KR20220092004A - Long fiber-reinforced thermoplastic resin composition with feeling of Korean traditional paper, and a method for preparing the same and molded article comprising the same - Google Patents

Abstract

The present invention relates to a long fiber-reinforced thermoplastic resin composition, a preparation method thereof, and a molded article comprising the same, and more particularly, to a long fiber-reinforced thermoplastic resin composition which comprises a thermoplastic resin, long glass fiber, and mica in a specific content ratio and is prepared by impregnating a resin mixture including the thermoplastic resin and mica with the glass long fiber under specific conditions so that the long fiber-reinforced thermoplastic resin composition has excellent appearance and gloss while maintaining excellent mechanical strength (impact strength), and in particular, can improve the aesthetics of a product by exhibiting the texture of Korean traditional paper on the appearance, a preparation method thereof, a molded article comprising the same.

Description

Long fiber-reinforced thermoplastic resin composition with feeling of Korean traditional paper, and a method for preparing the same and molded article comprising the same

The present invention relates to a long fiber-reinforced thermoplastic resin composition, a manufacturing method thereof, and a molded article including the same, and more particularly, to a thermoplastic resin, glass filament, and mica in a specific content ratio, including the thermoplastic resin and mica It is manufactured by impregnating the long glass fiber with a resin mixture under specific conditions, and has excellent appearance and gloss while maintaining excellent mechanical strength (impact strength). It relates to a long-fiber-reinforced thermoplastic resin composition that can be made, a method for manufacturing the same, and a molded article comprising the same.

As polymer materials become more functional, functional, and diversified, they have reached a level where they can replace metals in certain industrial fields. However, in order to realize a performance that cannot be expressed by a polymer material alone, a long fiber reinforced thermoplastic resin (LFT), which is a composite material with high impact and high stiffness, is being developed.

Specifically, long fiber reinforced composite materials such as Glass Fiber Reinforced Plastic (GFRP) Composite Material and Carbon Fiber Reinforced Plastic (CFRP) Composite Material are used as reinforcement. Manufactured by impregnating phosphor fiber with a matrix, and exhibiting excellent mechanical properties despite its low specific gravity compared to metal materials This is expanding.

However, when a product is manufactured using the existing long fiber-reinforced thermoplastic resin composition, the long fiber protrusion occurs due to aggregation of the long fiber, which is a reinforcing agent, resulting in a poor appearance. Conventionally, in order to solve the defect of the appearance and improve the aesthetics of the appearance, the length of the long fiber was adjusted and improved, but in this case, there was a problem in that the mechanical properties of the product were lowered.

Therefore, as a long-fiber-reinforced plastic composite material, there is a demand for the development of a long-fiber-reinforced thermoplastic resin composition with improved appearance while maintaining excellent mechanical properties such as impact strength and rigidity.

An object of the present invention is to provide a long-fiber-reinforced thermoplastic resin composition capable of exhibiting excellent mechanical properties, such as impact strength and rigidity, and at the same time, excellent appearance, a method for manufacturing the same, and a molded article including the same.

In order to solve the above technical problem, the present invention, based on 100 parts by weight of the total composition, (A) 19 to 92 parts by weight of a thermoplastic resin; (B) 6 to 79 parts by weight of long glass fibers; and (C) 0.2 to 4.9 parts by weight of mica; it is prepared by impregnating the glass filament with a resin mixture including the thermoplastic resin and mica, wherein the impregnation is, Spreading Bar 4 to 10 Provided is a long fiber reinforced thermoplastic resin composition carried out in an impregnation apparatus having a dog.

According to another aspect of the present invention, (1) melting a resin mixture comprising a thermoplastic resin and mica; and (2) impregnating the glass filament with the melt obtained in step (1) to prepare a long fiber reinforced thermoplastic resin composition; It is carried out in an impregnation device having 10 pieces, and the prepared long fiber reinforced thermoplastic resin composition is, based on 100 parts by weight of the total composition, 19 to 92 parts by weight of the thermoplastic resin; 6 to 79 parts by weight of the long glass fiber; and 0.2 to 4.9 parts by weight of the mica; it provides a method for producing a long fiber reinforced thermoplastic resin composition comprising.

According to another aspect of the present invention, there is provided a molded article comprising the long fiber reinforced thermoplastic resin composition of the present invention.

