KR20090022835A - Long fiber reinforced pellet containing inorganic material and resin article manufactured by using the same - Google Patents

Abstract

A long fiber reinforced pellet containing an inorganic material is provided to ensure excellent mechanical property and to show excellent flexural modulus without the degradation of tensile strength and impact strength. A long fiber reinforced pellet containing an inorganic material comprises a thermosetting polymer resin 20-80 weight% having the melt index of 0.1-80 g/10min at a temperature of 230 °C and under the load of 2.16 kg; a fiber reinforcing material 10-40 weight% having the length of 5-50 mm; and an inorganic material 10-40 weight% having the average particle size of 1-10 micrometer. The inorganic material comprises talc, calcium carbonate and barium sulfate, wherein the weight ratio of talc : calcium carbonate : barium sulfate is 1 : 0.5~2 : 0.5~2. The fiber reinforcing material has the average diameter of 0.3-50 micrometer and has the same length as the inorganic material-containing long fiber reinforced pellet.

Description

Long fiber reinforced pellet containing inorganic material and resin article manufactured by using the same}

The present invention relates to inorganic-containing long-fiber reinforced pellets and molded articles prepared using the same, more specifically, inorganic-containing long fiber reinforced pellets, inorganic-containing pellets and long-fiber reinforced pellets, etc., which can further enhance the mechanical properties of the molded article. It relates to the mixed pellet composition for reinforcing resin, and a resin molded article produced using the same.

Long-fiber reinforced thermoplastic polymers are used throughout the industry such as home appliances and construction materials because of their recyclability and ease of molding, and their superior mechanical properties and low linear expansion coefficient compared to short-fiber reinforced polymer materials. Increasing use in the automotive industry is required for its characteristics.

Meanwhile, thermoplastic polymer compounds that reinforce physical properties by adding inorganic materials such as talc, mica and calcium carbonate are widely used polymer materials due to their high thermal and mechanical properties reinforcing effect at a low price.

When the long fiber reinforced thermoplastic polymer and the inorganic-containing thermoplastic material are combined, it is expected to have industrially high utility in that both high mechanical properties and low price can be satisfied at the same time. It is not. Particularly, the particle size, type and content of the inorganic material that can optimize the mechanical properties of the molded article in the thermoplastic polymer material containing the inorganic material and the long fiber at the same time, and the properties of the thermoplastic polymer resin which can exhibit excellent mechanical properties when the inorganic material is contained. We need to study.

The present invention has been made in view of the above problems, and an object thereof is to provide an inorganic-containing long fiber reinforced pellet exhibiting excellent mechanical properties. In particular, the present invention increases the flexural modulus of the molded article as the inorganic content increases in the thermoplastic polymer resin, but depending on the type of inorganic material, there may be a decrease in specific mechanical properties such as tensile strength and impact strength. And to provide an inorganic-containing long fiber reinforced pellets that can solve the phenomenon of degradation of mechanical properties by optimizing the kind and the like.

It is another object of the present invention to provide a pellet composition for reinforcing resin which can exhibit the same composition and effect as the inorganic-containing long fiber reinforced pellets in the production of molded articles.

The present invention also aims to provide an inorganic-containing resin molded article made of the inorganic-containing long fiber reinforced pellet or the pellet composition for the reinforced resin and excellent in mechanical properties.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

The inorganic-containing long fiber reinforced pellet according to one aspect of the present invention includes a thermoplastic polymer resin, a fiber reinforcing material having a length of 5 to 50 mm, and an inorganic material having an average particle size of 1 to 10 μm. The thermoplastic polymer resin has a melt index (MI) at a temperature of 230 ° C. and a load of 2.16 kg of 0.1 to 80 g / 10 min.

Inorganic-containing long fiber reinforced pellets according to another aspect of the present invention is 20 to 80% by weight of thermoplastic polymer resin, 10 to 40% by weight of fiber reinforcement material having a length of 5 to 50mm and 10 to 40 inorganic material having an average particle size of 1 to 10㎛ Weight percent.

The inorganic material includes talc, calcium carbonate and barium sulfate, and the weight ratio of talc: calcium carbonate: barium sulfate may be 1: 0.5-2: 0.5-2.

In the inorganic-containing long fiber reinforced pellets according to another aspect of the present invention, the fiber reinforcing material has an average diameter of 0.3 to 50 µm, and is impregnated in the pellets so as to be parallel to the length direction of the pellets, and substantially the same as the pellets. It has a length.

The fiber reinforcing material is glass fiber, carbon fiber, metal fiber, nylon fiber, polyethylene terephthalate (PET) fiber, poly ether ether ketone (PEEK) fiber, liquid crystal polymer (LCP) fiber, polyacrylonitrile (PAN) fiber, ultra high molecular weight PE ( polyethylene) fiber, aramid fiber, natural fiber (natural fiber) is characterized in that at least one fiber selected from the group consisting of.

In the inorganic-containing long fiber reinforced pellet according to another aspect of the present invention, the inorganic material is talc, mica, clay, calcium carbonate, barium sulfate, glass bubble, glass beads at least one selected from the group consisting of glass beads, ceramic bubbles, whiskers, chopped glass fibers, carbon nanotubes, and carbon nanofibers It is characterized in that the substance.

In the inorganic-containing long fiber reinforced pellet according to another aspect of the present invention, the thermoplastic polymer resin is polypropylene, polyamide, polystyrene, styrene-acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS), poly Carbonate (PC), polyurethane (PU), polyoxymethylene (POM), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyphenylene sulfide (PPS) , Polyphenylene ether (PPE), polyether ether ketone (PEEK), liquid crystalline polymer (LCP), polyarylate (PAR), polymethylpentene (PMP), polysulfone (PSU), polyethersulfone (PES) and It characterized in that it comprises at least one polymer resin selected from the group consisting of polyimide (PI).

