KR101347245B1 - Scratch self-healing polyurethane composition and mouldings produced therefrom - Google Patents

Abstract

The present invention relates to a scratch self-healing polyurethane resin composition and a molded product manufactured from the same and, more specifically, to a scratch self-healing polyurethane resin composition comprising: a thermoplastic poly urethane resin; a microcapsule (A) including a silicone compound with a vinyl group as a core; a microcapsule (B) including a silicone compound with a hydride group as a core; and a metallic catalyst. The polyurethane-based molded product prevents the release of volatile materials while maintaining excellent mechanical properties and soft touch feelings, exhibits excellent scratch resistance while having scratch self-healing properties and is able to be usefully used in surface materials of a motor vehicle interior component.

Description

Scratch self-healing polyurethane composition and mouldings produced therefrom

The present invention relates to a novel scratch self-healing polyurethane-based resin composition and molded articles prepared therefrom. More particularly, the present invention relates to a new scratch self-healing polyurethane-based resin composition suitable for the skin material of automotive interior having excellent scratch self-healing properties and molded articles produced therefrom.

Polyurethane resins, which are widely applied to the skin materials of automobile interior materials such as instrument panel, door trim, and built-in trim, have a disadvantage that the price is slightly higher than that of polypropylene resin, but due to many advantages such as soft touch feeling, It is in the spotlight as a skin material of a luxurious car interior material. In recent years, there is a serious problem that surface damage caused by scratch, which is an important factor of visual sensitivity, which is more emphasized in recent years, is a serious problem.

So-called "scratch self-healing" paint, which has a resilient ability to cure itself by itself over time and scratches can not be seen easily and returns to its original shape, has recently been introduced into automotive exterior materials, It is required to develop a new concept of high sensitivity polymer new material and parts having excellent scratch self-healing property while satisfying the required properties in the past for automobile interior materials made of polymers such as polyurethane resin and polypropylene resin in the same way .

Until now, as a means for solving scratches on a molded article made of a polymer, a method of coating a molded article has been most widely used. However, as the coating process is added, the manufacturing process becomes complicated and the unit price is increased. In addition, volatile substances are released due to the organic solvent used in the coating process, and thus exposure to environment- It is necessary to have a material which is suitable for environmentally friendly non-painted automobile interior material free from the risk of releasing volatile substances, and at the same time, can be drastically improved in scratch resistance.

As a solution to this problem, a method of adding a silicone resin such as polydimethylsiloxane having a high molecular weight as a lubricant to a polypropylene resin composition as a raw material for a conventional unpainted automobile interior part has been newly proposed (Elastomer, 43 (3), 183 (2008)). The addition of such a lubricant improves the scratch resistance to some extent by dispersing the impact applied from the outside to the surface by smoothing the surface of the product and reducing the friction coefficient, but the effect is considerably smaller than that of the coating, There is a disadvantage in that the quality of the molded article is deteriorated and scratch healing property is hardly obtained.

Examples of other solutions include polypropylene resins containing an acid anhydride group, thermoplastic elastomers, epoxy group-containing polyolefin copolymers, amine compounds, etc., as described in Korean Patent Registration Nos. 10-1202699, 10-0981393 and 10-0981391 Is a so-called polypropylene-based resin-elastomer nanoalloy formed by the reaction of an acid anhydride group and an epoxy group under the catalytic action of an amine-based compound, and thus has not only excellent heat resistance and impact resistance, The scratch self-healing property due to the elastic restoring force of the extensively well-dispersed elastomer was exhibited. However, since the healing level of the elastomer did not reach to the extent that the user could appreciably feel, it satisfied the conventional required properties and at the same time, Self-healing auto The advent of new manufacturing techniques for polymer materials suitable for skin materials of interior material has been keenly requested.

Korean Patent No. 10-1202699 (November 13, 2012) Korean Patent No. 10-0981393 (September 03, 2010) Korean Patent No. 10-0981391 (September 03, 2010)

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 is suitable for the skin material of the environmentally friendly unpainted automobile interior material which has good mechanical properties and soft touch feeling, and has no fear of volatile emission, and has high scratch resistance and at the same time high scratch self-healing. The present invention provides a scratch self-healing polyurethane-based composition and a molded article prepared therefrom.

The present invention relates to a scratch self-healing polyurethane based composition and a polyurethane based molded article prepared therefrom.

