KR101202699B1 - Manufacturing method of scratch self-healing mouldings using polypropylene-elastomer nano alloys composition - Google Patents

Abstract

PURPOSE: A manufacturing method of scratch self-healing molded products using polypropylene - elastomer nano-alloy composition is provided to have soft touch feeling and scratch self-reproducing properties. CONSTITUTION: A manufacturing method of scratch self-healing molded products using polypropylene - elastomer nano-alloy composition comprises the following steps: manufacturing a polypropylene - elastomer nano-alloy composite by melting and extruding the polypropylene - elastomer nano-alloy composition; manufacturing a molded product by extruding or emitting the polypropylene - elastomer nano-alloy composite. The polypropylene - elastomer nano-alloy composition comprises 20-500 parts by weight of thermoplastic elastomer, 5-100.0 parts by weight of ceramic particles or ceramic particles coated with hydroxy-terminated silane compound, and 1-10 parts by weight of fluorine-containing polyolefin based on 100 parts by weight of acid anhydride group-contained polypropylene based resin.

Description

Manufacturing method of scratch self-healing mouldings using polypropylene-elastomer nano alloys composition

The present invention relates to a novel polypropylene-elastomer nanoalloy composition and a method for producing a scratch self-renewing molded article using the same.

More specifically, the new polypropylene has excellent heat resistance and impact resistance by reaction extrusion as well as excellent scratch self regeneration, and is suitable for automobile interior parts having excellent electric conductivity, scratch resistance, impact resistance, abrasion resistance and modulus. Elastomer nanoalloy compositions and molded articles made therefrom.

Polypropylene-based resins, which are widely applied to automobile interior parts such as crash pads, doatrims and interior trims, have been spotlighted due to many advantages, such as good mechanical properties, light weight materials, and recyclability, but they lack impact resistance and heat resistance. This required improvement. First, as a method of improving impact resistance, a method of preparing a composite by adding an appropriate amount of elastomer such as thermoplastic olefin elastomer and thermoplastic styrene elastomer to polypropylene resin has been attempted. In this case, the composite is usually made of a polypropylene resin matrix ( The elastomer in the matrix forms a micrometer-sized domain and takes the form of a so-called micro alloy. In addition, in order to overcome the lack of heat resistance, which has been further insufficient due to the addition of elastomer, a composite having reinforced impact resistance and heat resistance by adding inorganic fillers such as talc and glass fibers has been developed and is widely used today (Polymer Composites, 9, 72 (1988) ), U.S. Patent 5,591,795 and the like.

However, the molded article of such a composite is a product that emphasizes “stiffness” which greatly improves the flexural modulus, and is a serious problem in which the surface damage caused by scratches, which is a bad soft touch feeling and the important factor of visual sensitivity, easily occurs. There is an urgent need for countermeasures.

Recently, "scratch self-renewable paint", which is made of material that emphasizes "elastic recovery power" rather than rigidity, has been developed and introduced as a vehicle exterior paint, but similarly, the automotive interior materials made of polypropylene-based composite resins have conventional heat resistance and There is an urgent need for the development of a new concept of highly sensitive polymer materials with a soft touch and scratch self-regeneration by excellent "elastic recovery".

Until now, the method of coating a molded article has been most widely used as a means of solving scratches on molded articles made of polypropylene composites. However, with the addition of the painting process, the manufacturing process is complicated and the unit cost increases, and the volatile substances are released due to the organic solvent used during the painting process. It is exposed. As another solution, a method of adding a silicone resin such as a high molecular weight polydimethylsiloxane as a kind of a lubricant in the preparation of a conventional polypropylene composite has been newly proposed (Elastomer, 43 (3), 183 (2008)). The addition of such lubricants smoothes the surface of the product and reduces the coefficient of friction, thereby distributing the impact from the outside to the surface. However, the scratch resistance is somewhat improved compared to the coating, and the surface gloss is also improved. Increasing the sensitivity of the molded product by reducing the quality of the molded article, when used in excess of the lack of compatibility with the polypropylene-based resin causes a phase separation phenomenon and the physical properties of the product, such as transition to the surface has been called for the emergence of a new technology.

In accordance with such a request, the present inventors have applied to the novel polypropylene-elastomer nanoalloy and the scratch self- regulating molded article manufactured therefrom in Korean Patent Nos. 10-0981393 (2010.09.03) and 10-0981391 (2010.09.03). There is a need for a novel polypropylene-elastomer nanoalloy that has a related application, but which has better electrical conductivity, scratch resistance, abrasion resistance, impact resistance and modulus than the above patent.

Korea Patent Registration No. 10-0981393 (2010.09.03) Korea Patent Registration No. 10-0981391 (2010.09.03)

In order to solve the above problems, the inventor of the present invention has made intensive studies and has come to the present invention. That is, the present invention has a new concept of highly sensitive polymer material having a soft touch feeling and scratch self-renewability due to excellent impact resistance and heat resistance and excellent "elastic recovery force" suitable for environmentally friendly, unpainted automotive interior parts which do not have volatile emission. A novel polypropylene-elastomer nanoalloy, which is a part, and molded articles made therefrom are provided.

In addition, the present invention is to provide a novel polypropylene-elastomer nanoalloy excellent in scratch resistance by preventing the inorganic particles are detached and molded articles prepared therefrom.

In addition, the present invention is to provide a novel polypropylene-elastomer nanoalloy with improved electrical conductivity and wear resistance, impact resistance and heat resistance and molded articles made therefrom.

The present invention for achieving the above object is a novel polypropylene-elastomer nanoalloy composition suitable for automobile interior parts having excellent heat resistance and impact resistance by reaction extrusion as well as excellent scratch self-renewability and a method for producing a molded article using the same It is about.