In the inorganic-containing long fiber reinforced pellet according to another aspect of the present invention, the thermoplastic polymer resin is a polyolefin-based polymer, and includes at least one selected from the group consisting of ethylene-α-olefin copolymers and styrene-diene copolymers having 3 or more carbon atoms. The copolymer is characterized in that it is mixed.

The ethylene in the inorganic-containing long fiber reinforced pellets according to another feature of the present invention

In the inorganic-containing long fiber reinforced pellet according to another aspect of the present invention, the styrene-diene copolymer may be a styrene-butylene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer, a styrene-isoprene-styrene At least one copolymer selected from the group consisting of a block copolymer, a styrene-ethylene-propylene block copolymer, and a styrene-ethylene-propylene-styrene block copolymer.

In the inorganic-containing long fiber reinforced pellets according to another aspect of the present invention, the polyolefin-based polymer is characterized by being modified with unsaturated carboxylic acid and derivatives thereof. The polyolefin-based polymer is grafted with at least one polar group selected from the group consisting of unsaturated carboxylic acids, derivatives thereof and organosilane compounds, characterized in that the graft rate is 0.3 to 5% by weight. 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. It is done. The organosilane compound is characterized in that at least one compound selected from the group consisting of aminosilane, epoxysilane, vinylsilane, methacryloxysilane.

Inorganic-containing long fiber reinforced pellet according to another aspect of the present invention is from the group consisting of antioxidants, neutralizing agents, nucleating agents, antistatic agents, flame retardants, varnishes, UV stabilizers, slip agents, mold release agents, colorants and dispersants having a surface hardness of 5 or less It further comprises at least one additive selected. The additives may be used for stabilization of polymers, cost reduction, and the like, and may be used within a range in which mechanical properties, appearance characteristics, deformation characteristics, and the like do not rapidly decrease. As the antioxidant, phenol-based antioxidants, phosphite-based antioxidants, thiodipropionate synergists, and the like may be used. As the neutralizing agent, calcium stearate, zinc oxide, or the like may be used. As the coloring agent, at least one compound selected from the group consisting of zinc sulfide, carbon black, and lithopone may be used. The carbon black may have an average particle diameter of 30 nm or less and an oil absorption number of 70 cc / 100 g to 150 cc / 100 g.

The pellet composition for reinforcing resins according to one aspect of the present invention comprises a) an inorganic material containing pellets consisting of 60 to 90% by weight of the first thermoplastic polymer resin and 10 to 40% by weight of inorganic material having an average particle size of 1 to 10 μm and b) agent 2 a long fiber reinforced pellet consisting of 10 to 90% by weight of the thermoplastic polymer resin and 10 to 90% by weight of the fiber reinforcing material having a length of 5 to 50mm. The inorganic-containing pellets and the long fiber-reinforced pellets are mixed in a weight ratio of 10:90 to 50:50. The reinforcing resin pellet composition may further include a resin pellet made of a third thermoplastic polymer resin. The third thermoplastic polymer resin may be the same kind as the first thermoplastic polymer resin or the second thermoplastic polymer resin.

Pellets composition for reinforcing resin according to another feature of the present invention is 20 to 80% by weight of the thermoplastic polymer resin, 10 to 40% by weight of the fiber reinforcing material having an average particle size of 5 to 50mm in the total composition of the reinforcing resin pellets The inorganic material-containing pellet and the long fiber-reinforced pellets are mixed so as to have a range of 10 to 40% by weight of an inorganic material having 1 to 10 μm. The thermoplastic polymer resin is a mixture of first and second thermoplastic polymer resins. The first and second thermoplastic polymer resins may be the same kind or different kinds.

Or the pellet composition for reinforcing resin according to another aspect of the present invention is 20 to 80% by weight of the thermoplastic polymer resin, 10 to 40% by weight of the fiber reinforcing material having a length of 5 to 50mm in the total composition of the reinforcing resin pellets, and the average particle The inorganic material-containing pellets, the long fiber reinforced pellets and the resin pellets are mixed so as to have a range of 10 to 40% by weight of inorganic material having a size of 1 to 10 µm. The thermoplastic polymer resin is a mixture of first, second and third thermoplastic polymer resins. The first, second and third thermoplastic polymer resins may be the same kind or different kinds.

The first thermoplastic polymer resin, the second thermoplastic polymer resin and the third thermoplastic polymer resin may have the same type as the thermoplastic polymer resin included in the inorganic-containing long fiber reinforced pellets. That is, the first thermoplastic polymer resin, the second thermoplastic polymer resin and the third thermoplastic polymer resin are polypropylene, polyamide, polystyrene, styrene-acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS), respectively. ), Polycarbonate (PC), polyurethane (PU), polyoxymethylene (POM), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polyphenylene ether (PPE), polyether ether ketone (PEEK), liquid crystal polymer (LCP), polyarylate (PAR), polymethylpentene (PMP), polysulfone (PSU), polyethersulfone ( PES) and polyimide (PI) may include at least one polymer resin selected from the group consisting of.

Or the first thermoplastic polymer resin, the second thermoplastic polymer resin, and the third thermoplastic polymer resin are polyolefin-based polymers, and include at least one selected from the group consisting of an ethylene-α-olefin copolymer and a styrene-diene copolymer having 3 or more carbon atoms. The copolymer of is characterized by being mixed. Specific types and properties of the ethylene-α-olefin copolymer, styrene-diene copolymer, and polyolefin-based polymer are the same as described above in the description related to the inorganic-containing long fiber reinforced pellet, and thus will be omitted.