One aspect of the invention is a thermoplastic polyurethane resin; Microcapsules (A) comprising a vinyl group-containing silicone compound as a core; (B) a microcapsule containing a hydride group-containing silicone compound as a core; And it relates to a scratch self-healing polyurethane-based resin composition comprising a metal catalyst.

In this case, the thermoplastic polyurethane-based resin may be one or two or more selected from the group consisting of ether-based thermoplastic polyurethanes, ester-based thermoplastic polyurethanes, and carbonate-based thermoplastic polyurethanes.

In addition, the thermoplastic polyurethane-based resin may be an aliphatic polyurethane-based resin obtained by reaction with a polyol, aliphatic isocyanates and chain extenders.

In addition, the vinyl group-containing silicone-based compound may be a vinyl-terminated polydimethylsiloxane, a vinyl-terminated polydiethylsiloxane, a vinyl-terminated polydiphenylsiloxane, a vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, a vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, Vinyl-terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, Vinylmethylsiloxane homopolymer, vinylmethylsiloxane-octylmethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-phenylmethylsiloxane-dimethylsiloxane copolymer, vinylmethoxysiloxane homopolymer, vinylethoxysiloxane homopolymer and vinylethoxysiloxane From the group consisting of -propylethoxysiloxane copolymer The hydride group-containing silicone-based compound may be any one or two or more selected from the group consisting of hydride-terminated polydimethylsiloxane, hydride-terminated polydiethylsiloxane, hydride-terminated polydiphenylsiloxane, hydride-terminated polyphenylmethylsiloxane and trimethylsiloxane. Sea terminal methylhydrosiloxane-dimethylsiloxane copolymer, hydride terminal methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxy terminal polymethylhydrosiloxane, triethylsiloxy terminal polyethylhydrosiloxane, hydride terminal polyphenyl- (dimethyl Hydrosiloxy) silane, hydride terminated methylhydrosiloxane-phenylmethylsiloxane copolymer and methylhydrosiloxane-octylmethylsiloxane copolymer.

The wall material of the microcapsule may be any one or two or more selected from the group consisting of melamine-formalin resin, urea-formalin resin, polyurethane resin and inorganic material, and the average size of the microcapsules may be 0.01 to 100 μm.

In addition, the metal catalyst is any one or two selected from the group consisting of platinum, nickel, palladium, titanium, rhodium, ruthenium, platinum-based complex, nickel-based complex, palladium-based complex, titanium-based complex, rhodium-based complex and ruthenium-based complex It may be abnormal.

The polyurethane composition includes 1 to 20 parts by weight of the microcapsules (A), 1 to 20 parts by weight of the microcapsules (B) and 0.0001 to 0.5 parts by weight of the metal catalyst, based on 100 parts by weight of the thermoplastic polyurethane resin. (A) and the microcapsules (A) / microcapsules (B) in the content ratio of the microcapsules (B) may be made to satisfy the 0.5 to 2.0 weight ratio.

Another aspect of the present invention, the polyurethane-based resin composition further comprises any one or two or more additives selected from the group consisting of sunscreen, antioxidant, heat-resistant, pigment, dye, lubricant and blowing agent. It relates to a urethane resin composition.

Another aspect of the present invention relates to a powdery scratch self-healing polyurethane-based resin composition obtained by pulverizing pellets prepared from the polyurethane-based resin composition into powder form. At this time, the average particle diameter of the powder may be 50 to 500㎛.

In the present invention, the powdery scratch self-healing polyurethane resin composition includes talc, calcium carbonate, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, titanium oxide, alumina, It may further comprise any one or two or more inorganic particles selected from the group consisting of mica, asbestos, zeolite, clay silicate, glass fiber and whiskers.

In another embodiment of the present invention, the powdered scratch self-healing polyurethane-based resin composition is put into a box, and the mold and the box heated to a high temperature are shaken and rotated with each other to melt the polyurethane-based resin composition in the mold, followed by cooling, It relates to a scratch self-healing polyurethane-based molded article obtained by a powder slush molding (PSM) method to solidify.

Another aspect of the present invention relates to a scratch self-healing polyurethane-based molded article obtained by melting the scratch self-healing polyurethane-based resin composition and then extruding or injection molding.

Another aspect of the present invention relates to a scratch self-healing skin material comprising the scratch self-healing polyurethane-based molded article.