Specifically, the production method of the polypropylene-elastomer nanoalloy of the present invention

Polypropylene-elastomer nanoalloy composition containing 20 to 500 parts by weight of thermoplastic elastomer, 5 to 100 parts by weight of ceramic particles coated with ceramic particles or hydroxy-terminated silane compound, based on 100 parts by weight of acid anhydride group-containing polypropylene resin. Melt extrusion to prepare a polypropylene-elastomer nanoalloy composite;

Extruding or injecting the polypropylene-elastomer nanoalloy composite to prepare a molded article;

It includes.

In addition, the present invention is based on 100 parts by weight of the acid anhydride group-containing polypropylene resin, 20 to 500 parts by weight of thermoplastic elastomer, 1 to 30 parts by weight of the epoxy group-containing polyolefin copolymer, 0.001 to 0.5 parts by weight of the amine compound, aminosilane 0.01 to 0.5 parts by weight of the compound, 1 to 10 parts by weight of the fluorine-containing polyolefin compound and 0.1 to 50 parts by weight of inorganic particles coated with a hydroxy-terminated silane compound.

Another method for producing the polypropylene-elastomer nanoalloy of the present invention is

To 100 parts by weight of the acid anhydride group-containing polypropylene resin, 20 to 500 parts by weight of thermoplastic elastomer, 5 to 100 parts by weight of ceramic particles coated with ceramic particles or a hydroxy-terminated silane compound, and an epoxy group-containing polyolefin copolymer 1 to 30 parts by weight, 0.1 to 50 parts by weight of inorganic particles surface-treated with an amine compound, 0.01 to 0.5 parts by weight of aminosilane compound, 1 to 10 parts by weight of fluorine-containing polyolefin compound and 0.1 to inorganic particles coated with hydroxy terminal silane compound Preparing a polypropylene-elastomer nanoalloy composite by melt extruding the polypropylene-elastomer nanoalloy composition including ˜50 parts by weight;

Extruding or injecting the polypropylene-elastomer nanoalloy composite to prepare a molded article;

It includes.

In the present invention, the melt extrusion process is a cylinder temperature of 180 ~ 250 ℃, length / diameter ratio (L / D) is preferably using a twin screw extruder of 30 or more.

In addition, the present invention may further include 5 to 300 parts by weight of polypropylene resin, based on 100 parts by weight of the acid anhydride group-containing polypropylene resin.

In addition, the present invention provides a scratch self-regenerated molded article characterized in that the polypropylene-elastomer nanoalloy is obtained by melting and extrusion or injection processing.

In another aspect, the present invention provides a scratch self-renewing automotive component, characterized in that the polypropylene-elastomer nanoalloy is obtained by melting and extrusion or injection processing.

More specifically, one embodiment of the present invention will be described, the first embodiment is a coating treatment with 20 to 500 parts by weight of thermoplastic elastomer, ceramic particles or hydroxy-terminated silane compound based on 100 parts by weight of the acid anhydride group-containing polypropylene resin. Preparing a polypropylene-elastomer nanoalloy composite by melt-extruding the polypropylene-elastomer nanoalloy composition including 5 to 100 parts by weight of the ceramic particles; Extruding or injecting the polypropylene-elastomer nanoalloy composite to prepare a molded article; It includes.

Further, in the second aspect of the present invention, 1 to 30 parts by weight of the epoxy group-containing polyolefin copolymer, 0.001 to 0.5 part by weight of the amine compound, and aminosilane based on 100 parts by weight of the acid anhydride group-containing polypropylene resin in the first aspect. 0.01 to 0.5 parts by weight of the compound, 1 to 10 parts by weight of the fluorine-containing polyolefin compound and 0.1 to 50 parts by weight of inorganic particles coated with a hydroxy-terminated silane compound.

Further, the third aspect of the present invention further includes 5 to 300 parts by weight of polypropylene resin with respect to 100 parts by weight of the acid anhydride group-containing polypropylene resin in the first aspect.

Moreover, the 4th aspect of this invention contains 5-300 weight part of polypropylene resins with respect to 100 weight part of acid anhydride group containing polypropylene resins in the said 2nd aspect.

A fifth aspect of the present invention is based on 100 parts by weight of the acid anhydride group-containing polypropylene resin, 20 to 500 parts by weight of thermoplastic elastomer, 5 to 100 parts by weight of ceramic particles coated with ceramic particles or hydroxy-terminated silane compound, epoxy group 1 to 30 parts by weight of a containing polyolefin copolymer, 0.1 to 50 parts by weight of inorganic particles surface-treated with an amine compound, 0.01 to 0.5 parts by weight of an aminosilane compound, 1 to 10 parts by weight of a fluorine-containing polyolefin compound and a hydroxy-terminated silane compound 0.1 to 50 parts by weight of inorganic particles coated with.

The sixth aspect of the present invention further comprises 5 to 300 parts by weight of polypropylene resin, based on 100 parts by weight of the acid anhydride group-containing polypropylene resin in the fifth aspect.

Hereinafter, the present invention will be described in detail. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

As a result of increasing the content of the thermoplastic elastomer in the polypropylene composite composed of the conventional polypropylene resin, the thermoplastic elastomer, the inorganic particle particles, etc., it was found that the impact resistance and the soft touch were greatly increased and the scratch self-renewal was expressed. . However, the heat dimensional stability expressed by the heat deflection temperature, that is, the heat resistance, is extremely bad, and thus the level of the molded article for automotive interior parts cannot be used at all. Therefore, there is a need for a new technology that can drastically improve this. In recent years, the polymer or alloy system between polymers of different properties has extremely high compatibility between the constituent polymers, so that a very fine nano-sized domain is formed. In the so-called “polymer nanoalloy”, the compatibility between the constituent polymers is not very good. Research reports have been published that show breakthrough physical properties that have never been seen in conventional "polymer microalloys" in which micro-sized domains are formed. In view of this, the inventors of the present invention raise the compatibility between the polypropylene resin and the thermoplastic elastomer to extremely high levels of the thermoplastic elastomer which contributes to the impact resistance, the soft touch feeling and the scratch self-renewal expression in the polypropylene composite. Nevertheless, it came to the idea that the lowering of heat resistance could be extremely suppressed, and the present invention was started.

