KR100854322B1 - Pellet reinforced by long fiber and article manufactured by using the same - Google Patents

Abstract

A resin composition for impregnation of long fibers is provided to realize excellent impact resistance and heat resistance, and to satisfy the requirements of excellent flexural characteristics, weld line strength, urethane foam adhesion and minimized deformation of molded articles. A resin composition for impregnation of long fibers comprises: 100 parts by weight of a thermoplastic resin containing at least 50 wt% of propylene-ethylene copolymer; 5-400 parts by weight of a rubbery resin comprising ethylene-octene copolymer, styrene-diene copolymer or a blend thereof; and 1-100 parts by weight of a copolymer having at least one polar group selected from the group consisting of a modified propylene to which a polar group is grafted and hydroxyl group-containing polyolefin polyol.

Description

Pellet reinforced by long fiber and article manufactured by using the same}

The present invention relates to a long fiber-impregnated resin composition, a long fiber reinforced pellets, a resin pellet composition, and a molded article prepared therefrom, and more particularly, to an excellent impact resistance and heat resistance, and particularly to flexure represented by flexural strength and flexural modulus. Long fiber impregnated resin composition, long fiber reinforced pellet, resin pellet composition, and the like, which are suitable for the interior and exterior parts of automobiles such as crash pads, door trims, door modules, etc. It relates to a molded article.

In general, polypropylene resins used for manufacturing automotive interior and exterior parts are excellent in formability, impact resistance, chemical resistance, etc., and have low specific gravity and low cost, so they are used for interior materials such as bumpers and various fillers in automobiles. It is widely used. However, in the case of large automobile parts such as instrument panels, they must have excellent impact resistance for the safety of passengers in the event of a collision, and at the same time, increase the ease of work at the stage of taking out, transporting, assembling, and mounting after molding the molded parts. In order to maintain a stable shape, excellent bending characteristics are required, and in the case of a three-layer instrument panel, adhesion with urethane foam or polyolefin foam, which is usually used for intermediate layers, is also required.

In addition, efforts to reduce the thickness of the molded article to reduce the weight of the molded article in order to solve the challenges such as fuel efficiency, cost reduction, etc., in this case, the thinner the thickness, the lower the bending characteristics of the molded product As a result, it is necessary to develop a new polymer material having a significantly improved bending property than the existing material.

 Some polypropylene resin compositions developed to automotive interior materials such as instrument panels have good products in terms of physical properties such as impact resistance and stiffness, but when the thickness is reduced, the flexural characteristics do not meet the required level or require flexural characteristics. Even if the level is adjusted to have a large deformation, the rigid line and impact resistance of the weld line is poor, there is a problem that cracks occur in the affected area even in a weak impact. For example, in Korean Patent Nos. 10-0387648, 10-0263332, 10-0387649, 10-0412452, and 10-0535611 invented by the present inventors, inventions to which special properties such as paintability and scratch resistance are given while maintaining excellent impact resistance Exemplary but when reducing the thickness of the molded article there is a problem that the bending characteristics do not reach the required level. In order to solve this problem, instead of a plate-shaped inorganic filler, a fibrous reinforcing agent such as glass fiber, carbon fiber, metal fiber, nylon fiber and polyethylene Terephthalate fiber (PET Fiber), polyethylene ethylene ketone fiber (PEEK Fiber), liquid crystal polymer fiber (LCP Fiber), polyacrylonitrile fiber (PAN Fiber), ultra-high molecular weight polyethylene fiber (PE Fiber), aramid fiber (Aramid Fiber), Although a method of using a fibrous reinforcing agent made of natural fiber or the like can be considered, there is a problem that excessive deformation occurs when using a fibrous reinforcing agent in the form of a fibrous reinforcing agent. Difficult to apply

In order to solve this problem, US Pat. No. 4983647 illustrates an invention in which a large amount of plate-shaped inorganic filler is mixed with a glass fiber of 촙 type to reduce the deformation amount, but in this case, the injection molded product is increased as the content of the plate-shaped inorganic filler is increased. There is a problem that the strength and impact resistance of the weld line portion is inferior, so there is a high possibility of cracking even a weak impact applied to the weld line portion during use.

Therefore, development of a resin composition not only excellent in impact resistance but also excellent in flexural characteristics and weld line portion strength and small in deformation amount is required.

The present invention has been made in view of the above problems, and can satisfy all of the requirements of excellent bending characteristics, weld line part strength, urethane foam adhesion, and minimizing deformation of molded articles, which have excellent impact resistance and heat resistance characteristics, which have not been achieved in the prior art. An object of the present invention is to provide a resin composition for long fiber impregnation.

It is another object of the present invention to provide a long fiber reinforced pellet prepared from the long fiber impregnated resin composition.

The present invention also aims to provide a resin pellet composition having the same composition ratio as the long fiber impregnated resin composition.

It is also an object of the present invention to provide a molded article prepared from the long fiber reinforced pellet or the resin pellet composition, which has excellent impact resistance, flexural characteristics, weld line portion strength, and a small deformation amount.

The resin composition for long fiber impregnation according to an aspect of the present invention is an ethylene-α-olefin copolymer composed of 100 parts by weight of a thermoplastic resin including at least 50% by weight of propylene-ethylene copolymer, α-olefins having 3 or more carbon atoms, and ethylene. Or a copolymer having at least one polar functional group selected from the group consisting of 5 to 400 parts by weight of a rubber resin which is a styrene-diene copolymer, or a mixture thereof, and a polyolefin polyol containing a propylene modified with a polar functional group and a hydroxyl group. 1 to 100 parts by weight.

