° C, for example, about 220 to about 260 ° C, using a conventional twin screw extruder. Can be.

In one embodiment, the thermoplastic resin composition (molded product) is a 1/4 "thickness specimen measured according to ASTM D256 when the thermoplastic resin is a diene rubber-modified aromatic vinyl copolymer resin (g-ABS / SAN, etc.). Notched Izod impact strength may be about 9 to about 50 kgf · cm / cm, for example about 10 to about 30 kgf · cm / cm.

In one embodiment, the thermoplastic resin composition (molded article) is a thickness measured according to ASTM D256 when the thermoplastic resin is a combination of a polycarbonate resin and a diene rubber-modified aromatic vinyl copolymer resin (g-ABS / SAN, etc.). The notched Izod impact strength of the 1/4 "specimen may be about 15 to about 50 kgfcm / cm, for example about 18 to about 40 kgfcm / cm.

In an embodiment, the thermoplastic resin composition (molded product) is based on ASTM D256, when the thermoplastic resin is a combination of a polycarbonate resin and a (meth) acrylate rubber-modified aromatic vinyl copolymer resin (g-ASA / SAN, etc.). The notched Izod impact strength of the measured 1/4 "specimen may be about 9 to about 50 kgfcm / cm, for example about 10 to about 40 kgfcm / cm.

In one embodiment, the thermoplastic resin composition (molded product) is a load of 18.56 kgf / cm ² , a temperature increase rate based on ASTM D648 when the thermoplastic resin is a diene rubber-modified aromatic vinyl copolymer resin (g-ABS / SAN, etc.). The heat deflection temperature (HDT) measured at 120 ° C./hr may be about 82 to about 125 ° C., for example about 85 to about 115 ° C.

In an embodiment, the thermoplastic resin composition (molded product) has a load of 18.56 kgf based on ASTM D648 when the thermoplastic resin is a combination of a polycarbonate resin and a diene rubber-modified aromatic vinyl copolymer resin (g-ABS / SAN, etc.). / cm ² , the heat deflection temperature (HDT) measured under conditions of a heating rate of 120 ° C./hr may be about 108 to about 125 ° C., for example about 110 to about 120 ° C.

In an embodiment, the thermoplastic resin composition (molded article) is based on ASTM D648 when the thermoplastic resin is a combination of a polycarbonate resin and a (meth) acrylate rubber-modified aromatic vinyl copolymer resin (g-ASA / SAN, etc.). The heat deflection temperature (HDT) measured under conditions of a load of 18.56 kgf / cm ² and a heating rate of 120 ° C./hr may be about 82 to about 125 ° C., for example about 84 to about 115 ° C.

The molded article of the present invention is formed from the thermoplastic resin composition, and a three-dimensional pattern is formed on at least one surface, and the three-dimensional pattern has a ten point average roughness Rz of about 50 to about 500 µm, for example, about 70 to about 450 µm. will be. If the ten-point average roughness Rz of the three-dimensional pattern is out of the above range, the color spectrum (number of different brightness values) of the molded article may be reduced, so that fabric texture may be difficult to implement.

Herein, the ten point height of irregularity Rz is extracted from the roughness curve measured through a microscope by a reference length in the direction of the average line, as shown in Equation 1 below, The sum of the average of the absolute values of the elevations (Yp) from the highest peak to the fifth peak in the direction and the average of the absolute values of the elevations (Yv) of the valleys from the lowest valley floor to the fifth valley, This value is represented by the micrometer (micrometer).

[Equation 1]

In an embodiment, the molded article scans a 3 mm x 3 mm wide portion of the three-dimensional pattern, converts it into an image represented by 4900 pixels, and calculates the brightness of each pixel based on the CIE 1976 / CIE LAB color difference. The number of different brightness values calculated after measuring L ^* ) values may be about 30 to about 60, for example, about 30 to about 50. When the number of different brightness values is less than about 30, the color spectrum of the molded article may be too small to implement a fabric texture, and when it exceeds about 60, the fabric texture and beautiful appearance may be difficult.

In an embodiment, the molded article may be manufactured by injecting the thermoplastic resin composition by a conventional injection molding method using an injection molding machine applying a mold capable of implementing the three-dimensional pattern on at least one surface.

In embodiments, the injection may be carried out at an injection temperature of about 200 to about 320 ° C., for example about 210 to about 290 ° C., a mold temperature of about 40 to about 80 ° C., for example about 50 to about 70 ° C. . Within this range, molded articles having the three-dimensional pattern formed on at least one surface can be obtained.