At least one thermoplastic polymer resin of the first thermoplastic polymer resin and the second thermoplastic polymer resin has a melt index (MI) of 0.1 to 80 g / 10 min at a temperature of 230 ° C. and a 2.16 kg load. The third thermoplastic polymer resin may also have a melt index (MI) of 0.1 to 80 g / 10 min at a temperature of 230 ° C. and a load of 2.16 kg.

Pellet composition for reinforcing resin according to another feature of the present invention is a) 20 to 80% by weight of the fourth thermoplastic polymer resin, 10 to 40% by weight of the fiber reinforcing material having a length of 5 to 50mm, and the average particle size of 1 to 10㎛ Inorganic-containing long fiber reinforced pellets composed of 10 to 40% by weight of phosphorus minerals, b) 60 to 90% by weight of the fifth thermoplastic polymer resin and 10 to 40% by weight of inorganic materials having an average particle size of 1 to 10 μm, and c) a long fiber reinforced pellet composed of 10 to 90% by weight of the sixth thermoplastic polymer resin and 10 to 90% by weight of the fiber reinforcing material having a length of 5 to 50mm. The reinforcing resin pellet composition may further include a resin pellet made of a seventh thermoplastic polymer resin.

The reinforcing resin pellet composition is characterized by consisting of 10 to 70% by weight of a) inorganic fiber-containing long fiber reinforced pellets, b) 5 to 80% by weight of inorganic-containing pellets and c) 10 to 90% by weight of long fiber reinforced pellets.

The pellet composition for reinforcing resin according to another aspect of the present invention is 20 to 80% by weight of the thermoplastic polymer resin, 10 to 40% by weight of the fiber reinforcing material having a length of 5 to 50mm in the total composition and the average particle size of 1 to 10㎛ The inorganic-containing long fiber reinforced pellets, the inorganic-containing pellets and the long fiber-reinforced pellets are mixed so as to be in the range of 10 to 40% by weight of the inorganic material. The thermoplastic polymer resin is a mixture of fourth, fifth, and sixth thermoplastic polymer resins.

Alternatively, the pellet composition for reinforcing resins according to another aspect of the present invention may include 20 to 80 wt% of thermoplastic polymer resin, 10 to 40 wt% of fiber reinforcing material having a length of 5 to 50 mm, and an average particle size of 1 to 10 μm in the whole composition. The inorganic material-containing long fiber reinforced pellets, the inorganic material-containing pellets, the long fiber-reinforced pellets and the resin pellets are mixed so as to be in the range of 10 to 40% by weight of phosphorus inorganic material. The thermoplastic polymer resin is a mixture of fourth, fifth, sixth and seventh thermoplastic polymer resins.

The fourth thermoplastic polymer resin has a melt index (MI) of 0.1 to 80 g / 10 min at a temperature of 230 ° C. and a load of 2.16 kg.

Inorganic-containing resin molded article according to one aspect of the present invention comprises a fiber reinforcement, the average length of the fiber reinforcement is 1 to 5 mm and the resin molded article is characterized by containing an inorganic material having an average particle size of 1 to 10㎛ It is done. The fiber reinforcing material is contained 10 to 40% by weight relative to the total weight of the molded article, the inorganic material is contained 10 to 40% by weight relative to the weight of the total molded article. The molded article is characterized by having a tensile strength of 730 to 1000 kgf / cm ² and IZOD impact strength of 9.0 to 15.0 kgfcm / cm.

The inorganic-containing resin molded article is formed of an inorganic-containing long fiber reinforced pellet, a pellet composition for reinforced resin, or a mixture thereof.

The average length of the fiber reinforcing material finally remaining in the molded article produced from the long fiber reinforced pellet or the pellet composition for reinforcing resin is 1 mm or more, preferably 2 mm or more. The content of the fiber reinforcement having a length of at least 1 mm of the total fiber reinforcement contained in the molded article is 10 to 70% by weight, the average length of the fiber reinforcement is approximately 1 to 5 mm.

Injection molding, compression molding, extrusion molding, blow molding, foam molding, gas injection molding, metal insert injection molding, metal insert compression molding, etc. are not particularly limited as a method of molding the molded article, but injection molding, metal insert injection molding, etc. More preferred.

The molded article is characterized by comprising a resin having a melt index (MI) of 0.1 to 80 g / 10 min at a temperature of 230 ° C. and a 2.16 kg load.

When molded into a reinforcing resin pellet composition in which the inorganic-containing long fiber reinforced pellet or the inorganic-containing pellet and the long fiber reinforced pellet according to the present invention are mixed, excellent tensile strength and impact strength are exhibited. In addition, high flexural modulus can be exhibited without lowering the tensile strength and impact strength of the molded article, thereby optimizing the mechanical properties.

In addition, by using inorganic-containing long fiber reinforced pellets containing both inorganic and long fibers at the same time, it is possible to reduce not only high mechanical properties but also manufacturing cost. In particular, when producing a molded article, a pellet composition for reinforcing resin exhibiting the same composition as the inorganic-containing long fiber-reinforced pellets also has the same effect as the inorganic-containing long fiber-reinforced pellets.

The inorganic-containing long fiber reinforced pellet according to the present invention includes a thermoplastic polymer resin, a fiber reinforcing material having a length of 5 to 50 mm, and an inorganic material having an average particle size of 1 to 10 m.