The long fiber reinforced pellet according to an aspect of the present invention is 100 parts by weight of a thermoplastic resin, 5 to 400 parts by weight of a rubber resin, 1 to 100 parts by weight of a copolymer having a polar functional group, and a long fiber reinforcement having a length of 3 to 100 mm. To 500 parts by weight.

The thermoplastic resin is a propylene-ethylene copolymer or a blending resin of a propylene-ethylene copolymer and a propylene polymer, wherein the weight ratio of the propylene polymer to the propylene-ethylene copolymer in the blending resin is 1 to 50%. The propylene-ethylene copolymer has an extreme viscosity [η] of xylene extract of at least 3.0 dl / g and an ethylene content of 3 to 20% by weight, and the propylene polymer has a pentad fraction (% mmmm) measured by 13 C-NMR. It is 96% or more and intrinsic viscosity [eta] is 1.0-3.0 dl / g.

The rubber resin is an ethylene-α-olefin copolymer or styrene-diene copolymer, or a mixture thereof, and the ethylene-α-olefin copolymer is composed of α-olefin and ethylene having 3 or more carbon atoms, and the ethylene is the ethylene 10 to 90% by weight of the -α-olefin copolymer. The content of the aromatic vinyl compound in the styrene-diene copolymer is 10 to 50% by weight.

The copolymer having the polar functional group is a modified polypropylene, or a polyolefin polyol, or a mixture thereof, and the modified polypropylene is graphed with at least one polar group selected from the group consisting of unsaturated carboxylic acids, derivatives thereof, and organosilane compounds. Graft ratio is 0.3 to 5% by weight, the polyolefin polyol has 150 to 200 carbon atoms and 20 to 80 (KOH mg / g) hydroxyl value.

The long fiber reinforcement has an average diameter of 0.5 to 100 μm and has a length substantially equal to that of the pellets.

Resin pellet composition according to an aspect of the present invention is 10 to 90% by weight of a first pellet comprising a first resin consisting of at least one component from the group consisting of a thermoplastic resin, a rubber resin and a copolymer having a polar functional group, and i) A second resin composed of at least one component from the group consisting of a thermoplastic resin, a rubber resin and a copolymer having a polar functional group, and a second resin different from the first resin, and ii) a long fiber reinforcement having a length of 3 to 100 mm. Pellets from 10 to 90% by weight.

When the first pellets and the second pellets are mixed, they are included in the composition ratio of the long fiber-reinforced pellets, and the first pellets are made of a thermoplastic resin and a rubber resin, and the second pellets have a thermoplastic resin and a polar functional group. Copolymer, and long fiber reinforcement.

The molded article according to an aspect of the present invention is manufactured by molding the long fiber reinforced pellet or the resin pellet composition, the average length of the total long fiber reinforced material is 1mm or more.

Hereinafter, the present invention will be described in more detail.

The thermoplastic resin (A) of the present invention is a propylene polymer, and a propylene sole composed of propylene having an intrinsic viscosity [η] of 1.0 to 3.0 dl / g with a pentad fraction (% mmmm) measured by 13 C-NMR of 96% or more. The polymer (homopolymer) and the propylene ethylene copolymer composed of 3 to 20% by weight of the total ethylene content of the intrinsic viscosity [η] of the xylene extract of 3.0 dl / g or more were mixed in a range of 0:10 to 5: 5, respectively. Composition. The content rate of the said thermoplastic resin in the whole long fiber impregnation resin composition is 10 to 80 weight%.

In the resin composition for long fiber impregnation of the present invention, the polypropylene polymer used as the thermoplastic resin (A) component is a propylene polymer composed mainly of propylene monomer, that is, propylene homopolymer (1) and propylene-ethylene containing ethylene. It is a crystalline polymer composed of the block copolymer (2). As the polypropylene polymer, a propylene-ethylene copolymer (2) component is used alone, or a part of the propylene homopolymer (1) component is used. When the propylene homopolymer has a pentad fraction (mmmm fraction) measured by 13 C-NMR, if the pentad fraction is less than 96%, the stiffness, heat resistance, etc. will be lowered, so that the value of the pentad fraction is 96% or more, preferably 96.5% or more, more preferably 97% or more. In addition, since the propylene homopolymer has an intrinsic viscosity of less than 1.0 dl / g, the impact strength is lowered, and when the propylene homopolymer is more than 3.0 dl / g, the moldability is lowered. [] is 1.0 to 3.0 dl / g, preferably 1.5 to 2.5 dl / g.

The propylene-ethylene copolymer (2) is 3.0 dl / g or more, since the impact strength is lowered when the ultimate viscosity [η] of the xylene extract in 135 ° C decalin is less than 3.0 dl / g. Is at least 3.5 dl / g, even more preferably at least 4.0 dl / g. In addition, the content of ethylene in the propylene-ethylene copolymer is 3 to 20% by weight, preferably 5 to 15% by weight.

The thermoplastic resin component includes at least 50% or more of propylene-ethylene copolymer, and may be used alone or as a blending resin containing a part of propylene polymer. In the case of the propylene polymer (1), the impact resistance is insufficient, and since the propylene-ethylene copolymer (2) lacks moldability, rigidity, heat resistance, and the like, the propylene polymer (1) and the propylene-ethylene copolymer (2) ) Is preferably 0:10 to 5: 5, more preferably 0:10 to 3: 7, in terms of impact strength and fluid balance.