The long-fiber-reinforced thermoplastic resin composition according to the present invention maintains excellent mechanical properties (impact strength, etc.) inherent in the long-fiber-reinforced plastic composite material, and at the same time has excellent appearance and luster, in particular, it shows the texture of Korean paper in appearance. It can improve the aesthetics of the product.

1 is a diagram schematically showing the structure of an impregnating device that can be used for manufacturing a long fiber-reinforced thermoplastic resin composition of the present invention according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The long fiber reinforced thermoplastic resin composition of the present invention comprises (A) a thermoplastic resin; (B) long glass fibers; and (C) mica;

(A) Thermoplastic resin

As the thermoplastic resin included as a basic resin component in the long fiber-reinforced thermoplastic resin composition of the present invention, a thermoplastic resin commonly used in this field may be used without particular limitation, and the thermoplastic resin may be a crystalline, semi-crystalline or amorphous resin can be

In one embodiment, the thermoplastic resin may be selected from the group consisting of polypropylene resin, polyamide, polycarbonate, polyurethane, polyphenylene sulfide, or a combination thereof, and more specifically, polypropylene resin , more specifically, a high crystallinity polypropylene resin may be used.

In the long fiber-reinforced thermoplastic resin composition of the present invention, the thermoplastic resin is included in an amount of 19 to 92 parts by weight based on 100 parts by weight of the total composition. If the content of the thermoplastic resin in the total 100 parts by weight of the composition is less than 19 parts by weight, the appearance of the composition is poor due to the protrusion of the relatively excessive long glass fibers. The impact resistance of the composition is poor, and the appearance of the Korean paper texture cannot be obtained.

More specifically, the content of the thermoplastic resin in the resin composition based on a total of 100 parts by weight of the long fiber-reinforced thermoplastic resin composition of the present invention is 19 parts by weight or more, 20 parts by weight or more, 21 parts by weight or more, 22 parts by weight or more, 23 parts by weight or more. or more, 24 parts by weight or more, 25 parts by weight or more, 26 parts by weight or more, 27 parts by weight or more, or 28 parts by weight or more, and also 92 parts by weight or less, 91 parts by weight or less, 90 parts by weight or less, 89 parts by weight or less; 88 parts by weight or less, 87 parts by weight or less, 86 parts by weight or less, 85 parts by weight or less, 84 parts by weight or less, or 83 parts by weight or less.

(B) long glass fiber

The long glass fiber may be derived from a glass long fiber roving converged with an epoxy resin or the like, and passing the glass long fiber roving through an impregnation device containing a resin mixture including the thermoplastic resin and mica to be described later. After impregnating the fiber with the resin mixture, for example, it may be included in the long fiber-reinforced thermoplastic resin composition of the present invention by cutting it into pellets, and thus, the long glass fiber included in the resin composition has a length corresponding to the long axis of the pellet. will have

In one embodiment, the glass long fiber included in the long fiber-reinforced thermoplastic resin composition of the present invention may have a length of 5 to 30 mm, and more specifically, have a length of 10 to 25 mm, or 15 to 20 mm. However, it is not limited thereto, and the length may be varied according to the purpose of use.

In addition, the glass long fiber may have various diameters, for example, the diameter may be 10 μm to 20 μm, or 10 μm to 15 μm, but is not limited thereto, and glass long fibers of various diameters may be used according to the purpose of use. can be used

In addition, as the long glass fiber, a flat glass long fiber may be used, and the aspect ratio (aspect ratio) thereof may vary depending on the purpose of use. In one embodiment, the aspect ratio of the flat glass long fiber may be 1:2 to 1:8, more specifically, 1:3 to 1.6, or 1:3 to 1:4.

In one embodiment, the long glass fiber may be surface-treated, and in this case, a silane-based polymer, titanate-based polymer, polyamide-based polymer, polyurethane-based polymer, or a combination thereof, which are commonly used as a surface treatment agent, may be used. and if a plurality of surface treatment agents are used, at least one of them is preferably a surface treatment agent having good affinity with the thermoplastic resin.

In the long fiber-reinforced thermoplastic resin composition of the present invention, the glass long fiber is included in an amount of 6 to 79 parts by weight based on 100 parts by weight of the total composition. If the content of long glass fibers in 100 parts by weight of the composition is less than 6 parts by weight, the impact resistance of the composition is poor and the appearance of the Korean paper texture cannot be obtained. becomes

More specifically, the content of long glass fibers in the resin composition based on a total of 100 parts by weight of the long fiber-reinforced thermoplastic resin composition of the present invention is 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more. parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, or 15 parts by weight or more, and also 79 parts by weight or less, 78 parts by weight or less, 77 parts by weight or less, 76 parts by weight or less , 75 parts by weight or less, 74 parts by weight or less, 73 parts by weight or less, 72 parts by weight or less, 71 parts by weight or less, or 70 parts by weight or less.