The inorganic-containing long fiber reinforced pellets consist of 20 to 80% by weight of thermoplastic polymer resin, 10 to 40% by weight of fiber reinforcing material having a length of 5 to 50mm, and 10 to 40% by weight of inorganic material having an average particle size of 1 to 10 μm.

When the ratio of the thermoplastic polymer resin in the inorganic-containing long fiber reinforced pellets exceeds 80% by weight, the impact strength and the bending property are lowered, and when the ratio is less than 20%, the moldability is lowered. To 80% by weight.

In addition, when the melt index (MI) at 230 ° C. and a 2.16 kg load of the thermoplastic polymer resin is less than 0.1 g / 10 min, a decrease in productivity and a flow mark may occur in the final product, and the melt index may occur. If (MI) is greater than 80g / 10min, it is difficult to obtain desired physical properties in impact resistance, tensile strength, impact strength, flexural strength, and the like. Accordingly, the melt index (MI) at 230 ° C. and a 2.16 kg load of the thermoplastic polymer resin is 0.1 to 80 g / 10 min.

Examples of the thermoplastic polymer resin include polypropylene, polyamide, polystyrene, styrene-acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC), polyurethane (PU), and polyoxymethylene ( POM), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polyphenylene ether (PPE), polyether ether ketone (PEEK) ), At least one polymer resin selected from the group consisting of liquid crystal polymer (LCP), polyarylate (PAR), polymethylpentene (PMP), polysulfone (PSU), polyethersulfone (PES) and polyimide (PI) May be used alone or in combination.

Among the thermoplastic polymers, the polyolefin polymer may be used alone or in admixture with a rubber resin. The rubber resin is a mixture of at least one copolymer selected from the group consisting of ethylene-αolefin copolymers having 3 or more carbon atoms and styrene-diene copolymers.

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.

The ethylene-α-olefin copolymer includes at least one copolymer selected from the group consisting of ethylene-propylene copolymers, ethylene-butene-1 copolymers and ethylene-octene copolymers.

The styrene-diene copolymer may include an aromatic vinyl compound in an amount of 10 to 50% by weight in the styrene-diene copolymer. 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. 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 and styrene -Ethylene-propylene-styrene block copolymers, and the like, and these copolymers may be used alone or in combination.

In addition, the polyolefin-based polymer is characterized in that it is modified with unsaturated carboxylic acid and derivatives thereof. The polyolefin-based polymer is grafted with at least one polar group selected from the group consisting of unsaturated carboxylic acids, derivatives thereof and organosilane compounds, characterized in that the graft rate is 0.3 to 5% by weight.

Modified polypropylene may be used as the modified polyolefin-based polymer. The modified polypropylene is obtained by grafting polar functional groups such as unsaturated carboxylic acid, derivatives thereof, and organosilane compounds to polypropylene. At this time, if the graft rate 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 modified polypropylene may be prepared by grafting one or two or more polar groups selected from the polar functional groups listed above to a polypropylene resin.

When the content of the modified polypropylene is less than 1% by weight, it is difficult to have an effect on improving rigidity, flexural characteristics and urethane adhesion, and when the content of the modified polypropylene is higher than 10% by weight, the modified polypropylene may be deteriorated. It is preferably included by 1 to 10% by weight based on the total inorganic-containing long fiber reinforced pellets.

The inorganic-containing long fiber reinforced pellets may have a variety of shapes such as cylindrical, oval, rugby ball, flat cylindrical, and the like. The length of the pellet is 5 to 50 mm. The fiber reinforcing material has an average diameter of 0.3 to 50 µm and is impregnated parallel to the length direction of the pellets, which is substantially the same as the length of the pellets. The length of the fiber reinforcement in the inorganic fiber containing long fiber reinforcement pellets is suitable 5 ~ 50mm, if less than 5mm the deformation is increased and the strength of the weld line portion is reduced, if it is longer than 50mm it is well put into the cylinder from the molding machine hopper It may not be able to be formed and moldability may deteriorate.

The 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 or more selected from fibers 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.

In addition, in order to increase the wettability of the polymer, the 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 fiber reinforcement in the total inorganic-containing long fiber reinforcement pellets is less than 10% by weight, the amount of deformation is increased, the required flexural characteristics cannot be expressed, the mechanical properties reinforcement effect is decreased, and the fiber reinforcement may be cut if it is larger than 40% by weight. And moldability deteriorates. Therefore, the fiber reinforcing material is contained by 10 to 40% by weight in the inorganic-containing long fiber reinforced pellets.

In the inorganic-containing long fiber reinforced pellets, the inorganic material is talc, mica, clay, calcium carbonate, barium sulfate, glass bubble, glass bead, ceramic bubble. at least one inorganic material selected from the group consisting of bubbles, whiskers, chopped glass fibers, carbon nanotubes and carbon nanofibers, with an average particle size of 1 to It is characterized by a 10㎛.

Talc, calcium carbonate and barium sulfate may be used as the inorganic material, and the weight ratio of talc: calcium carbonate and barium sulfate is 1: 0.5-2: 0.5-2, and the total weight of the inorganic material is 10-40 in the pellet. Weight percent.