When the blending ratio of the thermoplastic resin (A) component in the long fiber impregnated resin composition exceeds 80% by weight, the impact strength and bending property are lowered, and when the blending ratio is less than 10%, the moldability is lowered. The resin is contained by 10 to 80% by weight.

The rubber resin (B) of the present invention is an ethylene-α-olefin copolymer or styrene-diene copolymer, or a mixture thereof, and is used to improve impact resistance. The content of the rubber resin (B) component in the total long fiber impregnation resin composition is 5 to 40% by weight, or about 5 to 400 parts by weight based on 100 parts by weight of the thermoplastic resin. This is because the flexural properties and formability are lowered when the content exceeds 40% by weight, and the impact strength is lowered when the amount is less than 3% by weight. It is preferable that the content rate of the said rubber resin component is 5-35 weight% in the long fiber impregnation resin composition.

The ethylene-α-olefin copolymer is composed of α-olefin and ethylene having 3 or more carbon atoms, and the ethylene is contained in the ethylene-α-olefin copolymer by 10 to 90% by weight, preferably 15 to 85% by weight. do. In addition, the ethylene-α-olefin copolymer has a dispersion mark when the melt index (MI) at a temperature of 230 ° C. and a load of 2.16 kg is less than 0.1 g / 10 min, resulting in a flow mark, and impact resistance when exceeding 50 g / 10 min. There is a problem of deterioration. Accordingly, the melt index (MI) at 230 ° C. and a 2.16 kg load of the ethylene-α-olefin copolymer is 0.1 to 50 g / 10 min. The ethylene-α-olefin copolymer rubbers include ethylene-propylene copolymer rubbers, ethylene-butene-1 copolymer rubbers, ethylene-octene copolymer rubbers, and the like. These copolymers may be used alone or in combination.

The styrene-diene copolymer may include an aromatic vinyl compound in the styrene-diene copolymer by 10 to 50% by weight, and has a melt index (MI) of 0.1 to 50 g / 10 min at a load of 2.16 kg at 230 ° C. The styrene-diene copolymer rubber is a block copolymer composed of aromatic vinyl compounds such as styrene, vinyl toluene and methyl styrene, and diene compounds such as butadiene and isoprene, and also includes a compound in which hydrogen is added to the styrene-diene copolymer. Representative styrene-diene copolymer rubbers include styrene-butylene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-propylene block copolymers, styrene -Ethylene-propylene-styrene block copolymers, and the like, and these copolymers may be used alone or in combination. If the content of the aromatic vinyl compound in the styrene-based copolymer rubber is less than 10% by weight, the moldability is inferior, and if the content is more than 50% by weight, there is a problem of low temperature impact resistance. Accordingly, the content of the aromatic vinyl compound in the styrene copolymer rubber is 10 to 50% by weight.

The copolymer (C) having a polar functional group of the present invention is a modified polypropylene or polyolefin polyol, or a mixture thereof.

The copolymer (C) having a polar functional group is a polypropylene containing a polar group to increase the bonding strength of the polypropylene and the long fiber reinforcement to strengthen the rigidity and flexural characteristics, and additionally improve the adhesion to the urethane foam do. As the polar group-containing resin of the present invention, a modified polypropylene (modified PP) obtained by grafting a polar functional group on the side chain and a polyolefin polyol containing a hydroxyl group on the terminal group may be used alone, or a mixture thereof may be used. In particular, when the content of the copolymer (C) having a polar functional group is less than 1% by weight, it is difficult to have an effect on the improvement of rigidity, flexural properties and urethane adhesion properties, and when higher than 10% by weight, it may cause a decrease in impact strength. As such, the copolymer having the polar functional group is included by 1 to 10% by weight based on the total long fiber impregnation resin composition. Or when the thermoplastic resin (A) is 100 parts by weight, the copolymer having the polar functional group is included by about 1 to 100 parts by weight.

The modified polypropylene is obtained by grafting a polar functional group such as unsaturated carboxylic acid, derivatives thereof, and organosilane compound to polypropylene. At this time, if the graft ratio is less than 0.3% by weight, the bending property, rigidity and adhesion with the urethane foam are not improved, and when 5.0% by weight is exceeded, the impact strength is lowered. Therefore, the graft ratio is 0.3 to 5.0% by weight, preferably 0.5 to 5.0% by weight. Specific examples of the unsaturated carboxylic acid and derivatives thereof usable in the graft reaction include unsaturated carboxylic acids such as maleic acid, fumaric acid, acrylic acid, itaconic acid and methacrylic acid, and derivatives thereof such as maleic anhydride and maleic anhydride such as maleic anhydride and maleic acid monoamide, Esters such as acrylic acid amide and sodium methacrylate, amides, metal salts, and the like. Examples of the organosilane compound include aminosilane, epoxysilane, vinylsilane, methacryloxysilane, and the present invention. Other compounds that can achieve the same object as the present invention can also be applied. The copolymer having the polar functional group, that is, the polar group-containing polypropylene, can be used by grafting one or two or more polar groups selected from the polar functional groups listed above to the polypropylene resin.

