KR102298369B1 - Thermoplastic resin composition capable of realizing a fabric-like appearance and feel and a molded article comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition capable of implementing a fabric-like appearance and feel, and a molded article comprising the same, and more particularly, to a cellulose fiber for expressing a fabric-like appearance, a silicone masterbatch for imparting a fabric-like feel, and It relates to a thermoplastic resin composition having a fabric-like appearance and feel by including a thermoplastic resin, and a molded article comprising the same.

Description

Thermoplastic resin composition capable of realizing a fabric-like appearance and feel and a molded article comprising the same

The present invention relates to a thermoplastic resin composition capable of implementing a fabric-like appearance and feel, and a molded article comprising the same.

Recently, as the era of human-centered technology arrives, the satisfaction of consumers' sensibility is causing changes in consumer needs, and the paradigm of the industry is demanding a change. In the past, the industrial paradigm of technology push is changing to human-centered (demand pull). is being converted In recent years, as the importance of technology has been maintained, human emotions are acting as an important determinant of purchasing. Accordingly, companies began to build “emotional power” that affects the emotions of buyers, such as design, touch, and UI (User Interface).

Visual and tactile senses play a very large role in stimulating consumer sensibility. What is important from a consumer's visual point of view is to realize a feeling of appearance similar to that of natural materials. It can be said that a fabric material technology that can realize the color and appearance characteristics of natural materials such as fiber, marble, and wood without an additional painting process is very rare, and such a fabric material can be used in various fields. In addition, if the tactile effect when the injection product is touched is similar to the fabric, it can stimulate consumers in terms of tactile feel. However, until now, there is no known material that realizes the appearance of the fabric material and similarly implements the texture of the fabric at the same time.

One of the fields of application of fabric materials is injection molding using thermoplastic resins. After injection molding, thermoplastic resins are manufactured into various products, including electrical and electronic products and automobile parts, and delivered to consumers. After injection molding, the exterior of the product is designed by painting and spraying, which is environmentally harmful and uneconomical due to the additional cost of painting processing. Accordingly, as the demand for eco-friendly unpainted materials increases, there is an increasing demand for fabric materials capable of implementing the fiber texture appearance and feel similar to natural appearance powder coating with the material itself without a painting process.

Recently, the development of a fabric material containing cellulose particles in a thermoplastic resin is continuously progressing, but in the case of an existing fabric material, there is a problem that it only has a general smooth plastic feeling when touched, and cannot realize the fiber feel. In addition, with the currently known technology, it is not easy to improve the fiber texture in researching a material that is similar to the appearance of a natural material and has a perfect fiber texture after injection molding. There is a problem in that there is a limitation in material development because a method for evaluating sexuality has not been established.

Therefore, there is an urgent need to develop a thermoplastic resin composition for interior and exterior materials that can simultaneously improve the fiber-like appearance and tactile properties compared to existing products by realizing an appearance that is visually similar to the fiber texture and at the same time adding a touch similar to the fiber. am. In addition, it is a reality that requires a study on a fiber texture evaluation method that can evaluate the fiber index in the resin composition.

3D printer technology, which has recently become a hot topic, is being applied in various ways in the overall industry including the electronics industry, the semiconductor industry, and the automobile industry. The combination of 3D printer technology and natural textured fabric material is becoming more necessary as customer needs for environmentally friendly materials increase. Therefore, it is necessary to develop a fabric-like thermoplastic resin composition that can be used for 3D printing filaments while satisfying the needs of consumers.

In order to solve the above problems, the present invention provides a thermoplastic resin composition having a fabric-like appearance and feel by including a cellulose fiber for expressing a fabric-like appearance, a silicone masterbatch for imparting a fabric-like feel, and a thermoplastic resin, and An object of the present invention is to provide a molded article including the same.

In order to solve the above technical problem, the present invention, based on 100% by weight of the total composition, (A) 60 to 90% by weight of thermoplastic resin, (B) 0.1 to 30% by weight of cellulose fiber and (C) 6 to 20 silicone masterbatch It provides a thermoplastic resin composition comprising % by weight.

According to another aspect of the present invention, there is provided a molded article including the thermoplastic resin composition.

The thermoplastic resin composition according to the present invention can realize the appearance and tactile effect of a fabric-like material superior to that of the conventional thermoplastic composition. Therefore, the thermoplastic resin composition of the present invention can be used in molded articles applied to the interior and exterior of various products, and further can be used as a filament for 3D printing.