Hereinafter, the scratch self-healing polyurethane-based composition, the scratch self-healing molded article, and the scratch self-healing skin material according to the present invention will be described in detail. In describing the present invention, however, the description of related art or configuration will be omitted so as not to obscure the gist of the present invention.

In the present invention, it is environmentally friendly and suitable for the skin material of non-painted automobile interior materials, while having good mechanical properties and soft touch feeling, having excellent scratch resistance and at the same time having self-healing property against scratches The core of the technology introduced in order to obtain a scratch self-healing polyurethane-based composition and a polyurethane-based molded article manufactured therefrom is a novel high-sensitivity polymer new material or component.

First of all, it is suitable as a skin material of environmentally friendly unpainted automotive interior as matrix resin, and adopts polyurethane-based resin with excellent mechanical properties and soft touch.

Secondly, when scratches are generated in the skin material for automobile interior made of the polyurethane-based molded article, the microcapsules contained in the skin material are broken, so that the liquid scratch self-healing compound flows into the recessed area where scratches are generated The present invention introduces a new concept that scratch self-healing is exhibited by allowing a catalyst present in the vicinity to react rapidly at room temperature to be converted into a solid polymer.

Third, the microcapsule-containing microcapsules filled with the core material of the odorless liquid scratch self-healing compound were included. Self-healing materials developed in the past had a high reactivity but a bad smell. However, the intended use in the present invention is an environment-friendly, unpainted automobile interior material having no odor and no concern of releasing volatile substances, so that a silicone compound having excellent reactivity, which basically has no odor but affects the healing rate, Compound. Further, it is also considered that such a liquid silicone compound is converted into a solid polymer after the curing reaction, and the scratch resistance can be further improved based on inherent slipperiness.

Fourth, even if a self-healing compound that has no odor and excellent reactivity is selected, it is very disadvantageous in terms of reaction rate because the reaction must take place at a room temperature, not high temperature, for use. A suitable metal catalyst can be contained in the polyurethane composition.

Scratch self-healing polyurethane-based composition according to the present invention is a thermoplastic polyurethane-based resin; Microcapsules (A) containing a vinyl group-containing silicone compound as a core; (B) a microcapsule containing a hydride group-containing silicone compound as a core; And a metal-based catalyst.

The thermoplastic polyurethane-based resin is commonly used in the art, and examples thereof include ether-based thermoplastic polyurethanes, ester-based thermoplastic polyurethanes, carbonate-based thermoplastic polyurethanes, and the like. Preferably, the aliphatic isocyanates obtained by the reaction with aliphatic isocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate, polyols and chain extenders having excellent light resistance in terms of being exposed to sunlight for a long time. Use of a polyurethane-based resin is preferred, and specific examples thereof include Bayer Material Science, Inc., Desmopan W DP 89085A, DP 89043D, DP 89051D, DP 89056D, and the like.

The polyol is commonly used in the art for preparing a thermoplastic polyurethane-based resin, and means a compound having a hydroxyl group and reacting with an isocyanate to be a polyurethane. Examples of the polyol that can be used include, for example, conventional ether polyols and esters. Polyols, carbonate polyols, and the like.

The chain extender is a reactive monomolecule used for strengthening polymerization or intermolecular bonds, for example, diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, glycerin, Triols such as trimethylolpropane, tetraols such as pentaerythritol, polyoxypropylenediamine, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, 1,4-cyclohexyldiamine, tetramethylpropylenediamine, tetramethylhexamethylenediamine Any one or two or more selected from amino alcohols such as diamine, diethanolamine, triethanolamine, and the like, and m-phenylenediamine and toluenediamine can be used.