In addition, the polyolefin polyol has a viscosity of 10 to 16 poise (100 DEG C), and a low molecular weight polymer having 150 to 200 carbon atoms in olefins is used. If the hydroxyl value of the polyolefin polyol is less than 20 KOH mg / g, the scratch resistance does not improve, and if 80 KOH mg / g is exceeded, the hydroxyl group of the surface is contained in a large amount, so that the impact strength is lowered, the polyolefin The hydroxyl value of the polyol is 20 to 80 KOH mg / g, preferably 30 to 60 KOH mg / g.

The long fiber reinforced pellet of the present invention is 100 parts by weight of thermoplastic resin, 5 to 400 parts by weight of rubber resin, 1 to 100 parts by weight of copolymer having a polar functional group, and 10 to 500 parts by weight of long fiber reinforcement having a length of 3 to 100mm. Included as much as The long fiber reinforced pellets are prepared by impregnating the long fiber reinforcing material with the resin composition for long fiber impregnation. Since the thermoplastic resin, the rubber resin, and the copolymer having the polar functional group of the long fiber reinforced pellet are the same as described above, the long fiber reinforced material and the long fiber reinforced pellet will be described below.

The long fiber-reinforced pellets may have a variety of shapes such as cylindrical, oval, rugby ball, flat cylindrical, etc., and the length of the pellet is typically 3 to 100 mm. The long fiber reinforcing material has an average diameter of 0.5 to 100 µm and an average length of 3 to 100 mm, which is impregnated in parallel with the length direction of the pellets, and is substantially the same as the length of the pellets. The length of the long fiber reinforcement in the long fiber reinforcement pellets is suitable 3 ~ 100mm, if the length is less than 3mm, the amount of deformation increases and the strength of the weld line portion falls, if it is longer than 100mm it is not well put into the cylinder from the molding machine hopper It does not have good moldability.

The long fiber reinforcing material is glass fiber, carbon fiber, metal fiber, metal fiber, nylon fiber, polyethylene terephthalate fiber, polyethylene ethylene ketone fiber, PEEK fiber One or two selected from fiber reinforcing agents such as liquid crystal polymer fiber (LCP fiber), polyacrylonitrile fiber (PAN fiber), ultra high molecular weight polyethylene fiber (PE fiber), aramid fiber (natural fiber), and the like. It may consist of a mixture of species or more.

In addition, in order to increase the wettability of the polymer, the long fiber reinforcing material may use a suitable surface treatment agent, for example, a coupling agent in the form of silane, titanate, aluminum, chromium, zirconium, borane, or the like, or may be subjected to acid treatment. Especially in the case of the glass fiber which is used abundantly, silane coupling agents, such as gamma-aminopropyl trimethoxysilane, epoxy coupling agents, such as gamma-glycidoxy propyl trimethoxysilane, and vinylsilane coupling agents, such as vinyl trichlorosilane When using can greatly improve the wettability of the polymer.

If the content of the long fiber reinforcing material is less than 10% by weight in the total long fiber reinforcing pellets, the deformation amount is large, and the bending property of the required level cannot be expressed, and when the weight is more than 50% by weight, the moldability deteriorates. Thus, the long fiber reinforcing material is included in the long fiber reinforced pellets by 10 to 50% by weight, preferably 15 to 45% by weight. This is about 10 to 500 parts by weight of the long fiber reinforcing material is contained with respect to 100 parts by weight of the thermoplastic resin contained in the long fiber reinforced pellets.

The resin pellet composition of the present invention comprises a first pellet comprising a first resin composed of at least one component selected from the group consisting of thermoplastic resins, rubber resins and copolymers having polar functional groups, and i) thermoplastic resins, rubber resins and polarities. And a second pellet composed of at least one component from the group consisting of a copolymer having a functional group, and composed of a second resin different from the first resin and ii) a long fiber reinforcing material having a length of 3 to 100 mm. The first pellets and the second pellets are dry blended to form a resin pellet composition. The first pellet is included by 10 to 90% by weight based on the total resin pellet composition, the second pellet is also included by 10 to 90% by weight relative to the total resin pellet composition, but the present invention is not limited thereto and appropriate ratio as necessary It can be mixed with.

The pellet according to the present invention may be in the form of a single pellet in which a long fiber reinforcing material is impregnated in a resin composition for long fiber impregnation comprising a thermoplastic resin, a rubber resin, and a copolymer having a polar functional group. 2 pellets are in the form of a dry mixed form of resin pellet compositions. Mixing the first pellet and the second pellet is the same as the composition of the long fiber reinforced pellet in the form of the single pellet. Therefore, when the molded article is manufactured from pellets, a molded article having the same composition ratio when using a single pellet and when using a resin pellet composition can be produced.