(C) Mica

The mica contained in the long fiber reinforced thermoplastic resin composition of the present invention is used to impart gloss to the appearance of a molded article prepared from the resin composition of the present invention, to impart color if necessary, and to improve mechanical strength. used

In one embodiment, the mica may be selected from white mica, colored mica, or a mixture thereof.

In one embodiment, the colored mica may be selected from brown mica, black mica, gold mica, or a mixture thereof.

The mica may have various diameters, for example, the diameter may be 1 μm to 20 μm, or 2 μm to 15 μm, but is not limited thereto, and mica of various diameters may be used depending on the purpose of use.

In addition, the refractive index of the mica may be, for example, 1.2 to 2.0, 1.5 to 2.0, or 1.5 to 1.7, but is not limited thereto.

In the long fiber-reinforced thermoplastic resin composition of the present invention, the mica is included in an amount of 0.2 to 4.9 parts by weight based on 100 parts by weight of the total composition. If the mica content in 100 parts by weight of the composition is less than 0.2 parts by weight, the effect of imparting gloss to the appearance of the composition is insignificant, and if it exceeds 4.9 parts by weight, the glossiness of the composition is rather reduced and the impact resistance is poor.

More specifically, the content of mica in the resin composition based on a total of 100 parts by weight of the long fiber reinforced thermoplastic resin composition of the present invention is 0.2 parts by weight or more, 0.5 parts by weight or more, 0.7 parts by weight or more, 1 parts by weight or more, 1.2 parts by weight or more. , 1.5 parts by weight or more, 1.7 parts by weight or more, or 2 parts by weight or more, and also 4.9 parts by weight or less, 4.8 parts by weight or less, 4.5 parts by weight or less, 4.3 parts by weight or less, 4 parts by weight or less, 3.8 parts by weight or less, 3.5 It may be less than or equal to 3.3 parts by weight, or less than or equal to 3 parts by weight.

In addition to the above-mentioned components, one or more other additives may be added to the long fiber-reinforced thermoplastic resin composition of the present invention as needed within a range capable of achieving the object of the present invention. The type of these other additives is not particularly limited, and additives commonly used in the thermoplastic resin composition may be used without limitation.

In one embodiment, the long fiber-reinforced thermoplastic resin composition of the present invention is an antioxidant, an inorganic filler, a compatibilizer, a lubricant, a neutralizer, a nucleating agent, a heat stabilizer, a light stabilizer, a hydrolysis stabilizer, a UV stabilizer, a release agent, a colorant, a brightener, an electrification agent It may further include an additive selected from the group consisting of an inhibitor, a conductivity-imparting agent, a magnetism-imparting agent, a crosslinking agent, an antibacterial agent, a processing aid, an anti-friction agent, an anti-wear agent, a coupling agent, an anti-drip agent, or mixtures thereof.

The content of the other additives is not particularly limited, and may be used up to 5 parts by weight, for example, within the range of about 0.5 to 5 parts by weight, based on 100 parts by weight of the resin composition of the present invention, depending on the purpose and use.

The long fiber-reinforced thermoplastic resin composition of the present invention is prepared by impregnating the glass fiber with a resin mixture comprising the above-described thermoplastic resin and mica, and optionally further comprising an additional additive, wherein the impregnation is a spreading bar (Spreading bar). Bar) carried out in an impregnation apparatus with 4 to 10 bars. The spreading bar serves to spread the aggregated long glass fibers in the impregnation device.

Accordingly, according to another aspect of the present invention, (1) melting a resin mixture comprising a thermoplastic resin and mica; and (2) impregnating the glass filament with the melt obtained in step (1) to prepare a long fiber reinforced thermoplastic resin composition; It is carried out in an impregnation device having 10 pieces, and the prepared long fiber reinforced thermoplastic resin composition is, based on 100 parts by weight of the total composition, 19 to 92 parts by weight of the thermoplastic resin; 6 to 79 parts by weight of the long glass fiber; and 0.2 to 4.9 parts by weight of the mica; it provides a method for producing a long fiber reinforced thermoplastic resin composition comprising.