Under these circumstances, the innovative solution introduced in the present invention is to introduce a reactive group (I) which may cause covalent bonds by mutual reaction into a polypropylene resin, while having excellent compatibility with the thermoplastic elastomer and having a polypropylene system. A polyolefin resin having a reactive group (II) which can easily react with the reactive group (I) introduced into the resin is introduced into a so-called reactive compatibilizer to react with the polypropylene resin and the thermoplastic elastomer through a reactive extrusion process. To form a nanoalloy of. As a specific attempt, reaction extrusion was carried out using a composition composed of an acid anhydride group-containing polypropylene resin, a thermoplastic elastomer, and an epoxy group-containing polyolefin copolymer, and as a result, the reaction between the acid anhydride group and the epoxy group was not surprising. It was found that compatibility between the polypropylene resin and the thermoplastic elastomer was expressed. However, the domain size was a little short of the expression of several tens of nanoscale ultrafine nanoalloys originally desired at the level of several hundred nano or submicro. As a method of solving this problem, a longer reaction extrusion time resulted in a nanoalloy of a desired target level, but a new problem of yellowing occurred due to the decomposition of some polymers, and a problem of rising costs required a new solution.

As a means to solve the above problem, an amine compound or an inorganic particle whose surface treatment has been introduced is introduced. That is, the reaction extrusion is performed using a composition in which an amine compound or an inorganic particle surface-treated with an amine compound is additionally added in addition to the acid anhydride group-containing polypropylene resin, thermoplastic elastomer, and epoxy group-containing polyolefin copolymer. In the reaction reaction between acid anhydride and epoxy group within a short reaction extrusion time such that polymer decomposition does not occur, an inorganic particle having an amine compound or an amine compound surface treatment is surprisingly surprising due to its unique action as a kind of catalyst. The excellent compatibility between the thermoplastic elastomer and the thermoplastic elastomer was expressed, and the thermoplastic elastomer in the polypropylene resin matrix was able to successfully express the ultrafine nanoalloy formed by the domains of several to several tens of nano-sizes that we want. - nano-alloyed elastomer is known that not only has excellent heat resistance and impact resistance to the initial purpose at the same time exhibit excellent scratch self regeneration, thereby completing the present invention.

In addition, in the case of including the ceramic particles in the present invention, the durability, scratch resistance and hardness is further improved by the high hardness of the ceramic particles to complete the present invention.

In addition, in the present invention, it was found that as the fluorine-containing polyolefin compound is added, excellent electric conductivity, wear resistance, and heat resistance are improved.

In addition, the hydroxy-terminated silane compound on the surface of the inorganic particles in order to improve the separation of the inorganic particles with the addition of the inorganic particles, and to generate scratches, to induce even distribution of the inorganic particles to have more excellent modulus and scratch resistance. It was found that the target physical properties are further improved by using the coating treatment to complete the present invention.

In the present invention, the acid anhydride group-containing polypropylene resin includes a polypropylene homopolymer or propylene obtained by graft reaction of an acid anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. in a biaxial extruder, a reaction vessel, or the like. As the copolymer, the graft ratio is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, and the melt index is 1 to 100 g / 10 minutes, preferably 2 to 50 g / 10 minutes. For example, the acid anhydride group-containing polypropylene resin obtained from a twin screw extruder is 0.1 to 10 parts by weight of an acid anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, and preferably 0.2 to 3 parts by weight of polypropylene resin. Parts by weight, such as azo compounds such as 2,2-azobisisobutyronitrile and 2,2-azobis (2,4,4-trimethylvaleronitrile), peroxides such as dicumyl peroxide and t-butyl peroxide. 0.01-3 parts by weight of the radical initiator, preferably 0.02-1 parts by weight, is obtained by carrying out the graft reaction through a twin screw extruder (cylinder temperature; 180-250 ° C). More specific examples of the acid anhydride group-containing polypropylene resin (A) include Mitsui Chemical Co., Ltd. Admer QB510A, QF551A, DuPont, Bynel 50E662, 50E739, Fusabond P613, P353 and the like, which are maleic anhydride graft polypropylene. .

In the present invention, the thermoplastic elastomer is an propylene-αolefin-based elastomer such as ethylene-hexene elastomer, ethylene-octene-based elastomer, propylene-hexene-based elastomer, propylene-hexene-based elastomer, propylene-octene-based elastomer, ethylene- Thermoplastic olefin elastomers including propylene-diene elastomers and the like, styrene-butadiene block copolymers, styrene-isoprene block copolymers, hydrogenated styrene-butadiene elastomers, styrene-butadiene-styrene elastomers, styrene-ethylene-butylene Thermoplastic styrene elastomers including styrene-based elastomers, styrene-ethylene-propylene-styrene-based elastomers, and the like, and the like can be used alone or as a mixture thereof. As a more specific example of such a thermoplastic elastomer, Dow Chemical Engage 8200, an ethylene-octene elastomer, JSR, Dynaron 2324P, a hydrogenated styrene-butadiene elastomer, Kraton polymers, Kraton G1643M, a styrene-ethylene-butylene-styrene elastomer, Etc. can be mentioned.

In the present invention, the thermoplastic elastomer content may be 20 to 500 parts by weight based on 100 parts by weight of the acid anhydride group-containing polypropylene resin. If it is less than 20 parts by weight, it is difficult to achieve the purpose of securing a soft touch feeling and scratch self-renewal, and if it exceeds 500 parts by weight, heat resistance may be poor.