In the present invention, the method for producing the long fiber reinforced pellets is not particularly limited. For example, the first pellet may be manufactured by a conventional method using a single screw extruder, a twin screw extruder, a multi-wheel screw extruder, a bandari mixer, a kneader mixer, and the like. However, in order to make the length of the long fiber reinforcing material impregnated in the pellets as the second pellets is approximately the same as the pellets, the long fiber reinforcing material in the roving form is continuously passed through the impregnation tank in which the long fiber impregnation resin composition is supplied in a molten state. It can be prepared by melting or kneading the polymer while injecting a long fiber reinforcing material into the cylinder using a single screw extruder manufactured while making a special or manufactured. However, when the conventional compounding method is used, the length of the fiber reinforcing agent is shorter than that of the pellets, and thus, when the molded article is manufactured from such pellets, satisfactory stiffness and bending characteristics cannot be obtained. For example, a single screw extruder or a twin screw extruder is used to inject the melted long fiber impregnated resin composition into a hopper, and the long fiber reinforcement cut into chops is hopper or a dedicated side feeder provided separately. It is used to pelletize or pelletize the kneaded composition by adding a long fiber-impregnated resin composition and a long fiber reinforcing material to a short-barrier mixer or a kneader mixer using a single screw or twin screw extruder. In this case, even if the length of the fibrous reinforcing agent in the form of sapling satisfies 3 to 100 mm at the initial input, the length of the long fiber reinforcing material that remains in the final pellet due to breakage of the fiber reinforcing agent, that is, the long fiber reinforcing material, during kneading in the cylinder Is very shorter than the length of the pellets so that it cannot satisfy the required length of 3 to 100 mm.

In the present invention, the additive which may be additionally added to the long fiber reinforced pellet is commonly used for stabilization, coloration, cost reduction, etc. of polymers, such that bending characteristics, weld line strength, impact resistance, and deformation characteristics are drastically reduced. It can be used within the range not to be used, for example, antioxidants, neutralizing agents, nucleating agents, antistatic agents, flame retardants, brighteners, UV stabilizers, slip agents, mold release agents, inorganic fillers, coloring agents and the like can be used. More detailed examples of the colorant may include phenolic antioxidants, phosphite antioxidants, thiodipropionate synergists, and the like, and calcium stearate, zinc oxide, etc. may be used as the neutralizing agent. Examples of the inorganic fillers include talc, mica, clay, calcium carbonate, barium sulfate, glass bubbles, glass beads, ceramic bubbles, whiskers, and glass fibers in the form of glass. . In addition, the additive may be further added to the first pellet or the second pellet in the resin pellet composition.

 When the melt index (MI) at 230 ° C. and 2.16 kg load of the long fiber reinforcing material pellets or the resin pellet composition is less than 1 g / 10 min, a decrease in productivity and a flow mark may occur in the final product. If the index MI is greater than 40 g / 10 min, it is difficult to obtain desired properties in terms of stiffness, impact strength, bending characteristics, weld line portion strength, and the like. Accordingly, the melt index (MI) at 230 ° C. and a 2.16 kg load of the long fiber reinforcement pellet or the resin pellet composition is 1 to 40 g / 10 min.

When the molded article is manufactured by molding the long fiber reinforced pellet or the resin pellet composition, the average length of the long fiber reinforced material finally remaining in the molded article is 1 mm or more, preferably 2 mm or more. The long fiber reinforcing material having a length of 1 mm or more of the total long fiber reinforcing material contained in the molded article is 50 to 80% by weight.

Injection molding, compression molding, extrusion molding, blow molding, foam molding, gas injection molding, metal insert injection molding, metal insert compression molding, etc. may be used as a method of molding using the long fiber reinforced pellet or the resin pellet composition of the present invention. Among them, injection molding, metal insert injection molding and the like are particularly suitable.

By molding the long-fiber reinforced pellets or resin pellet composition of the present invention by molding an instrument panel, an instrument panel carrier, a door module, a hatchback, a seatback, a seat pan, a front end module, a bumper beam or an engine undercover, and the like. It can manufacture. In addition, a molded article having a urethane foam or a polyolefin foam attached to the instrument panel can be produced. This is because the pellets of the present invention are excellent in adhesion with urethane foam or polyolefin foam as well as rigidity and flexural characteristics.

Hereinafter, the present invention will be described in detail by Examples and Comparative Examples using the long fiber-impregnated resin composition, the long fiber reinforced pellet, and the resin pellet composition according to the present invention, but the following examples further illustrate the contents of the present invention. As illustrative, the contents of the present invention are not limited to the following examples.

 EXAMPLE

Next, the resin composition for long fiber impregnation was prepared by the composition and content of Tables 1 to 4, and the pellet was prepared by impregnating the long fiber reinforcing material or other inorganic filler of Table 5 in the composition. The component ratios in the final pellets are shown in Table 6.

Table 1 and Table 2 show the thermoplastic resin component (A) used in the experiment.

Table 1 shows the melt index (MI) and intrinsic viscosity of the propylene homopolymer, and Table 2 shows the melt index (MI) of the propylene-ethylene copolymer and the ethylene content (Ec) in the propylene-ethylene copolymer. ), The content of xylene extract in the propylene-ethylene copolymer component is represented by Rc (wt%), and the intrinsic viscosity of the extract component is represented by [η] EP (dl / g). Melt index (MI) was measured under the conditions of ASTM D1238 (temperature 230 ° C., load 2.16 kg), and ethylene content (Ec) in the propylene-ethylene copolymer was measured by Fourier Transform Infrared Spectrometer (FT-IR).

Division (A) MI (g / 10 min) Intrinsic viscosity (dl / g) PP-1 12.0 1.9 PP-2 26.3 1.3

Division (A) MI (g / 10min) Ec (wt%) Rc (wt%) [η] EP (dl / g) PP-3 9.0 60 16 4.1 PP-4 28.4 60 15 3.5

Table 3 shows the components of the rubber resin (B) used in the experiment. As the rubber component (B), an ethylene propylene copolymer (RB-1), an ethylene-butene 1 copolymer component (RB-2), and a styrene-diene copolymer as an ethylene-?-Olefin copolymer are used. Butylene-styrene copolymer component (RB-3) was used. Melt index (MI) was measured at a temperature of 230 ° C. and a load of 2.16 kg, Cc was the comonomer content in the ethylene-α-olefin copolymer measured by FT-IR, and Sc was the styrene-diene measured by FT-IR. Styrene content in the copolymer.