If the average particle size of the inorganic material is larger than 10 μm, there is a problem in that tensile strength and IZOD impact strength are lowered. In addition, when the content of the inorganic material is less than 10% by weight in the pellet, the reinforcement effect of the flexural modulus is inferior, and when the content of the inorganic material is more than 40% by weight, the molding processability is deteriorated. When the kind of the inorganic material is the same, and the content of the inorganic material is the same as a specific value in the range of 10 to 40% by weight, the degree of reinforcement for the flexural modulus of the molded article is not significantly related to the average particle size of the inorganic material. However, the use of inorganic materials with an average particle size larger than 10 μm results in a significant decrease in tensile and IZOD impact strengths, while the use of inorganic materials less than 10 μm can reinforce flexural modulus without deterioration in tensile and IZOD impact strengths. Will be. As such, the reinforcing effect on the mechanical properties is different depending on the content or particle size of the inorganic material, the present invention is to provide an inorganic-containing long fiber reinforced pellets that can maximize the reinforcement of the mechanical properties by the inorganic material.

The inorganic-containing long fiber reinforced pellets are characterized by further comprising at least one additive selected from the group consisting of antioxidants, neutralizers, nucleating agents, antistatic agents, flame retardants, varnishes, UV stabilizers, slip agents, mold release agents, colorants and dispersants. . The colorant is characterized in that the surface hardness is 5 or less, the colorant may be used at least one compound selected from the group consisting of zinc sulfide, carbon black and lithopone. The carbon black has an average particle diameter of 30 nm or less and an oil absorption number of 70 cc / 100g to 150 cc / 100g is used.

When the surface hardness of the colorant is greater than 5, the fiber reinforcement may be damaged due to the collision and friction of the colorant and the fiber reinforcement during the production of the inorganic-containing long fiber-reinforced pellets or during the molding of the final molded product using the inorganic-containing long fiber-reinforced pellets. Breakage may occur, resulting in deterioration of mechanical properties. Therefore, this invention uses the coloring agent whose surface hardness is five or less. However, among pigments having a surface hardness of 5 or less, deterioration of mechanical properties may occur due to other properties such as particle size in the case of specific pigments. In particular, in the case of carbon black, the larger the particle size and the smaller the oil absorption number, the lower the mechanical properties. That is, the mechanical properties of the molded article are lowered due to the properties of the specific colorant. In order to minimize the decrease in the physical properties, the present invention determines the type and characteristics of the pigment used as the colorant.

As the colorant, at least one compound selected from the group consisting of zinc sulfide, carbon black and lithopone may be used. All of the above compounds have a surface hardness of 5 or less. However, in the case of carbon black, the average particle diameter is 30 nm or less, and the oil absorption number must satisfy 70 cc / 100 g to 150 cc / 100 g. The oil absorption coefficient is a measure of the ability of carbon black to absorb liquids. When the oil absorption coefficient of the carbon black is less than 70 cc / 100g, the mechanical properties of the molded article are lowered, and when it is larger than 150 cc / 100g, the moldability is deteriorated. In addition, when the average particle diameter of the carbon black is greater than 30nm, the coloring ability and the mechanical properties of the molded article may be reduced.

Hereinafter, the pellet composition for reinforcement resin in which the inorganic substance containing pellet, the long fiber reinforced pellet, etc. are mixed.

The pellet composition for reinforcing resin is a) an inorganic containing pellet consisting of 60 to 90% by weight of the first thermoplastic polymer resin and 10 to 40% by weight of inorganic material having an average particle size of 1 to 10 µm, and b) 10 to 90% by weight of the second thermoplastic polymer. It consists of long fiber reinforced pellets consisting of 10 to 90% by weight of fiber reinforcement with a% and a length of 5 to 50 mm. The first thermoplastic polymer resin and the second thermoplastic polymer resin may be the same or different kinds.

The first and second thermoplastic polymer resins, inorganic materials, and fiber reinforcing materials are the same as those described above with respect to the inorganic-containing long fiber reinforcing pellets, and thus, redundant descriptions thereof will be omitted.

The pellet composition for reinforcing resin is dry mixed form of the a) inorganic-containing pellets and the b) long fiber-reinforced pellets in a weight ratio of 10:90 to 50:50, the composition ratio of each component after mixing is the inorganic-containing sheet It is characterized by being included in the composition ratio of the fiber-reinforced pellets. That is, a molded article manufactured by molding a pellet composition for reinforcing resin in which a) inorganic-containing pellets and b) long fiber-reinforced pellets are mixed may have the same composition ratio as a molded article manufactured by molding inorganic-containing long fiber reinforced pellets. In addition, the composition of the pellet composition for reinforcing resin may further be added d) resin pellets consisting of only the third thermoplastic polymer resin, thereby adjusting the overall composition ratio of the pellet composition for reinforcing resin.

Meanwhile, the pellet composition for reinforcing resin may further include an inorganic-containing long fiber reinforced pellet. That is, the pellet composition for reinforcing resin is a) 20 to 80% by weight of the fourth thermoplastic polymer resin, 10 to 40% by weight of the fiber reinforcing material having a length of 5 to 50mm, and 10 to 40% by weight of the inorganic material having an average particle size of 1 to 10㎛ Inorganic-containing long fiber reinforced pellet consisting of, b) 60 to 90% by weight of the fifth thermoplastic polymer resin and 10 to 40% by weight of inorganic material having an average particle size of 1 to 10㎛ and c) the sixth thermoplastic polymer resin Long fiber-reinforced pellets consisting of 10 to 90% by weight and 10 to 90% by weight of fiber reinforcements of 5 to 50 mm in length may be formed by dry mixing. Similarly, d) resin pellets composed of only the seventh thermoplastic polymer resin may be further added to the pellet composition for reinforcing resin. A molded article prepared by molding a pellet composition for reinforcing resin which is a mixture of a), b) and c) or a pellet composition for reinforcing resin which is a mixture of a), b), c) and d) may be formed of an inorganic-containing long fiber reinforced pellet. It may have the same composition ratio as the molded article manufactured by molding.