This invention contains 5-100 weight part of ceramic particles with respect to 100 weight part of acid anhydride group containing polypropylene resins. The ceramic particles may further improve durability, scratch resistance and hardness as compared with the case where only inorganic particles are added by high hardness. Specifically, the type of the ceramic particles may be, for example, one single particle or two selected from zinc oxide, titanium oxide, alumina, zirconia, yttria, ceria, gallium oxide, iron oxide, nickel oxide, cobalt oxide, and copper oxide. The above composite oxide can be used, but it is not limited to these. In addition, the average particle diameter of the ceramic particles is preferably 1 to 10,000 nm, preferably 1 to 1,000 nm, more preferably 1 to 500 nm.

The composite oxide may be zirconium salt, aluminum salt, yttrium salt, magnesium salt, calcium salt, cerium salt, niobium salt, scandium salt, neodymium salt, plutonium salt, praseodymium salt, samarium salt, europium salt, gadolinium salt, promethium salt, And it may be prepared by sintering a metal salt such as erbium salt, for example, zirconia-alumina nano-composite powder may be used, but is not limited thereto.

The epoxy group-containing polyolefin copolymer in the present invention is glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ester, aryl glycidyl ether, 2-methyl aryl glycidyl ether, styrene-p Examples of copolymers of olefins with epoxy group-containing compounds such as glycidyl ether and the like include ethylene-glycidyl methacrylate copolymers, Arkema Lotader AX8840 and ethylene-methacrylate-glycidyl methacrylate copolymers. The chain Arkema company Lotader AX8900, AX8920, the DuPont company Elvaloy PTW etc. which are ethylene- butylacrylate- glycidyl methacrylate copolymers are mentioned.

The epoxy group-containing polyolefin copolymer content is preferably added 1 to 30 parts by weight based on 100 parts by weight of the acid anhydride group-containing polypropylene resin. If it is less than 1 part by weight, the role as a reactive compatibilizer may not be expressed, and ultimately, it may be difficult to secure scratch self-regeneration and heat resistance. If it exceeds 30 parts by weight, the physical properties thereof may be soft and the heat resistance may be weak.

As the amine compound in the present invention, any of aliphatic, aromatic or cyclic primary to quaternary amines can be used. Specific examples thereof include methylamine, dimethylamine, trimethylamine, tetramethylamine, ethylamine and diethylamine. , Triethylamine, tetraethylamine, triethanolamine, N, N-dimethylbenzylamine, N-methylaniline, N, N'-dimethylaniline, N, N'-diethylaniline, ethylenediamine, tetramethylenediamine, hexa Methylenediamine, triethylenetetramine, diethylenetriamine, pyridine, quinoline, 4,4'-methylenedianiline, 2,4,6-tris (dimethylaminomethyl) phenol and the like.

The content of the amine compound may be added in an amount of 0.001 to 0.5 parts by weight based on 100 parts by weight of the acid anhydride group-containing polypropylene resin. If it is less than 0.001 parts by weight, the role as a unique catalyst is not manifested and ultimately it is difficult to secure scratch self-regeneration and heat resistance. If it exceeds 0.5 parts by weight, it may be transferred to the surface of the molded product due to its low molecular weight, thereby deteriorating the appearance quality.

In the present invention, the fluorine-containing polyolefin compound is used to improve the balance of physical properties of excellent electrical conductivity, wear resistance and heat resistance, and specifically, for example, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / Any one or a mixture of two or more selected from vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer and ethylene / tetrafluoroethylene copolymer can be used.

The fluorine-containing polyolefin compound may be added in an emulsion or powder state, and when used in a powder state, the particle size is 0.01 ~ 500㎛, more preferably 1 ~ 300 ㎛, most preferably 3 ~ 50㎛, specific gravity Preference is given to using 1.2 to 2.3 g / cm 3.

It is preferable to use 1-10 weight part of said fluorine-containing polyolefin compound with respect to 100 weight part of acid anhydride group containing polypropylene resins. If the amount is less than 1 part by weight, the effect is insignificant, and even if it is used in excess of 10 parts by weight, no further improvement in physical properties can be obtained, thereby obtaining the best balance of electrical conductivity, wear resistance, and heat resistance in the above range. .

In the present invention, in the inorganic particles coated with the hydroxy-terminated silane compound, the inorganic particles are talc, calcium carbonate, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, aluminum hydroxide, magnesium hydroxide, mica, Asbestos, zeolite, clay silicate, glass fibers, whiskers, and the like, and these may be used alone or as a mixture thereof. The inorganic particles may be in the form of spheres, needles, plates, and the like, and have an average particle diameter of 1 to 10,000 nm, preferably 1 to 1,000 nm, more preferably 1 to 500 nm. Also preferred are fibrous inorganic particles such as glass fibers and whiskers.

In addition, in the present invention, the surface of the inorganic particles is coated with a hydroxy-terminated silane compound to prevent dispersibility and detachment, and to improve heat resistance, durability, scratch resistance and modulus.

As the hydroxy-terminated silane compound, hydroxy-terminated silane compound of Formula 1 or hydroxy-terminated poly (dimethylsiloxane) may be used.

[Formula 1]

HO- (Si (CH ₃ ) ₂ ) -O-) nH

(Wherein n is an integer selected from 1 to 100).

The inorganic particles coated with the hydroxy-terminated silane compound are preferred because 0.1 to 50 parts by weight of the inorganic anhydride group-containing polypropylene resin is used in an amount of 0.1 to 50 parts by weight.