The molded article according to the present invention can realize the appearance and natural texture similar to the actual fabric material, it is excellent in impact resistance, heat resistance, etc., interior / exterior materials, wallpaper, and the like, which require a high-quality appearance, and It can be used in the field of building exterior materials.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, it is presented as a preferred example of the present invention and should not be construed as limiting the present invention by any means.

Example

The specifications of each component used in the following Examples and Comparative Examples are as follows.

(A) thermoplastic resin

(a) polycarbonate resin

Bisphenol-A type polycarbonate resin (weight average molecular weight (Mw): 28,000 g / mol) was used.

(b1) Rubber modified vinyl graft copolymer

55 wt% of styrene and acrylonitrile (weight ratio: 75/25) were added to a butadiene rubber having a Z-average of 310 nm (45 Pa) by weight, and g-ABS was used.

(b2) Rubber modified vinyl graft copolymer

55 wt% of styrene and acrylonitrile (weight ratio: 75/25) were added to a butyl acrylate rubber having an average particle diameter of 45 nm by weight, and g-ASA was used.

(c) aromatic vinyl copolymer resin

SAN resin (weight average molecular weight: 130,000 g / mol) polymerized with 80% by weight of styrene and 20% by weight of acrylonitrile was used.

(B) colored particles

(B1) A needle-like carbon fiber (brightness value: 23) having an average particle size of 270 µm and an aspect ratio of cross section of 0.056 was used.

(B2) Needle-shaped cellulose particles (brightness value: 45) having an average particle size of 500 µm and an aspect ratio of a cross section of 0.03 were used.

(B3) Needle-shaped cellulose particles (brightness value: 28) having an average particle size of 3,000 mu m and an aspect ratio of a cross section of 0.033 were used.

(B4) A needle-shaped carbon fiber (brightness value: 23) having an average particle size of 150 µm and an aspect ratio of cross section of 0.33 was used.

(B5) Needle-shaped cellulose particles (brightness value: 27) having an average particle size of 3,300 µm and an aspect ratio of a cross section of 0.009 were used.

(B6) Needle-shaped cellulose particles (brightness value: 32) having an average particle size of 500 mu m and an aspect ratio of a cross section of 0.03 were used.

Example  1 to 3 and 10 to 12 and Comparative example  1, 2 and 7 to 10

According to the composition and content of Tables 1, 2 and 3, after mixing the components, L / D = 35, 45 mm diameter twin screw type extruder, melted and extruded at 220 ℃ Pellets were prepared. The prepared pellets were dried at 80 ° C. for at least 2 hours, and then injected at a injection temperature of 230 ° C. and a mold temperature of 60 ° C. using a 10 oz injection machine using a mold capable of realizing a three-dimensional pattern having a ten-point average roughness Rz of 401 μm. To prepare a specimen. The physical properties of the prepared specimens were evaluated by the following methods, and the results are shown in Tables 1, 2, and 3 below.

Example  4 to 9 and Comparative example  3 to 6 and 11

According to the composition and content of Tables 1, 2 and 3, after mixing the components, L / D = 35, 45 mm diameter twin screw type extruder, and melted and extruded at 260 ℃ Pellets were prepared. The prepared pellets were dried at 100 ° C. for at least 2 hours, and then injected at a injection temperature of 270 ° C. and a mold temperature of 60 ° C. using a 10 oz injection machine using a mold capable of realizing a three-dimensional pattern having a ten-point average roughness Rz of 401 μm. To prepare a specimen. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.

Comparative example  9

A specimen was prepared in the same manner as in Example 1, except that a mold capable of implementing a three-dimensional pattern having a 10-point average roughness Rz of 25 μm was applied. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Table 2 below.

Property measurement method

(1) Color Spectrum: For the specimens prepared in each of the Examples and Comparative Examples, a 3 mm x 3 mm wide portion of the three-dimensional pattern was scanned and converted into an image represented by 4900 pixels, and the CIE 1976 / Based on the CIE LAB chrominance reference, the brightness (L ^* ) value of each pixel was measured, and then the number of different brightness values was calculated.

(2) Evaluation of impact resistance: According to ASTM D256, the notched Izod impact strength (unit: kgf · cm / cm) of the 1/4 ”thickness specimen was measured.

(3) Heat resistance evaluation: Based on ASTMD648, heat distortion temperature (HDT, unit: degreeC) was measured on the conditions of 18.56 kgf / cm <^{2> of} loads and the temperature increase rate of 120 degreeC / hr.