1 is a photograph comparing and evaluating the case of using a dye-divided-type cellulose fiber and a semi-dyed-type cellulose fiber of the same color in a specimen prepared from a thermoplastic resin composition of the present invention.
Figure 2 shows the evaluation criteria of the filament moldability for 3D printing of the thermoplastic resin composition of the present invention.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention, based on 100% by weight of the total composition, (A) 60 to 90% by weight of the thermoplastic resin, (B) 0.1 to 30% by weight of cellulose fibers and (C) 6 to 20% by weight of the silicone masterbatch As a thermoplastic resin composition comprising, when a molded article is manufactured by using the thermoplastic resin composition of the present invention, it is possible to realize the appearance and tactile effect of a fabric-like material superior to that of the existing thermoplastic composition.

(A) Thermoplastic resin

Cellulose fibers and silicone masterbatch to be described later may be dispersed in the thermoplastic resin used in the present invention. The thermoplastic resin may have a processing temperature of 300° C. or less, for example, 250° C. or less or 100 to 250° C. If the processing temperature exceeds 300 ℃, there is a problem that a part of the cellulose fibers included together during injection molding is melted or decomposed, so that the effects of the present invention cannot be sufficiently implemented.

The thermoplastic resin of the present invention is not particularly limited, but acrylonitrile-butadiene-styrene (ABS) resin, modified acrylonitrile-butadiene-styrene (mABS) resin, polyolefin resin such as polyethylene and polypropylene, polyether ether ketone (PEEK) resin, modified polyphenylene ether (mPPE) resin, polymethyl methacrylate (PMMA) resin, polybutylene terephthalate (PBT) resin, or one selected from the group consisting of a combination thereof may be used. For example, acrylonitrile-butadiene-styrene (ABS) resin or polyolefin resin may be used.

When an acrylonitrile-butadiene-styrene (ABS) resin or polypropylene is used, the heat resistance temperature limitation of the cellulose fiber is relatively less, so that it can be processed in a wider temperature range.

The content of the thermoplastic resin used in the present invention may be 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight or more, or 80% by weight or more, 90% by weight or less, based on 100% by weight of the total composition; 88 wt% or less, 86 wt% or less, 85 wt% or less, or 83 wt% or less, for example, 60 to 90 wt%, 65 to 88 wt%, or 75 to 88 wt%. When the content of the thermoplastic resin is less than the above range, there may be a problem of resin heat resistance and a decrease in strength. Conversely, when the content of the thermoplastic resin is higher than the above range, the content of cellulose fibers and silicon masterbatch is relatively reduced, such as fiber properties and filament properties. The physical properties may be deteriorated.

(B) Cellulose fibers

Cellulose fibers may be broadly divided into two types of cellulose fibers: a dye-divided type cellulose fiber and a semi-dyed-type cellulose fiber. In the case of transfer dye type cellulose fiber, it has the effect of transferring the color of the entire base resin to the color of the fiber. can

Therefore, the cellulose fiber used in the present invention may use a dichromatic type cellulose fiber, a semi-dyed type cellulose fiber, or a mixture thereof, for example, a mixture of two or more types of fibers may be used. If you mix and use the color transfer type and the half transfer color type, you can give various color effects by mixing the color of the entire color and mixing the unique color of cellulose.

The cellulose fiber used in the present invention is not particularly limited in its shape, but may be in the form of a fiber, and may be, for example, needle-shaped. The diameter (D50) may be 6 μm or more, 7 μm or more, 8 μm or more, 9 μm or more, or 10 μm or more, 14 μm or less, 13 μm or less, 12 μm or less, 11 μm or less, or 10 μm or less, For example, it may be 6 to 14 μm, 8 to 12 μm, or 9 to 11 μm. If the diameter of the cellulose fiber is out of the above range, fiber properties and filament properties may be poor.

In addition, the cellulose fiber of the present invention may have a length of 0.2 mm or more, 0.5 mm or more, 0.8 mm or more, 1.0 mm or more, or 1.2 mm or more, and 2 mm or less, 1.8 mm or less, 1.5 mm or less, or 1.3 mm or less. may be, for example, 0.2 to 2 mm, 0.5 to 1.8 mm, or 0.6 to 1.5 mm. When the length of the cellulose fiber is less than the above range, the fiber does not appear well on the surface of the resin, so it may be difficult to realize fiber properties or the effect of combining two or more types of cellulose fibers. It may appear too large and cause an unnatural feeling.