Division (B) MI (g / 10 min) Cc (wt%) Sc (wt%) RB-1 4.0 32 - RB-2 2.5 21 - RB-3 4.0 - 14

Table 4 shows the polar group-containing resin (C) used in the experiment. mPP means modified propylene and Polyol means polyolefin polyol. Fc means the graft rate of the polar functional group, measured by FT-IR.

Division (C) Fc (% by weight) Fisheries Value (KOH mg / g) Polar group type mPP 1.5 - -COOH Polyol - 45 -OH

Table 5 shows the plate-shaped inorganic filler and the 촙 type fiber reinforcing agent as the long fiber reinforcing material (D) used in the experiment and other fillers (E) used for the comparative evaluation. In Examples 1 to 4, glass fibers (RF-1) having a length of 10 mm were used. In Comparative Examples 1 to 5, glass fiber (RF-2) was used as a short-shape fibrous reinforcing agent having a length of 1.5 mm, and talc (T-1) and mica (M-1) were used as plate-shaped inorganic fillers. The average particle diameter of the plate-shaped inorganic filler was measured by the laser sedimentation method. In Table 5, the lengths of RF-1 and RF-2 refer to the lengths of the glass fibers included in the prepared polypropylene resin composition.

RF-1 (D) Glass fiber with an average diameter of 17 µm and a length of 10 mm RF-2 (E) Glass fiber with an average diameter of 17 µm and a length of 1.5 mm T-1 (E) Talc with an average particle diameter of 7㎛ M-1 (E) Mica with an average particle diameter of 90 µm

Table 6 shows the component ratios of the pellets prepared in Examples 1 to 4 and Comparative Examples 1 to 5.

Examples 1 to 4 and Comparative Examples 1 to 2 are formulated to meet the content ratios of (A), (B), (C) and other components shown in Table 1 to Table 5 and Table 6 below in the Henschel mixer After dry blending for 3 minutes, melt-kneading was carried out using a twin screw extruder (diameter 45 mmψ) set at 230 ° C., introduced into the impregnation tank, and at the same time, the roving of the component (D) was passed through the impregnation tank to cut the pellet to a length of 10 mm. It was prepared by.

Comparative Examples 3 to 5 were formulated in accordance with the content ratio of Table 1 to Table 5 to dry blend for 3 minutes in a Henschel mixer, and then using a twin screw extruder (diameter 45 mmψ) set to 230 ℃ Melt kneading was followed by pelletization.

The pellets of the obtained resin compositions were injected under the conditions of an injection machine nozzle temperature of 250 ° C. and a cylinder temperature of 220 to 240 ° C., and experiments were performed after standing for 48 hours under constant temperature and humidity conditions of 23 ° C. and 50% relative humidity after specimen molding.

division (A) (B) (C) (D) (E) Example 1 PP-1: 10% PP-4: 52% RB-1: 10% RB-2: 10% mPP: 3% RF-1: 15% - Example 2 PP-1: 10% PP-3: 42% RB-2: 20% mPP: 1% Polyol: 2% RF-1: 15% - Example 3 PP-3: 50% RB-1: 15% RB-3: 5% Polyol: 3% RF-1: 30% - Example 4 PP-4: 50% RB-2: 15% RB-3: 5% mPP: 2% Polyol: 1% RF-1: 30% - Comparative Example 1 PP-1: 10% PP-3: 60% RB-2: 20% mPP: 1% Polyol: 2% RF-1: 5% - Comparative Example 2 PP-1: 10% PP-3: 68% RB-2: 2% mPP: 1% Polyol: 2% RF-1: 15% - Comparative Example 3 PP-3: 45% RB-2: 20% mPP: 1% Polyol: 2% - T-1: 30% Comparative Example 4 PP-1: 10% PP-3: 72% RB-2: 20% mPP: 1% Polyol: 2% - RF-2: 15% Comparative Example 5 PP-1: 10% PP-3: 25% RB-2: 20% mPP: 1% Polyol: 2% - RF-2: 10% M-1: 20%

[Property test]

In order to investigate the physical properties and workability, the molding materials manufactured using the pellets prepared in the present invention are subjected to flexural modulus, flexural strength, heat deformation temperature, weld line strength, impact strength, and deformation amount according to the following procedure. The evaluation is shown in Table 7 below. In addition, the measurement method of the intrinsic viscosity, pentad fraction, and melt index related to the physical properties of the components constituting the pellet are also summarized below.

(1) Intrinsic Viscosity

The propylene homopolymer and propylene-ethylene copolymer were used completely dissolved in decalin at 135 ° C. Ubbeholde viscometer was used to measure the viscosity of solutions having various concentrations from 0.1 to 0.5 g / dl. Reduced viscosity was obtained by extrapolating to zero concentration.

(2) isotactic pentad fraction measured by C13 NMR

The fraction of propylene monomers connected in series in the propylene units was measured by 13 C NMR.