		Example
		One	2	3	4	5	6
(A) (% by weight)	(a)	-	-	-	79	79	79
	(b1)	28	28	28	-	-	-
	(b2)	-	-	-	12.5	12.5	12.5
	(c)	72	72	72	8.5	8.5	8.5
(B) (part by weight)	(B1)	0.5	-	-	0.5	-	-
	(B2)	-	0.5	-	-	0.5	-
	(B3)	-	-	0.5	-	-	0.5
	(B4)	-	-	-	-	-	-
	(B5)	-	-	-	-	-	-
	(B6)	-	-	-	-	-	-
Brightness value of (A)		92	85	56	78	91	76
Brightness value of (B)		23	45	28	23	45	28
Brightness value difference		69	40	28	55	46	48
Color spectrum		49	49	50	48	47	49
Impact resistance		13.7	13.2	13.5	20.1	22	21.5
Heat resistance		88	87	87	113	113	112

* Parts by weight: parts by weight based on 100 parts by weight of the thermoplastic resin (A)

		Example
		7	8	9	10	11	12
(A) (% by weight)	(a)	89	89	89	-	-	-
	(b1)	4	4	4	28	28	28
	(b2)	-	-	-	-	-	-
	(c)	7	7	7	72	72	72
(B) (part by weight)	(B1)	0.5	-	-	0.1	1.5	0.5
	(B2)	-	0.5	-	-	-	-
	(B3)	-	-	0.5	-	-	0.3
	(B4)	-	-	-	-	-	-
	(B5)	-	-	-	-	-	-
	(B6)	-	-	-	-	-	-
Brightness value of (A)		93	91	84	84	92	72
Brightness value of (B)		23	45	28	23	23	23, 28
Brightness value difference		70	46	56	61	69	49, 44
Color spectrum		45	49	49	47	50	48
Impact resistance		12.5	10.4	10.3	15.2	12.2	14.3
Heat resistance		84	84	84	87	86	86

* Parts by weight: parts by weight based on 100 parts by weight of the thermoplastic resin (A)

		Comparative example
		One	2	3	4	5	6	7	8	9	10	11
(A) (% by weight)	(a)	-		79	79	89	89	-	-	-	-	79
	(b1)	28	28	-	-	4	4	28	28	28	28	-
	(b2)	-	-	12.5	12.5	-	-	-	-	-	-	12.5
	(c)	72	72	8.5	8.5	7	7	72	72	72	72	8.5
(B) (part by weight)	(B1)	-	-	-	-	-	-	0.01	5.5	0.5	-	-
	(B2)	-	-	-	-	-	-	-	-	-	-	-
	(B3)	-	-	-	-	-	-	-	-	-	-	-
	(B4)	0.5	-	0.5	-	0.5	-	-	-	-	-	-
	(B5)	-	0.5		0.5		0.5	-	-	-	-	-
	(B6)	-	-	-	-	-	-	-	-	-	0.5	0.5
Brightness value of (A)		84	86	81	75	93	71	75	86	74	36	39
Brightness value of (B)		23	27	23	27	23	27	23	23	23	32	32
Brightness value difference		61	59	58	48	70	44	52	63	51	2	7
Color spectrum		17	49	14	49	15	47	15	49	27	4	12
Impact resistance		13.5	8.5	20	18.5	10.7	11.2	17.7	4.3	13.5	13.7	21
Heat resistance		88	83	113	106	84	80	88	83	87	88	113

* Parts by weight: parts by weight based on 100 parts by weight of the thermoplastic resin (A)

From the above results, it can be seen that the molded article of the present invention has excellent impact resistance and heat resistance, and has a color spectrum of 30 to 60, which has a similar appearance (texture) to the actual fabric material (color spectrum: 42). .