Alternatively, the reinforcing resin pellet composition may be composed of 10 to 70% by weight of inorganic-containing long fiber reinforced pellets, 5 to 80% by weight of inorganic-containing pellets and 10 to 90% by weight of long fiber reinforced pellets. The pellet composition for the reinforcing resin is in the range of 20 to 80% by weight of the thermoplastic polymer resin, 10 to 40% by weight of the fiber reinforcing material having a length of 5 to 50mm and 10 to 40% by weight of the inorganic material having an average particle size of 1 to 10㎛ in the whole composition The inorganic-containing long fiber reinforced pellets, the inorganic-containing pellets and the long fiber reinforced pellets may be mixed to be. Or the resin pellet composition has a range of 20 to 80% by weight of thermoplastic polymer resin, 10 to 40% by weight of fiber reinforcing material having a length of 5 to 50mm and an inorganic material having an average particle size of 1 to 10 μm in the total composition. The inorganic-containing long fiber reinforced pellets, the inorganic-containing pellets, the long fiber-reinforced pellets and the resin pellets may be mixed. The inorganic material may be used in a single kind, but may be used in combination of several kinds. In addition, although the type or content of the inorganic material contained in the inorganic-containing pellet and the inorganic material contained in the inorganic-containing long fiber reinforced pellet may be the same, the present invention is not limited thereto.

In addition, a combination of suitable pellets selected from the group consisting of inorganic-containing long fiber reinforced pellets, inorganic-containing pellets, long fiber reinforced pellets and resin pellets can cause the composition ratio in the manufactured molded article to have a specific value.

The molded article includes a fiber reinforcement, wherein the average length of the fiber reinforcement is 1 to 5 mm and the resin molded article is characterized by containing an inorganic material having an average particle size of 1 to 10 μm.

The present invention will be described in more detail with reference to the following examples. The following examples are illustrative for explaining the inorganic-containing long fiber reinforced pellets, the pellet composition for reinforcing resins, and the inorganic-containing resin molded article according to the present invention in more detail, but the content of the present invention is not limited to the following examples. .

Example  1 to 4 and Comparative example  1 to 3

Polypropylene resin (PP) having a melt index (MI) of 12 g / 10min at a temperature of 230 ° C. and a 2.16 kg load, and a modified polypropylene (mPP) in which 1% of maleic anhydride was grafted to polypropylene. Mineral-containing long fiber reinforced pellets were prepared using glass fibers (LGF) and inorganics. Examples of the inorganic material include talc (T1) having an average particle size of 5 μm in Examples 1 and 4, calcium carbonate (CC) having an average particle size of 2 μm in Example 2, and an average particle size of 2 in Example 3. Barium sulfate (BS) having a thickness was used, and talc (T2) having an average particle size of 12 µm was used in Comparative Examples 1 and 2. In Comparative Example 3, no inorganic substance was added.

The weight ratio between the components used in Examples 1 to 4 and Comparative Examples 1 to 3 and each component is summarized in Table 1 below.

PP mPP LGF T1 T2 CC BS Example 1 50 10 10 30 Example 2 50 10 10 30 Example 3 50 10 10 30 Example 4 50 10 20 20 Comparative Example 1 50 10 10 30 Comparative Example 2 50 10 20 20 Comparative Example 3 80 10 10

According to the composition of Table 1, an inorganic substance-containing long fiber reinforced pellet having a length of 10 mm was prepared so that the length of the glass fiber was the same as the length of the pellet. Using the injection molding machine of 150 tons of clamping force, the specimens were prepared for tensile strength, flexural modulus, and IZOD impact strength using the injection machine of 150 ton clamping force. Tensile strength was measured according to ASTM D638, flexural modulus was measured according to ASTM D790, and IZOD impact strength was measured with a notched specimen at room temperature (23 ° C) according to ASTM D256.

 Ten specimens were evaluated for each physical property to obtain an average value, and the results are summarized in Table 2 below.

Tensile Strength (kgf / cm ² ) Flexural modulus (kgf / cm ² ) IZOD impact strength (kgfcm / cm) Example 1 750 59000 9.0 Example 2 735 45000 9.7 Example 3 758 42500 9.3 Example 4 985 60300 14.5 Comparative Example 1 650 58000 6.2 Comparative Example 2 857 59800 8.8 Comparative Example 3 740 31900 9.5

As can be seen from the experimental results, when comparing the mechanical properties of the pellets according to Examples 1 to 4 containing inorganic materials having an average particle size of 10 μm or less and the pellets of Comparative Example 3 containing only a fiber reinforcing material without containing inorganic materials, tensile strength And IZOD impact strengths are similar, but there is a big difference in the flexural modulus. That is, in the case of pellets containing an inorganic material having an average particle size of 10 μm or less, the flexural modulus can be significantly increased without decreasing tensile strength and IZOD impact strength.

On the other hand, when comparing the case of Example 1 and Comparative Example 1 and the case of Example 4 and Comparative Example 2 of the same inorganic content in the pellet, even if the same content, the fiber reinforcing material and the inorganic material of the same component is used It can be seen that there is a big difference in the mechanical properties that can be implemented depending on the size. In more detail, regardless of the average particle size of inorganic materials, the same type and content of inorganic materials contribute to the reinforcement of flexural modulus, but in case of using an inorganic material with an average particle size larger than 10 μm, the tensile strength and IZOD impact strength On the other hand, when the inorganic particles having an average particle size of 10 μm or less are used, the flexural modulus can be reinforced without damaging the tensile strength and the IZOD impact strength.