The average aspect ratio of the cellulosic fibers can be 0.1 or more, 0.15 or more, 0.18 or more, 0.2 or more, 0.22 or more, or 0.25 or more, and 1.0 or less, 0.8 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.35 or less, 0.32 or less, 0.3 or less, or It may be 0.28 or less, for example, 0.15 to 0.35, 0.18 to 0.32, or 0.2 to 0.3. When the average aspect ratio is out of the above range, there is a problem in that a natural appearance cannot be formed due to the shape of the particles. Here, the average aspect ratio of the fibers is the average of the ratio of the longest axis diameter to the shortest axis diameter of each cross section of the fibers.

The heat resistance of the cellulose fiber of the present invention may be 300 ℃ or less, 290 ℃ or less, 280 ℃ or less, 270 ℃ or less, 260 ℃ or less, 250 ℃ or less, 200 ℃ or more, 210 ℃ or more, 220 ℃ or more, 230 ℃ or less or more, it may be 240° C. or more. For example, it may be 200 °C to 300 °C, preferably 240 °C to 300 °C. If it exceeds 300 ℃, problems such as thermal decomposition and thermal discoloration occur during extrusion or injection molding.

The content of cellulose fibers used in the present invention may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 1.5% by weight or more, or 2% by weight or more, and 30% by weight or less, based on 100% by weight of the total composition; 20% by weight or less, 10% by weight or less, 5% by weight or less, or 4% by weight or less, for example, 0.1 to 30% by weight, 0.5 to 15% by weight, or 1 to 5% by weight. When the content of the cellulose fiber is less than the above range, contractility and spider silk properties among the filament properties may be reduced.

(C) Silicon masterbatch

Silicone masterbatch exists in the form of a mixture of siloxane polymer and resin, and depending on the type of base resin to be used, low-density polyethylene, high-density polyethylene, ethylene vinyl acetate copolymer, thermoplastic polyester elastomer, acrylonitrile- It can be prepared by dispersing the siloxane polymer in a resin selected from the group consisting of butadiene-styrene resin, polypropylene, polyethylene terephthalate, or a combination thereof.

The content of the silicone masterbatch used in the present invention may be 5.5 wt% or more, 6 wt% or more, 7 wt% or more, 8 wt% or more, 9 wt% or more, or 10 wt% or more, based on 100 wt% of the total composition, and , 20 wt% or less, 19 wt% or less, 18 wt% or less, 17 wt% or less, or 16 wt% or less, for example, 5.5 to 20 wt%, 6 to 20 wt%, 8 to 18 wt% or It may be 10 to 15% by weight. If the content of the silicon masterbatch is less than the above range, the fiber properties may be poor, and conversely, if the content is more than the above range, fluidity and rigidity may be reduced.

(D) additives

In addition to the components (A), (B) and (C) described above, the thermoplastic resin composition of the present invention may further include one or more other additives commonly added to the thermoplastic resin composition for injection molding or extrusion molding. That is, the thermoplastic resin composition of the present invention may further include an additive selected from the group consisting of a light diffusing agent, an antioxidant, a lubricant, an ultraviolet absorber, a light stabilizer, an impact modifier, a matting agent, a flame retardant, or a combination thereof. .

Specifically, the light diffusing agent may serve to assist the effect of improving the flow mark, for example, a silicone-based light diffusing agent, an acrylic light diffusing agent, a polystyrene-based light diffusing agent, or a mixture of two or more thereof. etc. may be used.

Specifically, as the antioxidant, phenol-based, phosphite-based, thioester-based, or a mixture of two or more thereof may be used.

Specifically, as the lubricant, polyethylene, ethylene-ester, ethylene glycol-glycerin ester, montan, ethylene glycol-glycerin-montanic acid ester, or a mixture of two or more thereof may be used.

The ultraviolet absorber is not particularly limited, and commercially available products may be used.

Specifically, as the light stabilizer, a benzotriazole-based compound, a hydroxyphenyltriazine-based compound, a pyrimidine-based compound, a cyanoacrylate-based compound, or a mixture of two or more thereof may be used.

Specifically, as the impact modifier, a methacrylate butadiene stylene (MBS)-based impact modifier having a core-shell structure, an acrylic-based impact modifier, a silicone-based impact modifier, and a chlorinated polyethylene (CPE)-based impact modifier may be used, but is not limited thereto.

Specifically, an inorganic compound or an organic compound may be used as the matting agent, and silica, magnesium oxide, zirconia, alumina, titania, or a mixture of two or more thereof may be used as the inorganic compound, and the organic compound is cross-linked A vinyl-based copolymer may be used, and the monomer of the vinyl-based copolymer is at least one monomer selected from styrene, acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate. can be

The content of the other additives is not particularly limited, and is an amount that can be used to add additional functions within a range that does not impair the desired physical properties of the thermoplastic resin composition of the present invention.