On the other hand, in Comparative Examples 1, 3, and 5 in which colored particles (B4) having an average particle size of less than the range of the present invention are applied instead of the colored particles of the present invention, it can be seen that the color spectrum and the like are deteriorated. In Comparative Examples 2, 4, and 6 to which the colored particles (B5), which exceeded the scope of the invention, it was found that heat resistance and the like were deteriorated, and when the colored particles (B6) having a brightness difference of less than 10 were applied to the thermoplastic resin (comparatively). Examples 10 and 11), it can be seen that the color spectrum and the like is degraded. In addition, when the content of the colored particles is less than the range of the present invention (Comparative Example 7), it can be seen that the color spectrum and the like is reduced, and when exceeding the range of the present invention (Comparative Example 8), impact resistance, heat resistance and the like is lowered It can be seen that, when the 10-point average roughness Rz of the formed fine pattern projections is less than the range of the present invention (Comparative Example 9), it can be seen that the color spectrum and the like are deteriorated.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (10)

1. It is a molded article having a structure in which colored particles are dispersed in a thermoplastic resin,

   The colored particles have an average particle size of about 250 to about 3,200 μm as measured by a particle size analyzer, about 0.05 to about 5 parts by weight, based on about 100 parts by weight of the thermoplastic resin,

   A three-dimensional pattern is formed on at least one side of the molded article,

   The three-dimensional pattern has a ten-point average roughness Rz of about 50 to about 500 μm, and the 3 mm × 3 mm wide portion of the three-dimensional pattern is scanned at 600 dpi and converted into an image represented by 4900 pixels. And, based on the CIE 1976 / CIE LAB color difference, the number of different brightness values calculated after measuring the brightness (L ^* ) value of each pixel is about 30 to about 60.
2. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin comprises at least one of a polycarbonate resin and a rubber-modified aromatic vinyl copolymer resin.
3. The rubber-modified aromatic vinyl copolymer resin according to claim 2, wherein the rubber-modified aromatic vinyl copolymer resin is about 10 to about rubber-modified vinyl-based graft copolymer in which an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer are graft copolymerized into a rubbery polymer. 100 wt%; And about 0 to about 90% by weight of an aromatic vinyl monomer and an aromatic vinyl copolymer resin copolymerized with the monomer copolymerizable with the aromatic vinyl monomer.
4. The molded article according to any one of claims 1 to 3, wherein the colored particles have a difference in brightness value from the thermoplastic resin in a range of about 20 to about 99.
5. The molded article according to any one of claims 1 to 4, wherein the colored particles include at least one of cellulose and carbon fibers.
6. The molded article according to claim 1, wherein the aspect ratio of the colored particles is about 0.015 to about 0.08. 7.
7. The notched Izod according to any one of claims 1 to 6, wherein the molded article is a 1/4 '' thick specimen measured according to ASTM D256 when the thermoplastic resin is a diene rubber-modified aromatic vinyl copolymer resin. 1/4 "specimen measured in accordance with ASTM D256 when impact strength is about 9 to about 50 kgfcm / cm and thermoplastic resin is a combination of polycarbonate resin and diene rubber modified aromatic vinyl copolymer resin Notched Izod impact strength of about 15 to about 50 kgfcm / cm, and when the thermoplastic resin is a combination of polycarbonate resin and (meth) acrylate rubber modified aromatic vinyl copolymer resin, measured according to ASTM D256 A molded article characterized in that the notched Izod impact strength of a 1/4 "specimen is between about 9 and about 50 kgfcm / cm.
8. The said molded article is a load of 18.56 kgf / cm <^2> and a temperature increase rate of 120 degreeC based on ASTMD648, when the thermoplastic resin is a diene rubber modified aromatic vinyl copolymer resin. When the heat deflection temperature (HDT) measured under the conditions of / hr is about 82 to about 125 ° C, and the thermoplastic resin is a combination of a polycarbonate resin and a diene rubber-modified aromatic vinyl copolymer resin, the load according to ASTM D648 The heat deflection temperature (HDT) measured at the conditions of 18.56 kgf / cm <^2> , the temperature increase rate of 120 degree-C / hr is about 108-125 degreeC, and a thermoplastic resin is a polycarbonate resin and a (meth) acrylate rubber modified aromatic vinyl type air In the case of a combination of the copolymer resin, the molded article, characterized in that the heat deflection temperature (HDT) measured in the conditions of load 18.56 kgf / cm ² , heating rate 120 ℃ / hr in accordance with ASTM D648 is about 82 to about 125 ℃.
9. Injecting the thermoplastic resin composition in an injection molding machine to which a mold capable of realizing a three-dimensional pattern having a ten-point average roughness Rz of about 50 to about 500 μm on at least one surface thereof is applied.

   The thermoplastic resin composition comprises about 100 parts by weight of a thermoplastic resin, and about 0.05 to about 5 parts by weight of colored particles having an average particle size of about 250 to about 3,200 μm measured by a particle size analyzer.
10. The method of claim 9, wherein the injection is performed at an injection temperature of about 200 to about 320 ° C., and a mold temperature of about 40 to about 80 ° C. 11.