Example  5 to 8 and Comparative example  4 to 5

Polypropylene resin (PP) having a melt index (MI) of 12 g / 10 min at 230 ° C. and a load of 2.16 kg, modified polypropylene (mPP) having 1% grafted on polypropylene, and a diameter of 17 μm. Long fiber reinforced pellets having a length of 10 mm were prepared using glass fiber (LGF), and the length of the glass fibers impregnated in the long fiber reinforced pellets was the same as that of the pellets.

In addition, an inorganic substance-containing pellet was prepared in which an inorganic substance was concentrated in a polypropylene resin (PP) having a melt index (MI) of 12 g / 10 min at a temperature of 230 ° C. and a 2.16 kg load. Examples of the inorganic material include talc (T1) having an average particle size of 5 μm in Examples 5 and 8, calcium carbonate (CC) having an average particle size of 2 μm in Example 6, and an average particle size of 2 in Example 7. Barium sulfate (BS), which is μm, was used, and talc (T2) having an average particle size of 12 μm was used in Comparative Examples 4 and 52. Herein, the inorganic-containing pellets were composed of the composition ratios of Table 3 below and were prepared using a twin screw extruder, and were dry mixed according to the mixing ratios of the separately prepared long fiber reinforced pellets and Table 3 below.

The components used in the long fiber reinforced pellets and the inorganic-containing pellets and the weight ratios between the respective components are summarized in Table 3 below. In the following Table 3, the dry mixing ratio is the weight ratio of the resin pellets consisting of long fiber reinforced pellets: inorganic containing pellets: polypropylene resin only.

Long fiber reinforced pellets Mineral-containing pellets Dry mix ratio PP mPP LGF PP T1 T2 CC BS Example 5 40 10 50 60 40 20: 75: 5 Example 6 40 10 50 60 40 20: 75: 5 Example 7 40 10 50 60 40 20: 75: 5 Example 8 40 10 50 66 34 50: 50: 0 Comparative Example 4 40 10 50 60 40 20: 75: 5 Comparative Example 5 40 10 50 60 40 20: 75: 5

Tensile strength, flexural modulus, and IZOD impact strength specimens were fabricated using the injection force of 150 tons of clamping force and manufactured according to ASTM test method. Ten specimens of each sample were evaluated to obtain an average value, and the results are summarized in Table 4 below.

Tensile Strength (kgf / cm ² ) Flexural modulus (kgf / cm ² ) IZOD impact strength (kgfcm / cm) Example 5 747 58300 9.2 Example 6 740 46300 10.1 Example 7 751 41700 9.8 Example 8 977 59900 14.1 Comparative Example 4 627 58500 6.3 Comparative Example 5 860 60300 8.1

Through the above experimental results, it can be seen that when an inorganic material having an average particle size of 10 μm or less is used, the flexural modulus can be reinforced without deterioration of tensile strength and IZOD impact strength.

In addition, when comparing the case of Examples 1 to 4 using the inorganic-containing long fiber reinforced pellets alone and the Examples 5 to 8 using the inorganic-containing pellets and the long fiber-reinforced pellets alone, When the composition ratio of the fiber reinforcing material is the same, and the kind and average particle size of the inorganic material used is the same, it can be seen that exhibits the reinforcing effect of the same to similar mechanical properties.

Inorganic-containing long fiber reinforced pellets and pellet composition for reinforced resins according to the present invention can exhibit excellent flexural modulus without lowering tensile strength and IZOD impact strength when manufacturing molded products, thereby optimizing mechanical properties and greatly reducing manufacturing costs. Therefore, it is expected to be utilized in various industries such as the automobile industry.

Claims (26)