In addition, the polyurethane-based resin may further include a curing catalyst during manufacture. Examples of the curing catalyst include triethylenediamine, pentamethyldiethylenetriamine, 1,8-diazabicyclo-5,4,0-undecene-7, dimethylaminoethanol, tetramethylethylenediamine, dimethylbenzylamine, N, N'-dimethyl ethanolamine, N, N'-dimethyl ethanolamine and 1-isobutyl-2 (2-dimethylaminoethyl) Tertiary amines such as methylimidazole, N-methyl-N'-hydroxyethylpiperazine, N, N'-dimethylaminoethoxyethanol and N, N, A metal such as a tertiary phosphine, magnesium, zinc, cadmium, lead, titanium, chromium, manganese, iron or cobalt and a metal such as acetylacetone, benzoyl acetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone -2-carboxylate, and esters, such as acetyl imine, which is a chelate compound with a ligand Acrylate compound, Ti (OR) _4, Sn (OR) _4, Sn (OR) _2, Al (OR) ₃ metal alcoholate or a metal phenolate, sodium acetate, potassium acetate, such as (wherein R is an alkyl group or an allyl group) , Metal organic acid salts such as potassium lactate, potassium octylate, potassium lactate, tin acetate, tin dioctylate, dibutyl tin dilaurate and cobalt naphthalate. The curing catalysts may be used alone or in combination. The amount of the curing catalyst is preferably adjusted so that the component curing time is in the range of 10 to 30 seconds, preferably 15 to 25 seconds.

The microcapsule (A) means that the vinyl group-containing silicone compound is contained as an internal core. Examples of the vinyl group-containing silicone compound include vinyl-terminated polydimethylsiloxane, vinyl-terminated polydiethylsiloxane, vinyl-terminated polydiphenylsiloxane, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diphenylsiloxane-dimethyl Siloxane copolymers, vinyl terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymers, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymers, silanol-terminated vinylmethylsiloxane-dimethylsiloxane copolymers, vinyl terminated vinylmethylsiloxane-dimethyl Siloxane copolymers, vinylmethylsiloxane homopolymers, vinylmethylsiloxane-octylmethylsiloxane-dimethylsiloxane copolymers, vinylmethylsiloxane-phenylmethylsiloxane-dimethylsiloxane copolymers, vinylmethoxysiloxane homopolymers, vinylethoxysiloxane homopolymers, Vinyl ethoxysiloxane-propylethoxysiloxane copolymer, and the like Considering the price side in the double vinyl terminated polydimethylsiloxane, vinyl terminated poly diphenyl siloxane, vinyl terminated diphenylsiloxane-it is preferred to use a dimethyl siloxane copolymer. The microcapsules (A) may contain any one or two or more of the vinyl group-containing silicone compounds.

The microcapsule (B) means that a hydride group-containing silicone compound is contained as an internal core. Examples of the hydride group-containing silicone compound include hydride-terminated polydimethylsiloxane, hydride-terminated polydiethylsiloxane, hydride-terminated polydiphenylsiloxane, hydride-terminated polyphenylmethylsiloxane, trimethylsiloxy-terminated methylhydroxylsiloxane -Dimethylsiloxane copolymer, hydride-terminated methylhydroxysiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated polymethylhydrosiloxane, triethylsiloxy-terminated polyethylhydroxylsiloxane, hydride-terminated polyphenyl- (dimethylhydroxyloxy) silane , Hydride-terminated methylhydroxysiloxane-phenylmethylsiloxane copolymer, methylhydroxysiloxane-octylmethylsiloxane copolymer and the like. Among these, in view of cost, hydride-terminated polydimethylsiloxane, hydride-terminated polydiphenylsiloxane, etc. To use It is desirable. The microcapsules (B) may contain any one or two or more of the hydride group-containing silicone compounds.

The microcapsule (A) or (B) may be any one selected from the group consisting of a melamine-formalin resin, a urea-formalin resin, a polyurethane resin and an inorganic material including silica, titania, zirconia, alumina and zinc oxide nanoparticles. One or two or more materials may be included. Among them, a melamine-formalin resin and a urea-formalin resin are preferable considering both heat resistance and ease of encapsulation.

For example, the microcapsules prepared by using the melamine-formalin resin or urea-formalin resin as a wall according to the present invention can be prepared by using a known in situ method.

First, an aqueous solution of an emulsifier is prepared as a first step. Emulsifiers are very useful for improving the viscosity and particle size distribution of capsules. Examples of the emulsifier in the present invention include alkali metal sulfates such as sodium dodecylsulfate, alkali metal salts of fatty acids such as alkali metal salts of octadecanoic acid, anionic emulsifiers such as sodium dodecyl ether sulfate such as sodium dodecyl ether sulfate, A polyoxyethylene alkyl ether, a polyethylene oxide, a polypropylene oxide, a polyoxyethylene sorbitan monostearate, a polyoxyethylene sorbitan monostearate, a polyoxyethylene sorbitan monostearate, a polyoxyethylene sorbitan monostearate, a polyoxyethylene sorbitan monostearate, a polyoxyethylene sorbitan monostearate, Polyoxyethylene sorbitan tristearate, and polyoxyethylene glyceryl monostearate. These may be used singly or in combination of two or more. The emulsifier aqueous solution can be obtained by adding ordinary water such as an emulsifier and distilled water to a homomixer and stirring at a temperature of 20 ° C to 40 ° C, and it is preferable that the emulsifier is usually prepared at a concentration of 1 to 15% by weight. When the amount of the emulsifier is less than 1% by weight, emulsification is unstable and it is difficult to produce emulsions having the desired particle size. When the amount is more than 15% by weight, the viscosity of the prepared capsule slurry increases and the use thereof becomes difficult.