In addition, the present invention may use inorganic particles surface-treated with amine-based compounds instead of amine-based compounds as a method for improving the amine-based compound having low molecular weight, which may be transferred to the surface of a molded article when an excessive amount is used. The inorganic particles surface-treated with the amine compound in the present invention are produced by treating the surface of the inorganic particle directly or indirectly with the amine compound. The amine-based compound is finally inorganic particles by treating the amine-based compound alone or with other compounds that are helpful for the surface treatment reaction, or by treating the amine compound with another compound that is helpful for the surface treatment reaction in advance. It is a type fixed to the surface. For example, an inorganic particle is coated with a reactant between an amine compound and a silane compound. Specifically, a triamine-alkyl / dimethyl copolymer (Genesee Polymers trade name GP-4) is coated on the surface of talc particles. The inorganic particle (Viton Product company brand name ABT-G B4) is mentioned, Glass fiber etc. which surface-treated the 3- (2-aminoethyl) -aminopropyl trimethoxy silane are mentioned.

The inorganic particle content treated with the amine compound may be added in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the acid anhydride group-containing polypropylene resin. If it is less than 0.1 part by weight, the role as a catalyst is not expressed and ultimately it is difficult to secure scratch self-regeneration and heat resistance. If it exceeds 50 parts by weight, the heat resistance is improved, but the soft touch feeling and self-regeneration may be deteriorated by the content of many inorganic particles. have.

In the present invention, the polypropylene resin is a propylene homopolymer, a block copolymer or a copolymer having a propylene in the form of a random copolymer as a main component, and the like, and a double block copolymer is more preferable, and a melt index of 2 to 100 g / 10 min. Is appropriate.

The polypropylene resin is used to improve the heat resistance, it is preferable to use 5 to 300 parts by weight because it exhibits excellent physical properties.

In the present invention, the aminosilane compound is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane, N- (2- Aminoethyl) -3-aminopropyl-methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl-triethoxysilane and N- (2-aminoethyl) -3-aminopropyl-triisopro Any one or more selected from foxysilanes may be used.

The aminosilane compound may be used to further improve scratch prevention and surface hardness, the content of which is preferably 0.01 to 0.5 parts by weight because it expresses excellent physical properties.

The polypropylene-elastomer nanoalloy according to the present invention can be prepared through reaction extrusion in a conventional twin screw extruder, in which case the length / diameter ratio (L / D) of the twin screw extruder is preferably 30 or more, preferably 40 or more. It is preferable that the furnace is 50 or more, and in particular, it is preferable to proceed with the cylinder temperature 180-250 degreeC in a twin screw extruder. As L / D is proportional to the reaction time, there is no big limitation on the upper limit of L / D in that the larger the L / D, the greater the compatibility improvement effect by the reaction. However, if the L / D exceeds 100, the extruder manufacturing technology is difficult. There is a problem that the equipment price rises sharply, and if it exceeds 200, there is a risk of thermal decomposition of the resin by heat as it stays in the extruder for too long.

In addition, the extrusion or injection process may be manufactured by a conventional manufacturing method according to the form required by the user, wherein the temperature during the extrusion or injection process is preferably 180 ~ 250 ℃.

In the polypropylene-elastomer nanoalloy according to the present invention, conventional additives such as antioxidants, ultraviolet stabilizers, processing aids, thermal stabilizers, lubricants, pigments, dyes, and the like can be blended in a range that does not impair the object of the present invention. have.

The molded article produced by extrusion or injection by a known method using the polypropylene-elastomer nanoalloy composition according to the present invention, more specifically, a crash pad, doatrim, interior parts such as interior trim are also included in the scope of the present invention.

As described above, the polypropylene-elastomer nanoalloy according to the present invention and the molded article prepared therefrom are very useful for automobile interior parts having not only excellent heat resistance, electric conductivity, abrasion resistance and impact resistance, but also excellent scratch self regeneration. It is expected to be used.

The present invention will be described in more detail with reference to the following examples, which are not limited to only one example of the present invention.

The impact strength, thermal deformation temperature, soft touch, and scratch self-renewal of the specimens prepared according to the following Examples and Comparative Examples were measured as follows.

1. Impact strength

After preparing the injection specimen, the impact strength at 23 ° C. was measured according to ASTM D-256 as a measure for impact resistance.

2. Heat Deflection Temperature

After the injection specimen was prepared, the heat deflection temperature was measured according to ASTM D-648 as a measure of heat resistance.

3. Soft touch

The soft touch feeling was obtained by averaging the results of evaluation of the soft touch feeling felt by hand pressing the specimens by 50 persons after making flat-type injection specimens having a thickness of 20 mm. According to the degree of excellent soft touch feeling, the evaluation was performed in the order of A (excellent), B (good), C (normal), and D (bad) grades.

4. Scratch self regeneration

Scratch self-regeneration was evaluated by mounting each specimen in a scratch tester (manufactured by HEIDON) with a 3Φ sapphire tip after forming the injection specimen, and forming a scratch under a 500g load. In particular, the scratch state was visually observed after 1 hour after the scratch was generated to see the scratch self-renewal by the elastic recovery force with time. According to the degree to which no scratch was observed, the evaluation was performed in order of A (excellent), B (good), C (normal), and D (bad) grades.

5. Surface Resistance (Ω / sq)

The surface resistance of each specimen was measured according to ASTM D257 using Wolfgang Warmbier's SRM-100.

6. Stretch resistance (wear resistance)

1) Dynamic Friction Coefficient: The dynamic friction coefficient of the specimen was measured according to JIS K 7218.

2) Abrasion: According to ASTM D4060, one 10cm × 10cm specimen and two aluminum circular specimens having a diameter of 5cm were fabricated, and the wear loss before and after friction was measured by rubbing for 10,000 cycles at 90 rpm using a Taber friction tester.