(3) Melt index (MI)

According to ASTM D1238 it was measured at a load of 2.16kg, 230 ℃.

(4) weld line strength

The injection molded specimen was used to form a weld line in the center of the injection molded specimen by placing gates at both ends of the longitudinal direction of the Type I type specimen of ASTM D638, and the specimens were measured according to the test procedure of ASTM D638.

(5) flexural modulus and flexural strength

It was measured according to ASTM D790.

(6) Izod impact strength

According to ASTM D256 was measured with a Notched test specimen at room temperature (23 ℃).

(7) heat deflection temperature

It was measured at a load of 6.4 kgf / cm ² according to ASTM D648.

(8) deformation

Rectangular specimens of 200 mm × 100 mm × 2.5 mm were prepared and the largest deformation at both short edges was measured with a vernier caliper.

(9) Mooney viscosity

It was measured at 121 ° C. according to ASTM D1646.

Flexural Modulus (kgf / cm ² ) Flexural Strength (kgf / cm ² ) Weldline Tensile Strength (kgf / cm ² ) Izod impact strength (kgfcm / cm) Heat Deflection Temperature (℃) Deformation amount (mm) Example 1 35200 1035 283 27.5 165 1.25 Example 2 34300 1092 275 29.1 165 1.08 Example 3 54800 1315 262 33.2 167 0.92 Example 4 56100 1342 269 31.0 167 0.85 Comparative Example 1 22800 588 175 25.5 156 4.35 Comparative Example 2 38800 1146 298 15.1 166 5.82 Comparative Example 3 27500 372 182 31.0 142 0.58 Comparative Example 4 30200 792 253 15.7 165 2.55 Comparative Example 5 37800 720 141 10.1 165 1.02

From the results shown in Table 7, any one of the pellets of Examples 1 to 4 can be obtained a molded article having excellent properties in terms of impact resistance, flexural modulus, flexural properties, weld line tensile strength, deformation amount, heat deformation temperature. However, as in the case of Comparative Example 1, when the component content of the long fiber reinforcing material (D) is small, it does not satisfy all the physical properties except the heat deformation temperature and impact resistance, the content of the copolymer rubber component of (B) as in Comparative Example 2 In this case, the stiffness characteristics such as flexural modulus, flexural strength, and weld line strength are excellent, but the impact resistance and deformation amount cannot be satisfied. In addition, when the plate-shaped inorganic filler is used instead of the long fiber reinforcement as in Comparative Example 3, the strength characteristics such as flexural modulus and flexural strength cannot be satisfied. On the other hand, when the plate-shaped inorganic filler is additionally used as in Comparative Example 5 to solve this problem, the flexural modulus, flexural strength, and deformation characteristics are excellent, but the impact resistance and weldline strength cannot be satisfied.

As described above, molded articles molded from the long fiber-reinforced pellets and the resin pellet composition by the long fiber-impregnated resin composition of the present invention have excellent impact resistance and heat resistance, and in particular, flexural characteristics and weld lines represented by flexural strength and flexural modulus. The negative strength is very good. In addition, it has excellent adhesion with other materials, so that the field of application is wide, and the deformation amount is small, so that it can be used in a large structure in which the thickness of the molded article is reduced.

As described above, the present invention has been described by way of a limited embodiment, but the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains may make various modifications and variations from this description. Do. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims below but also by the equivalents of the claims.

Claims (29)