According to one embodiment of the present invention, the content of the other additives may be 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the thermoplastic resin in the resin composition of the present invention. When the content of the other additives is less than 0.1 parts by weight, the effect of improving various functions according to the use of the other additives may be insignificant, and when the content of the other additives is more than 5 parts by weight, mechanical properties may be poor.

According to another aspect of the present invention, there is provided a molded article including the thermoplastic resin composition of the present invention.

The thermoplastic resin composition according to the present invention can realize the appearance and tactile effect of a fabric-like material superior to that of the existing thermoplastic composition, and the molded article including the thermoplastic resin composition of the present invention can be applied to the interior and exterior of various products. In addition, the thermoplastic resin composition of the present invention may be used in a molded article, and further may be used as a filament for 3D printing.

The manufacturing method of the molded article is not particularly limited, and for example, the molded article according to the present invention may be prepared by using a 32-pi twin-screw extruder (L/D= 40, 25mm), it can be manufactured using an injection machine having a clamping force of 100 tons to 200 tons under the same temperature conditions after extrusion.

According to an example of the present invention, the coefficient of friction measured according to JIS K 7218 of the composition or article made of the composition of the present invention may be 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, 0.25 or more, or 0.28 or more. , 0.43 or less, 0.40 or less, 0.38 or less, 0.36 or less, 0.34 or less, 0.32 or less, or 0.30 or less. For example, it may be 0.05 to 0.43, 0.05 to 0.40, 0.05 to 0.35, 0.05 to 0.30, 0.10 to 0.43, 0.10 to 0.40, 0.10 to 0.35, 0.10 to 0.30, 0.20 to 0.35, 0.25 to 0.35, or 0.25 to 0.35. When the coefficient of friction is within the above range, it is possible to realize a feel most similar to a fabric.

According to one embodiment of the present invention, the composition or the water repellency of the article made of the composition of the present invention may have a contact angle of 102° or more, 103° or more, 104° or more measured based on one-drop touch mode evaluation.

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.

[Example]

The components used in this Example and Comparative Example are specifically as follows:

(A) Thermoplastic resin

- ABS: acrylonitrile-butadiene-styrene (ABS) resin (LG Chem)

- PP: Polypropylene (PP) resin (SK Global Chemical)

(B) Cellulose fibers

In the specimen prepared from the thermoplastic resin composition of the present invention, a photograph comparing and evaluating the case of using a dye-divided cellulose fiber and a semi-dyed-type cellulose fiber of the same color is shown in FIG. 1 .

(C) Silicon masterbatch

- C-1: Dow Corning, MB50-008

- C-2: Dow Corning, MB50-001

- C-3: Dow Corning, MB50-315

(D) additives

- Lubricant: Polyethylene-based lubricant

- Antioxidant: phenolic antioxidant

Example 1

As shown in Table 1, 100 parts by weight of a mixture of thermoplastic resin, lubricant, antioxidant, cellulose fiber and silicone masterbatch was mixed well with a mixer at the indicated content and uniformly dispersed to prepare a thermoplastic resin composition according to the present invention. Thereafter, extrusion was performed on the prepared thermoplastic resin composition using a 32-pi twin-screw extruder (L/D=40, 25mm) under conditions of 200°C to 220°C and 200 rpm to 250 rpm, and 100 tons under the same temperature condition. An injection specimen was prepared using an injection machine having a clamping force of to 200 tons.

In the case of injection specimens for evaluation of fabric-like texture and tactile feel, a rectangular multi-stage specimen having a size of 900 mm × 650 mm was prepared.

Examples 2 to 9 and Comparative Examples 1 to 11

An injection specimen was prepared in the same manner as in Example 1, except that the type and content of the thermoplastic resin, cellulose and silicone masterbatch were changed as described in Table 1.

[Method of measuring physical properties]

As follows, fabric-like appearance and feel were evaluated as fiber properties, and filament formability for 3D printing was evaluated as filament properties.

(1) Fabric-like evaluation method

The fiber feel (fiber index) was evaluated by applying the Kansei engineering process. The evaluation items of fiber feeling (fiber index) are as follows.

The evaluation group was divided into a user (customer) group and a designer group, and the evaluators evaluated the overall fiber feeling score when touching and visually viewing each specimen. Low samples were evaluated as 0 points.