Example 1

As the acid anhydride group-containing polyolefin resin (A), maleic anhydride graft polypropylene (DuPont, Fusabond P613, hereinafter MAH-g-PP) having a melt index (230 ° C., 2.16 Kg) of 49 g / 10 minutes and a melting point of 162 ° C. A1)), an ethylene-octene-based elastomer (Dow Chemical, Engage 8200, hereinafter TPE (B1)) at 5.0 g / 10min as a melt elastomer (190 ° C., 2.16 Kg) as the thermoplastic elastomer (B), ceramic Zirconia-alumina nanocomposites (hereinafter referred to as CF (H1)) powders having an average particle diameter of 200 nm were prepared as particles.

To 100 parts by weight of MAH-g-PP (A1), a composition (see Table 1) containing 20 parts by weight of TPE (B1) and 20 parts by weight of CF (H1) was added to a twin screw extruder having a diameter of 70 mm and L / D 40. The melt was extruded at a cylinder temperature of 200 ° C. to obtain a final polypropylene composite (1).

The obtained polypropylene composite (1) was prepared in an injection molding machine by injection molding and evaluated for physical properties thereof, and the results are shown in Table 3.

[Example 2]

As the acid anhydride group-containing polyolefin resin (A), maleic anhydride graft polypropylene (DuPont, Fusabond P613, hereinafter MAH-g-PP) having a melt index (230 ° C., 2.16 Kg) of 49 g / 10 minutes and a melting point of 162 ° C. A1)), an ethylene-octene elastomer (Dow Chemical, Engage 8200, hereinafter TPE (B1)) of 5.0 g / 10 min as melt index (190 DEG C, 2.16 Kg) as thermoplastic elastomer (B), epoxy group Ethylene-glycidyl methacrylate copolymer (Lorkder AX8840 from Arkema, hereinafter referred to as EPO (C1)) of 5 g / 10 min as melt-containing polyolefin-based resin (C) (190 ° C, 2.16 Kg), amine compound (D) 2,4,6-tris (dimethylaminomethyl) phenol (Aldrich, hereinafter referred to as AM (D1), 3-aminopropyltrimethoxysilane as an aminosilane compound (hereinafter referred to as AS (E1))) Hydroxy-terminated polyolefin (Teflon 7AJ, hereinafter referred to as FPO (F1)), a fluorine-containing polyolefin compound, and inorganic particles coated with a hydroxy-terminated silane compound. Methylsiloxane (SIGMA-ALDRICH, product number: 432970) was prepared by coating 5% by weight of silica (average particle diameter: 500 nm, hereinafter referred to as SF (G1)) by zirconia with an average particle diameter of 200 nm. Alumina nanocomposite (hereinafter referred to as CF (H1)) powder was prepared.

To 100 parts by weight of MAH-g-PP (A1), 20 parts by weight of TPE (B1), 20 parts by weight of CF (H1), 5 parts by weight of EPO (C1), 0.07 parts by weight of AM (D1), AS (E1) 0.1 part by weight, 2 parts by weight of FPO (F1) and 30 parts by weight of SF (G1) were added to a twin screw extruder having a diameter of 70 mm and L / D 40, followed by melt extrusion at a cylinder temperature of 200 ° C. Polypropylene composite (2) was obtained.

The obtained polypropylene composite (2) was prepared in an injection molding machine by injection molding and evaluated for physical properties thereof, and the results are shown in Table 3.

[Example 3]

In Example 1, the polypropylene-based composite (3) was obtained in the same manner as in Example 1 except that the composition (see Table 1) containing 5 parts by weight of FPO (F1) was used.

The obtained polypropylene composite (3) was produced in an injection molding machine, and the physical properties thereof were evaluated, and the results are shown in Table 3.

Example 4

In Example 1, the polypropylene-based composite (4) was obtained in the same manner as in Example 1 except that the composition (see Table 1) in which the content of FPO (F1) was mixed at 10 parts by weight.

The obtained polypropylene composite (4) was prepared in an injection molding machine by injection molding and evaluated for physical properties thereof, and the results are shown in Table 3.

[Example 5]

As the thermoplastic elastomer (B), a styrene-ethylene-butylene-styrene-based elastomer (Kraton polymers, Kraton G1643M, TPE (B2)) having a melt index (230 ° C., 2.16 Kg) of 18.0 g / 10 minutes was used. Surface-treated with hydroxy terminated poly (dimethylsiloxane) (ALDRICH) with 20 wt% of the weight of alumina (average particle size 400nm) with ceramic particles coated with a terminal silane compound (hereinafter referred to as CF (H2)) A polypropylene composite (5) was obtained in the same manner as in Example 1 except that it was used.

The obtained polypropylene composite (5) was produced in an injection molding machine by injection molding and evaluated for physical properties thereof, and the results are shown in Table 3.

[Example 6]

As the epoxy group-containing polyolefin resin (C), Arkema's Lotader AX8900 (EPO (C2)), an amine having an ethylene-methacrylate-glycidyl methacrylate copolymer of 6.0 g / 10 minutes, melt index (190 ° C., 2.16 Kg). Tetraethylamine (Aldrich, AM (D2)) as a compound (D), a propylene block copolymer having a melt index (230 ° C., 2.16 Kg) of 30.0 g / 10 minutes and a melting point of 168 ° C. as a polypropylene resin. , Grade CB5230, PP (I1)) was prepared.

To 100 parts by weight of MAH-g-PP (A1), 75 parts by weight of TPE (B1), 20 parts by weight of CF (H2), 12 parts by weight of EPO (C2), 0.1 parts by weight of AM (D2), AS (E1) Except for using 0.5 parts by weight, 5 parts by weight of FPO (F1), 30 parts by weight of SF (G1), 50 parts by weight of PP (A) (see Table 1) was carried out in the same manner as in Example 1 polypropylene-based Composite 6 was obtained.