A thermoplastic polymer resin having a melt index (MI) of 0.1 to 80 g / 10 min at a temperature of 230 ° C. and a load of 2.16 kg; Fiber reinforcement having a length of 5 to 50 mm; And An inorganic-containing long fiber reinforced pellet comprising an inorganic substance having an average particle size of 1 to 10 µm. The method of claim 1, 20 to 80 wt% of the thermoplastic polymer resin; 10 to 40% by weight of the fiber reinforcing material; And Mineral-containing long fiber reinforced pellets, characterized in that consisting of 10 to 40% by weight of the inorganic material. The method of claim 2, The inorganic material includes talc, calcium carbonate and barium sulfate, and the weight ratio of talc: calcium carbonate: barium sulfate is 1: 0.5 to 2: 0.5 to 2. The method of claim 1, The fiber reinforcing material has an average diameter of 0.3 to 50㎛, inorganic-containing long fiber reinforced pellets, characterized in that the same length as the inorganic fiber-containing long fiber reinforced pellets. The method of claim 4, wherein The 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 ( polyethylene) fibers, aramid fibers, natural fibers containing at least one fiber selected from the group consisting of inorganic fibers, characterized in that the long fiber reinforced pellets. The method of claim 1, The inorganic material may be talc, mica, clay, calcium carbonate, barium sulfate, glass bubble, glass bead, ceramic bubble, whiskers, An inorganic-containing long fiber reinforced pellet, characterized in that it is at least one material selected from the group consisting of chopped glass fiber, carbon nanotube, and carbon nanofiber. The method of claim 1, The thermoplastic polymer resin is polypropylene, polyamide, polystyrene, styrene-acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC), polyurethane (PU), polyoxymethylene (POM) ), Polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polyphenylene ether (PPE), polyether ether ketone (PEEK) At least one polymer resin selected from the group consisting of liquid crystal polymer (LCP), polyarylate (PAR), polymethylpentene (PMP), polysulfone (PSU), polyethersulfone (PES) and polyimide (PI) Inorganic-containing long fiber reinforced pellets, characterized in that it comprises. The method of claim 1, The thermoplastic polymer resin is a polyolefin-based polymer, and inorganic-containing long fiber reinforced pellets, characterized in that at least one copolymer selected from the group consisting of ethylene-α-olefin copolymers having 3 or more carbon atoms and styrene-diene copolymers is mixed. . The method of claim 8, The ethylene-α-olefin copolymer is an inorganic-containing long fiber reinforced, 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 Pellets. The method of claim 8, 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 An inorganic-containing long fiber reinforced pellet comprising at least one copolymer selected from the group consisting of -propylene-styrene block copolymers. The method of claim 8, The polyolefin-based polymer is grafted with at least one polar group selected from the group consisting of unsaturated carboxylic acid, derivatives thereof, and organosilane compound, inorganic material-containing long fiber reinforced pellets, characterized in that the graft rate is 0.3 to 5% by weight. The method of claim 1, The inorganic-containing long fiber reinforced pellet further comprises at least one additive selected from the group consisting of antioxidants, neutralizers, nucleating agents, antistatic agents, flame retardants, varnishes, UV stabilizers, slip agents, mold release agents, colorants having a surface hardness of 5 or less, and dispersants. Mineral-containing long fiber reinforced pellets, characterized in that. The method of claim 1, The colorant is an inorganic-containing long fiber reinforced pellets, characterized in that the average particle diameter is 30nm or less, the oil absorption number (carbon absorption) of 70 cc / 100g to 150 cc / 100g. Inorganic-containing pellets consisting of 60 to 90% by weight of the first thermoplastic polymer resin and 10 to 40% by weight of inorganic material having an average particle size of 1 to 10 µm; And Long fiber reinforced pellets composed of 10 to 90 wt% of the second thermoplastic polymer resin and 10 to 90 wt% of the fiber reinforcement having a length of 5 to 50 mm; Reinforcing resin pellet composition comprising a. The method of claim 14, A pellet composition for reinforcing resin in which the inorganic-containing pellet and the long fiber reinforced pellet are mixed in a weight ratio of 10:90 to 50:50. The method of claim 14, The pellet composition for reinforcing resin further comprises a resin pellet comprising a third thermoplastic polymer resin of the same kind as the first thermoplastic polymer resin or the second thermoplastic polymer resin. The method according to claim 14 or 16, The pellet composition for reinforcing resin is in the whole composition, 20 to 80% by weight of a thermoplastic polymer resin; 10 to 40% by weight of the fiber reinforcement having a length of 5 to 50mm; And 10 to 40% by weight of inorganic material having an average particle size of 1 to 10 mu m; Pellet composition for reinforcing resin comprising a. The method of claim 14, At least one thermoplastic polymer resin of the first thermoplastic polymer resin and the second thermoplastic polymer resin has a melt index (MI) of 0.1 to 80 g / 10 min at a temperature of 230 ° C. and a load of 2.16 kg. Composition. a) an inorganic-containing long fiber reinforced pellet consisting of 20 to 80% by weight of the fourth thermoplastic polymer resin, 10 to 40% by weight of the fiber reinforcing material having a length of 5 to 50 mm, and 10 to 40% by weight of the inorganic material having an average particle size of 1 to 10 m. ; b) an inorganic-containing pellet consisting of 60 to 90% by weight of the fifth thermoplastic polymer resin and 10 to 40% by weight of inorganic material having an average particle size of 1 to 10 µm; And c) a long fiber reinforced pellet consisting of 10 to 90 wt% of the sixth thermoplastic polymer resin and 10 to 90 wt% of the fiber reinforcement having a length of 5 to 50 mm; This mixed pellet composition for reinforcing resin. The method of claim 19, The pellet composition for reinforcing resin further comprises a resin pellet made of a seventh thermoplastic polymer resin. The method of claim 19, The fourth thermoplastic polymer resin has a melt index (MI) at a temperature of 230 ° C. and a load of 2.16 kg of 0.1 to 80 g / 10 min. The method of claim 19, The pellet composition for reinforcing resin 10 to 70% by weight of the inorganic-containing long fiber reinforced pellets; 5 to 80% by weight of the inorganic containing pellets; And Reinforcing resin pellet composition, characterized in that consisting of 10 to 90% by weight of the long fiber reinforced pellets. The method of claim 19 or 20, The pellet composition for reinforcing resin is in the whole composition, 20 to 80% by weight of a thermoplastic polymer resin; 10 to 40% by weight of the fiber reinforcement having a length of 5 to 50mm; And 10 to 40% by weight of inorganic material having an average particle size of 1 to 10 mu m; Pellet composition for reinforcing resin comprising a. In the resin molded article containing a fiber reinforcement, The average length of the fiber reinforcement is 1 to 5 mm and includes 10 to 40% by weight relative to the total weight of the molded article, The resin molded article contains an inorganic material having an average particle size of 1 to 10㎛ 10 to 40% by weight relative to the total weight of the molded article, has a tensile strength of 730 to 1000 kgf / cm ² and an impact strength of 9.0 to 15.0 kgfcm / cm Inorganic-containing resin molded article characterized by the above-mentioned. The method of claim 24, The inorganic resin molded article is molded of at least one of the inorganic-containing long fiber reinforced pellets of claim 1, the pellet composition for reinforced resins of claim 14 or the pellet composition for reinforced resins of claim 19. The method of claim 24, The resin molded article is an inorganic-containing resin molded article, characterized in that the melt index (MI) at a temperature of 230 ℃, 2.16kg load comprises a resin of 0.1 to 80g / 10min.