100 parts by weight of a thermoplastic resin including at least 50% by weight of propylene-ethylene copolymer; 5 to 400 parts by weight of a rubber resin which is an ethylene-octene copolymer or a styrene-diene copolymer, or a mixture thereof; And A resin composition for long fiber impregnation comprising 1 to 100 parts by weight of a copolymer having at least one polar functional group selected from the group consisting of a modified propylene grafted with a polar functional group and a polyolefin polyol containing a hydroxyl group. 100 parts by weight of thermoplastic resin; 5 to 400 parts by weight of a rubber resin which is i) a styrene-diene copolymer or ii) a styrene-diene copolymer and an ethylene-α-olefin copolymer; 1 to 100 parts by weight of the copolymer having a polar functional group; And A long fiber reinforced pellet comprising 10 to 500 parts by weight of a long fiber reinforcement having a length of 3 to 100mm. The method of claim 2, The thermoplastic resin is a long fiber reinforced pellets, characterized in that the blending resin of propylene-ethylene copolymer or propylene-ethylene copolymer and propylene polymer. The method of claim 3, Long fiber reinforced pellets, characterized in that the weight ratio of the propylene polymer to the propylene-ethylene copolymer in the blending resin is 1 to 50%. The method of claim 3, The propylene-ethylene copolymer is a long fiber reinforced pellets, characterized in that the ultimate viscosity [η] of the xylene extract is 3.0 dl / g or more and ethylene content of 3 to 20% by weight. The method of claim 3, The propylene polymer has a long fiber reinforced pellet, characterized in that the pentad fraction (% mmmm) measured by 13 C-NMR is 96% or more and the intrinsic viscosity [η] is 1.0 to 3.0 dl / g. delete The method of claim 2, The ethylene-α-olefin copolymer is composed of α-olefins having 3 or more carbon atoms and ethylene, wherein the ethylene is contained in the ethylene-α-olefin copolymer by 10 to 90% by weight. The method of claim 2, Melt index (MI) at a temperature of 230 ° C., 2.16 kg load of the ethylene-α-olefin copolymer or the styrene-diene copolymer is 0.1 to 50 g / 10 min. The method of claim 2, The ethylene-α-olefin copolymer is a long fiber reinforced pellet, characterized in that it comprises at least one copolymer selected from the group consisting of ethylene-propylene copolymer, ethylene-butene-1 copolymer and ethylene-octene copolymer. The method of claim 2, The content of the aromatic vinyl compound in the styrene-diene copolymer is 10 to 50% by weight, characterized in that the long fiber reinforced pellets. The method of claim 2, The styrene-diene copolymers include styrene-butylene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-propylene block copolymers and styrene-ethylene A long fiber reinforced pellet comprising at least one copolymer selected from the group consisting of -propylene-styrene block copolymers. The method of claim 2, The copolymer having the polar functional group is a modified polypropylene, polyolefin polyol, or a long fiber reinforced pellets, characterized in that a mixture thereof. The method of claim 13, The modified polypropylene is grafted with at least one polar group selected from the group consisting of unsaturated carboxylic acids, derivatives thereof, and organosilane compounds, and has a graft ratio of 0.3 to 5% by weight. The method of claim 14, The unsaturated carboxylic acid and its derivatives are at least one compound selected from the group consisting of maleic acid, fumaric acid, acrylic acid, itaconic acid, methacrylic acid, maleic anhydride, itaconic anhydride, maleic acid monoamide, amide amide and sodium methacrylate. Long fiber reinforcing pellets made. The method of claim 14, The organosilane compound is a long fiber reinforced pellets, characterized in that at least one compound selected from the group consisting of aminosilane, epoxy silane, vinyl silane, methacryloxysilane. The method of claim 13, The polyolefin polyol has a carbon number of 150 to 200, a long fiber reinforced pellets, characterized in that the hydroxyl value is 20 to 80 (KOH mg / g). The method of claim 2, The long fiber reinforcing material has an average diameter of 0.5 to 100㎛, long fiber reinforced pellets, characterized in that the same length as the pellets. The method of claim 2, The long fiber reinforcing material is glass fiber, carbon fiber, metal fiber, nylon fiber, polyethylene terephthalate (PET) fiber, polyether ether ketone (PEEK) fiber, liquid crystal polymer (LCP) fiber, polyacrylonitrile (PAN) fiber, ultra high molecular weight PE Long fiber reinforced pellets, characterized in that at least one fiber selected from the group consisting of (polyethylene) fibers, aramid fibers, natural fibers (natural fibers). The method of claim 2, The long fiber reinforced pellet further comprises at least one additive selected from the group consisting of antioxidants, neutralizing agents, nucleating agents, antistatic agents, flame retardants, varnishes, UV stabilizers, slip agents, mold release agents, inorganic fillers and colorants. Fiber reinforced pellets. 10 to 90 wt% of a first pellet comprising a first resin consisting of a thermoplastic resin and a rubber resin; And i) a second resin composed of a thermoplastic resin and a copolymer having a polar functional group and different from the first resin; And ii) a resin pellet composition comprising 10 to 90% by weight of a second pellet made of a long fiber reinforcement having a length of 3 to 100 mm. The method of claim 21, The length of the said 2nd pellet and the length of the said long fiber reinforcing material are the same, The resin pellet composition characterized by the above-mentioned. The method of claim 21, Wherein the first pellet comprises a thermoplastic resin, a rubber resin and a copolymer having a polar functional group, and the second pellet comprises a thermoplastic resin, a rubber resin, a copolymer having a polar functional group, and a long fiber reinforcing material. Resin pellet composition. The method of claim 21, The resin pellet composition, 100 parts by weight of thermoplastic resin; 5 to 400 parts by weight of rubber resin; 1 to 100 parts by weight of the copolymer having a polar functional group; And A resin pellet composition comprising 10 to 500 parts by weight of a long fiber reinforcement having a length of 3 to 100mm. A molded article produced by molding the long fiber reinforced pellet of claim 2 or the resin pellet composition of claim 21, wherein an average length of all the long fiber reinforced materials is 1 mm or more. The method of claim 25, The molded article is a molded article, characterized in that the interior and exterior parts for automobiles including an instrument panel, an instrument panel carrier, a door module, a hatchback, a seatback, a seat pan, a front end module, a bumper beam or an engine undercover. The method of claim 26, Molded article is attached to the urethane foam or polyolefin foam on the instrument panel. 100 parts by weight of a thermoplastic resin including at least 50% by weight of propylene-ethylene copolymer; i) a styrene-diene copolymer having an aromatic vinyl compound content of 10 to 50% by weight, or ii) a rubber resin which is a mixture of a styrene diene copolymer and an ethylene-α-olefin copolymer composed of α-olefin having 3 or more carbon atoms and ethylene 5 to 400 parts by weight; And A resin composition for long fiber impregnation comprising 1 to 100 parts by weight of a copolymer having at least one polar functional group selected from the group consisting of a modified propylene grafted with a polar functional group and a polyolefin polyol containing a hydroxyl group. 100 parts by weight of thermoplastic resin; 5 to 400 parts by weight of a rubber resin which is an ethylene-octene copolymer or a styrene-diene copolymer, or a mixture thereof; 1 to 100 parts by weight of the copolymer having a polar functional group; And A long fiber reinforced pellet comprising 10 to 500 parts by weight of a long fiber reinforcement having a length of 3 to 100mm.