The obtained polypropylene composite 6 was prepared in an injection molding machine, and the physical properties thereof were evaluated, and the results are shown in Table 3 below.

[Example 7]

As the acid anhydride group-containing polyolefin resin (A), maleic anhydride graft polypropylene (Mitsui Chemical, Admer QB510A, MAH-g-PP) having a melt index (230 ° C., 2.16 Kg) of 3.3 g / 10 minutes and a melting point of 162 ° C. (A2)) was prepared and surface-treated polyhydroxy dimethylsiloxane (ALDRICH) with ceramic particles coated with a hydroxy-terminated silane compound at 20% by weight relative to the weight of alumina (average particle size 400 nm). (Hereinafter referred to as CF (H2)), and a polypropylene resin, a propylene block copolymer (melting index (230 ° C, 2.16Kg) 30.0g / 10min, melting point 168 ° C) (Korea Chemical Industries, Grade CB5230, PP (I1)) was prepared.

To 100 parts by weight of MAH-g-PP (A2), 60 parts by weight of TPE (B1), 20 parts by weight of CF (H2), 5 parts by weight of EPO (C1), 0.2 parts by weight of AM (D1), AS (E1) Example 1 except using the composition (refer Table 1) which mixed 0.5 weight part, 8 weight part of FPO (F1), 30 weight part of SF (G1), 20 weight part of CF (H1), and 50 weight part of PP (I1). In the same manner as in the above, a polypropylene-based composite (7) was obtained.

The obtained polypropylene composite 7 was prepared in an injection molding machine, and the physical properties thereof were evaluated, and the results are shown in Table 3 below.

[Example 8]

As inorganic particles (F) surface-treated with an amine compound, a glass fiber (AF (G2)) having a length of 3 mm having a surface treated with 3- (2-aminoethyl) -aminopropyl trimethoxy silane was prepared.

To 100 parts by weight of MAH-g-PP (A2), 80 parts by weight of TPE (B2), 20 parts by weight of CF (H1), 12 parts by weight of EPO (C2), 0.1 parts by weight of AS (E1), FPO (F1) A polypropylene composite composite (8) was obtained in the same manner as in Example 2, except that a composition (see Table 3) containing 5 parts by weight, 30 parts by weight of SF (G1) and 20 parts by weight of AF (G2) was used.

The obtained polypropylene composite 8 was prepared in an injection molding machine, and after evaluation of physical properties thereof, the results are shown in Table 3.

[Example 9]

As a polypropylene resin, a propylene block copolymer (Korea Chemical Industries, Grade CB5230, PP (I1)) having a melt index (230 ° C., 2.16 Kg) of 30.0 g / 10 minutes and a melting point of 168 ° C. was prepared.

Polypropylene-based composite (9) was obtained in the same manner as in Example 8 except that 50 parts by weight of PP (A) was further added.

The obtained polypropylene composite 9 was prepared in an injection molding machine, and the physical properties thereof were evaluated, and the results are shown in Table 3.

Comparative Example 1

It carried out similarly to Example 1 except having used the composition (refer Table 1) which mixed 30 weight part of TPE (B1) and 50 weight part of untreated talc (G3)) with respect to 100 weight part of PP (I1). Polypropylene composite 10 was obtained.

The obtained polypropylene composite 10 was prepared in an injection molding machine, and the physical properties thereof were evaluated, and the results are shown in Table 3 below.

Comparative Example 2

The polypropylene-based composite 11 was obtained in the same manner as in Example 1 except that a composition (see Table 1) mixed with 60 parts by weight of TPE (B1) was used based on 100 parts by weight of PP (I1).

The obtained polypropylene composite 11 was prepared in an injection molding machine, and the physical properties thereof were evaluated, and the results are shown in Table 3.

[Comparative Example 3]

Polypropylene was carried out in the same manner as in Example 1, except that 50 parts by weight of TPE (B1) and 10 parts by weight of EPO (C1) were used based on 100 parts by weight of MAH-g-PP (A1). System complex 12 was obtained.

The obtained polypropylene composite 12 was prepared in an injection molding machine, and the physical properties thereof were evaluated, and the results are shown in Table 3.

[Comparative Example 4]

Except having used the composition (refer Table 1) which mixed 600 weight part of TPE (B1), 12 weight part of EPO (C1), and 0.1 weight part of AS (E1)) with respect to 100 weight part of MAH-g-PP (A1). The polypropylene composite composite 13 was obtained in the same manner as in Example 1.

The obtained polypropylene composite 13 was prepared in an injection molding machine, and after evaluation of physical properties thereof, the results are shown in Table 3.

[Table 1]

[Table 2]

[Table 3]

N.B: no break

As can be seen in Examples 1 to 9, the polypropylene-based composite according to the present invention not only has excellent impact resistance and heat resistance, but also has excellent soft touch and scratch self-renewal, low surface resistance, and excellent wear resistance. Can be.

The present invention described above is not limited to the above-described embodiments, and various substitutions, modifications, and changes can be made without departing from the technical spirit of the present invention. It will be obvious to him.