The final fiber index was calculated through the summation of the raters' fiber index. The result of the example was determined by the total score of 100 points by designating a total of 10 evaluators.

In addition, the most important factors for the fiber index can be inferred through the detailed evaluation items of samples with excellent fiber properties and can be applied when configuring detailed design specifications.

(2) Tactile evaluation

Friction coefficient: JIS K 7218 (Ring-on-disc test)

Water repellency: Contact angle evaluation (One-drop touch mode)

(3) Filament moldability evaluation for 3D printing

Cobweb: The degree to which cobwebs are formed during 3D printing (5 points for not forming)

Shrinkage: The degree to which the corners are bent when printing a square box (5 points for not bending)

Support adhesion: The degree to which it adheres to the output during 3D printing (5 points for better adhesion)

The evaluation criteria for filament formability for 3D printing are shown in FIG. 2 .

[Table 1]

[Table 2]

From the above results, it was confirmed that by applying the cellulose fiber, visually similar appearance to the fabric can be realized, and by applying the silicone masterbatch, it can be confirmed that the tactile feel of the textile fabric can be realized. In particular, it could be confirmed that when the evaluator primarily judged through the sight in the textile evaluation and then felt the textile feel through the tactile test, it felt more similar to the fabric.

Specifically, in Examples 1 to 9, it was confirmed that not only the fabric-like appearance and touch were realized, but also the physical properties required as a 3D printing filament were excellent due to excellent fiber properties, friction coefficient and water repellency.

In particular, in the case of cellulose fiber, it was confirmed that the fiber index was increased by further increasing the two-tone effect, which is a characteristic of the fiber, in the order of transfer dye type, half transfer dye type, and mixing. In addition, from the evaluation of the 3D filament formability, it was confirmed that the added cellulose fiber acts as a needle-like reinforcing agent to improve contractility and spider silk properties, and does not inhibit adhesion.

Through these characteristics of cellulose fibers, it was confirmed that it is easy to manufacture various molded articles by using the thermoplastic resin of the present invention for 3D printer molding, and it was also confirmed that it was possible to secure a fabric-like appearance.

However, in Comparative Examples 1 to 8, even if the thermoplastic resin and cellulose fibers were used in various combinations, the silicone masterbatch was not included or was included in a small amount, so that the fiber properties were poor, and it was confirmed that the degree of implementation of the fabric-like feeling was reduced. .

In addition, in Comparative Examples 9 to 11, as the cellulose fiber was not included, it was found that the fiber feeling was significantly reduced, the contractility was significantly inhibited, and the spider silk properties were also decreased.

Claims (9)

Based on 100% by weight of the total composition,
(A) 60 to 90% by weight of a thermoplastic resin,
(B) 0.1 to 30% by weight of cellulose fibers and
(C) 6 to 20% by weight of the silicone masterbatch,
(B) the cellulose fiber is a dichromatic type cellulose fiber, a semi-dyed type cellulose fiber or a mixture thereof,
Thermoplastic resin composition. According to claim 1, wherein (A) the thermoplastic resin is acrylonitrile-butadiene-styrene resin, modified acrylonitrile-butadiene-styrene resin, polyolefin resin, polyether ether ketone resin, modified polyphenylene ether resin, polymethyl meta A thermoplastic resin composition selected from the group consisting of a acrylate resin, a polybutylene terephthalate resin, or a combination thereof. delete The thermoplastic resin composition according to claim 1, wherein (B) the cellulose fibers have a diameter (D50) of 6 to 14 μm. The thermoplastic resin composition according to claim 1, wherein (B) the cellulose fibers have a length of 0.2 to 2 mm. The thermoplastic resin composition according to claim 1, wherein (B) the cellulose fiber has a heat resistance of 200°C to 300°C. The method of claim 1, wherein (C) the silicone masterbatch is low-density polyethylene, high-density polyethylene, ethylene vinyl acetate copolymer, thermoplastic polyester elastomer, acrylonitrile-butadiene-styrene resin, polypropylene, polyethylene terephthalate, or a combination thereof. A thermoplastic resin composition prepared by dispersing a siloxane polymer in a resin selected from the group consisting of. The thermoplastic resin composition of claim 1 , further comprising an additive selected from the group consisting of a light diffusing agent, an antioxidant, a lubricant, an ultraviolet absorber, a light stabilizer, an impact modifier, a matting agent, a flame retardant, or a combination thereof. A molded article comprising the thermoplastic resin composition according to any one of claims 1, 2 and 4 to 8.

Images