In manufacturing the long fiber reinforced thermoplastic resin composition by passing the glass fiber roving through an impregnation device containing the resin mixture while pulling and squeezing, conventionally, it is considered bad that the glass fiber roving is less dispersed in the impregnation device due to aggregation. and an impregnation device having 11 or more spreading bars was used to remove such agglomeration of long glass fibers. However, in the present invention, as a counter idea to this conventional recognition, a long fiber-reinforced thermoplastic resin composition having a texture of Korean paper by inducing aggregation of glass fibers rather by using an impregnation device having 4 to 10 spreading bars. can provide

In the preparation of the long fiber reinforced thermoplastic resin composition of the present invention, if the number of spreading bars in the impregnation device is less than 4, the aggregation of the glass long fibers is severe, and the appearance of the composition is poor due to the protrusion of the aggregated long glass fibers. Conversely, if the number of spreading bars in the impregnation device exceeds 10, long glass fibers are not sufficiently aggregated, so that the appearance of the Korean paper texture cannot be obtained.

In one embodiment, the number of spreading bars in the impregnation device may be 4 or more or 5 or more, and may also be 10 or less, 9 or less, 8 or less, or 7 or less. In a preferred embodiment, the number of spreading bars in the impregnation device may be 5 to 7.

According to another aspect of the present invention, there is provided a molded article comprising the long fiber reinforced thermoplastic resin composition of the present invention.

The molded article may be manufactured by molding the long fiber-reinforced thermoplastic resin composition of the present invention by extrusion, injection, or other known processing.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

[Examples and Comparative Examples]

The components used in the following Examples and Comparative Examples are specifically as follows.

(A): Thermoplastic resin

High crystalline polypropylene (PP) resin having a melt index of 250 g/10 min measured at a temperature of 230°C and a load of 2.16 kg

(B): Glass long fiber

As a reinforcing agent, a glass long fiber roving having a diameter of 10 μm to 15 μm, condensed with an epoxy resin, and having a filament number of 2,000.

(C-1): white mica

White mica having a refractive index of 1.5 to 1.7 and a diameter of 2 to 10 μm

(C-2): brown mica

Brown mica having a refractive index of 1.5 to 1.7 and a diameter of 2 to 10 μm

(C-3): black mica

Black mica having a refractive index of 1.5 to 1.7 and a diameter of 2 to 10 μm

(C-4): gold mica

Gold mica having a refractive index of 1.5 to 1.7 and a diameter of 2 to 10 μm

<Production of Long Fiber Reinforced Thermoplastic Resin Composition>

Examples 1 to 8 and Comparative Examples 1 to 7

A resin mixture was prepared by mixing (A) polypropylene resin and (C) mica with the composition shown in Table 1 below, and the resin mixture was put into a twin-screw extruder having a cylinder temperature of 230° C. and 200 RPM, and melted and melted. A resin mixture was obtained, and the molten resin mixture was put into the resin injection part of the pultrusion device, and while passing it through a die, pulling and squeezing the (B) glass fiber in the roving form, the final product A long fiber-reinforced thermoplastic resin composition was prepared (the long-fiber-reinforced thermoplastic resin composition has a form in which glass filaments are impregnated with a resin mixture). At this time, (B) the number of spreading bars in the impregnation apparatus in which the impregnation of the molten resin mixture for the glass filament is performed was changed as shown in Table 1.

In the impregnated state, the continuous glass fiber strand was pulled out (pultrusion), passed through a water bath, cooled, and cut into pellets having a length of 15 mm to prepare long fiber reinforced thermoplastic resin pellets.

After drying the prepared pellets with hot air at 80° C. for 4 hours or more, injection molding was performed at a temperature of 235° C. to prepare a specimen. In this case, the injection molding machine (LGH-200N, LG Cable Co., Ltd.) was used. The physical properties of the prepared specimens were measured in the following way, and the results are shown in Table 1 below.

At this time, the specimen for measuring the impact strength was cut to the size of 64mm x 12.7mm x 6.4mm (length x width x thickness), and the specimen for measuring the appearance was cut to the size of 50mm x 80mm x 3mm (length x width x thickness).

<Method of measuring physical properties>

(1) IZOD impact strength (impact resistance) (J/m)

Based on ASTM D256, the IZOD impact strength was evaluated at room temperature (23° C.) by making a notch in each specimen of Examples and Comparative Examples. The higher the IZOD impact strength, the higher the impact resistance of the specimen.

(2) Appearance characteristics (esthetics)

1) Appearance: As a result of visually observing the surface of the specimen for measuring the appearance, it was determined whether the surface protruded to the outside.