Claims (22)

20 to 500 parts by weight of thermoplastic elastomer, 5 to 100 parts by weight of ceramic particles coated with ceramic particles or hydroxy-terminated silane compound, and 1 to 10 parts by weight of fluorine-containing polyolefin compound, based on 100 parts by weight of acid anhydride group-containing polypropylene resin. Preparing a polypropylene-elastomer nanoalloy composite by melt-extruding a polypropylene-elastomer nanoalloy composition comprising a polypropylene-elastomer nanoalloy composition comprising a portion;
Extruding or injecting the polypropylene-elastomer nanoalloy composite to prepare a molded article;
Method for producing a polypropylene-elastomer nanoalloy comprising a. The method of claim 1,
To 100 parts by weight of the acid anhydride group-containing polypropylene resin, 1 to 30 parts by weight of an epoxy group-containing polyolefin copolymer, 0.001 to 0.5 parts by weight of an amine compound, 0.01 to 0.5 parts by weight of an aminosilane compound and a hydroxy-terminated silane compound Method of producing a polypropylene-elastomer nanoalloy further comprises 0.1 to 50 parts by weight of inorganic particles coated with. To 100 parts by weight of the acid anhydride group-containing polypropylene resin, 20 to 500 parts by weight of thermoplastic elastomer, 5 to 100 parts by weight of ceramic particles coated with ceramic particles or a hydroxy-terminated silane compound, and an epoxy group-containing polyolefin copolymer 1 to 30 parts by weight, 0.1 to 50 parts by weight of inorganic particles surface-treated with an amine compound, 0.01 to 0.5 parts by weight of aminosilane compound, 1 to 10 parts by weight of fluorine-containing polyolefin compound and 0.1 to inorganic particles coated with hydroxy terminal silane compound Preparing a polypropylene-elastomer nanoalloy composite by melt extruding the polypropylene-elastomer nanoalloy composition including ˜50 parts by weight;
Extruding or injecting the polypropylene-elastomer nanoalloy composite to prepare a molded article;
Method for producing a polypropylene-elastomer nanoalloy comprising a. The method according to any one of claims 1 to 3,
The melt extrusion process is a polypropylene-elastomer nanoalloy using a twin screw extruder having a cylinder temperature of 180 ~ 250 ℃, length / diameter ratio (L / D) of 30 or more. The method according to any one of claims 1 to 3,
A method for producing a polypropylene-elastomer nanoalloy, further comprising 5 to 300 parts by weight of the polypropylene resin, based on 100 parts by weight of the acid anhydride group-containing polypropylene resin. 6. The method of claim 5,
The polypropylene-based resin is a method for producing a polypropylene-elastomer nanoalloy is a propylene homopolymer or a copolymer comprising propylene. 4. The method according to claim 2 or 3,
The aminosilane compound is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane, N- (2-aminoethyl) 3-aminopropyl-methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl-triethoxysilane and N- (2-aminoethyl) -3-aminopropyl-triisopropoxysilane Method for producing a polypropylene-elastomer nanoalloy which is at least one selected. 4. The method according to claim 2 or 3,
The acid anhydride group-containing polypropylene resin has a graft ratio of 0.1 to 10% by weight, and a melt index of 1 to 100 g / 10 min (230 ° C., 2.16 kg). 4. The method according to claim 2 or 3,
The thermoplastic elastomer is an olefin-based elastomer or a styrene-based elastomer, a method for producing a polypropylene-elastomer nanoalloy. 4. The method according to claim 2 or 3,
The epoxy group-containing polyolefin copolymer is glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ester, aryl glycidyl ether, 2-methylaryl glycidyl ether, styrene-p-glycidyl A method for producing a polypropylene-elastomer nanoalloy which is a copolymer of an epoxy group-containing compound selected from ether and an olefin. The method of claim 2,
The amine-based compound is a method for producing a polypropylene-elastomer nanoalloy is at least one primary to quaternary amine selected from the group consisting of aliphatic, aromatic, cyclic. 4. The method according to claim 2 or 3,
The inorganic particles may be any one or more selected from talc, calcium carbonate, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, aluminum hydroxide, magnesium hydroxide, mica, asbestos, zeolite, white silicate, glass fiber, and whiskers. Process for the preparation of propylene-elastomer nanoalloy. The method of claim 3, wherein
The inorganic particles surface-treated with the amine compound are talc, calcium carbonate, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, aluminum hydroxide, magnesium hydroxide, mica, asbestos, zeolite, clay silicate, glass fiber, A method for producing a polypropylene-elastomer nanoalloy, wherein the surface of any one or more inorganic particles selected from whiskers is treated with at least one primary to quaternary amine selected from the group consisting of aliphatic, aromatic, and cyclic shapes. 4. The method according to claim 2 or 3,
The fluorine-containing polyolefin compound includes polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer and ethylene / tetrafluoroethylene copolymer Method of producing a polypropylene-elastomer nanoalloy is any one or a mixture of two or more selected from. 4. The method according to claim 2 or 3,
The inorganic particles coated with the hydroxy-terminated silane compound are talc, calcium carbonate, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, aluminum hydroxide, magnesium hydroxide, mica, asbestos, zeolite, white silicate, glass A method for producing a polypropylene-elastomer nanoalloy, wherein a surface of at least one inorganic particle selected from fibers and whiskers is treated with a hydroxy-terminated silane compound of Formula 1 or a hydroxy-terminated poly (dimethylsiloxane).
[Formula 1]
HO- (Si (CH ₃ ) ₂ ) -O-) nH
(Wherein n is an integer selected from 1 to 100). The method according to claim 1 or 3,
The ceramic particles are any one single particle or two or more composite oxides selected from zinc oxide, titanium oxide, alumina, zirconia, yttria, ceria, gallium oxide, iron oxide, nickel oxide, cobalt oxide, and copper oxide polypropylene-elastomer Method for producing nanoalloy. The scratch self-regenerated molded article using the manufacturing method of the polypropylene-elastomer nanoalloy in any one of Claims 1-3. The scratch self-renewal molded article using the manufacturing method of the polypropylene-elastomer nanoalloy of Claim 4. Scratch self-regenerated molded article using the method for producing a polypropylene-elastomer nanoalloy according to claim 5. Scratch self-renewal automotive parts using the method for producing a polypropylene-elastomer nanoalloy according to any one of claims 1 to 3. Scratch self-renewal automotive parts using a method for producing a polypropylene-elastomer nanoalloy according to claim 4. Scratch self-renewal automotive parts using a method for producing a polypropylene-elastomer nanoalloy according to claim 5.