- Good: As a result of visual observation, the surface of the specimen does not protrude to the outside and is in a smooth state.

- Defect: As a result of visual observation, the surface of the specimen protrudes to the outside and is not smooth

2) Number of patterns: As a result of visually observing the surface of the specimen for measuring the appearance, the number of long glass fibers that had a pattern similar to that of Korean paper on the surface was counted.

3) Color: The color of the surface of the specimen for measuring the appearance was observed with the naked eye.

4) Glossiness: The glossiness of the specimen for measuring the appearance was measured using a gloss meter (BYK micro-TRI-gloss, BYK Gardenr (manufactured by BYK)). At this time, the glossiness is measured from 0 to 100, and the higher the value, the higher the glossiness.

As shown in Table 1, in the case of the long fiber-reinforced thermoplastic resin compositions of Examples 1 to 8 according to the present invention, while exhibiting excellent impact resistance, the external surface was smooth, and the surface pattern of the Korean paper texture was displayed, and the white Various colors such as , brown, black, and gold can be produced, and the luster is also excellent, so that balanced physical properties can be secured.

However, in the case of Comparative Example 1, which is a conventional long fiber reinforced thermoplastic resin composition, the impact resistance was poor, the surface pattern of the Korean paper texture could not be displayed, and the esthetic was poor due to poor glossiness.

In addition, in the case of Comparative Example 2, in which the glass long fiber was used below the range specified in the present invention, the impact resistance was very poor, the surface pattern of the Korean paper texture was not shown, and the glass long fiber was used in excess of the range specified in the present invention. In the case of Comparative Example 3, the appearance was poor due to the protrusion of the external surface, resulting in poor overall aesthetics.

In addition, in the case of Comparative Example 4 in which mica was used in less than the range set in the present invention, the gloss was poor, and in Comparative Example 5 in which the mica was used in excess of the range set in the present invention, the gloss was not only poor , and the impact resistance was also poor.

In addition, in the case of Comparative Example 6, in which the number of spreading bars in the impregnation apparatus was less than the range set in the present invention, the aggregation of the glass filaments was severe and the appearance was poor, such as the surface protruding, and the number of spreading bars in the impregnation apparatus was the present invention In the case of Comparative Example 7, which exceeded the range specified in , the impact resistance was poor, and in particular, the esthetic was poor because the surface pattern of the Korean paper texture could not be displayed.

10: fiber inlet
20: first resin inlet
30: impregnation device body
31: Spreading Bar

Claims (8)

Based on 100 parts by weight of the total composition,
(A) 19 to 92 parts by weight of a thermoplastic resin; (B) 6 to 79 parts by weight of long glass fibers; and (C) 0.2 to 4.9 parts by weight of mica;
It is prepared by impregnating a resin mixture containing the thermoplastic resin and mica into the glass long fiber,
The impregnation is carried out in an impregnation apparatus having 4 to 10 Spreading Bars,
A long fiber reinforced thermoplastic resin composition. The long fiber reinforced thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is selected from the group consisting of polypropylene resin, polyamide, polycarbonate, polyurethane, polyphenylene sulfide, or a combination thereof. The long fiber reinforced thermoplastic resin composition according to claim 1, wherein the mica is selected from white mica, colored mica, or a mixture thereof. The long fiber reinforced thermoplastic resin composition according to claim 3, wherein the colored mica is selected from brown mica, black mica, gold mica, or a mixture thereof. The long fiber reinforced thermoplastic resin composition according to claim 1, wherein the number of spreading bars in the impregnation device is 5 to 7. (1) melting a resin mixture comprising a thermoplastic resin and mica; and
(2) preparing a long fiber reinforced thermoplastic resin composition by impregnating the glass fiber with the melt obtained in step (1) above;
Here, the impregnation is carried out in an impregnation device having 4 to 10 spreading bars,
The prepared long fiber-reinforced thermoplastic resin composition, based on a total of 100 parts by weight of the composition, 19 to 92 parts by weight of the thermoplastic resin; 6 to 79 parts by weight of the long glass fiber; and 0.2 to 4.9 parts by weight of the mica;
A method for producing a long fiber reinforced thermoplastic resin composition. The method for producing a long fiber reinforced thermoplastic resin composition according to claim 6, wherein the number of spreading bars in the impregnation device is 5 to 7. A molded article comprising the long fiber-reinforced thermoplastic resin composition of any one of claims 1 to 5.

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