In the second step, an appropriate amount of a vinyl group-containing silicone compound or a hydride group-containing silicone compound to be an internal material of the capsule is added to the emulsifier aqueous solution prepared in the emulsifier, And the mixture is stirred at a high speed of 10,000 rpm for 20 to 60 minutes to prepare a fine emulsion mixture.

As a third step, melamine-formalin or urea-formalin prepolymer is prepared by adding water to a separate reactor, introducing melamine, formalin or urea and formalin, and reacting at a temperature of 50 to 70 ° C for 20 to 60 minutes.

As the fourth step, the melamine-formalin or urea-formalin prepolymer is added to the emulsion mixture contained in the emulsifier, and the mixture is stirred at a temperature of 50 to 70 ° C at a speed of 200 to 1,000 rpm for 1 to 2 hours The polymerization reaction is further advanced to obtain a microcapsule slurry.

As a fifth step, the obtained microcapsule slurry is dried through a dryer such as a spray dryer to obtain a microcapsule.

In the present invention, the size of the microcapsules is preferably in the range of 0.01 to 100 mu m, more preferably in the range of 0.1 to 10 mu m. When the average particle diameter is less than 0.01 탆, the thickness of the wall material of the microcapsule does not become extremely small proportionally, so that the self-healing material content per a microcapsule weight is small, and ultimately, the self-healing effect is lowered. There is a fear that the surface roughness of the surface material of the interior material becomes large and the contact feeling is lowered.

The metal catalyst promotes the reaction so that the self-healing compound in the capsule quickly reacts at a room temperature to effectively remove scratches when scratches are formed on the skin agent. Examples of the metal catalysts include gold, nickel, palladium, titanium, rhodium, ruthenium, platinum complexes, nickel complexes, palladium complexes, titanium complexes, rhodium complexes, ruthenium complexes, and the like. In view of reactivity, platinum, a platinum complex and the like are preferable.

Polyurethane resin composition according to the present invention is 1 to 20 parts by weight of the microcapsules (A), preferably 3 to 15 parts by weight, 1 to 20 parts by weight of the microcapsules (B) with respect to 100 parts by weight of the thermoplastic polyurethane resin , Preferably it may include 3 to 20 parts by weight, 0.0001 to 0.5 parts by weight of the metal catalyst, preferably 0.001 to 0.1 parts by weight, the microcapsules (A) and the content ratio of the microcapsules (B) microcapsules (A) The fine capsule (B) satisfies 0.5 to 2.0 weight ratio, preferably 0.7 to 1.5 weight ratio, which is good for scratch self-healing expression.

When the content of the microcapsules (A) or the microcapsules (B) is less than 1 part by weight, it is difficult to secure desired scratch self-healing and when the content exceeds 20 parts by weight, mechanical properties may be deteriorated. In addition, when the fine capsule (A) / fine capsule (B) is less than 0.5 or more than 2.0, there is a fear that the self-healing reaction efficiency is lowered.

In addition, when the addition amount of the metal-based catalyst is less than 0.0001 parts by weight, the self-healing reaction rate may be too low, and when the effect exceeds 0.5 parts by weight, there is a concern that the economic efficiency is impaired due to the high price.

In addition, the polyurethane-based resin composition is blended with any one or two or more selected from conventional additives such as sunscreens, antioxidants, heat-resistant agents, pigments, dyes, lubricants, blowing agents and the like in a range that does not impair the object of the present invention. can do.

The thermoplastic polyurethane-based composition according to the present invention can be manufactured into a molded article through a mold. Usually, a powdery thermoplastic polyurethane-based resin composition is applied to a box with a predetermined thickness, and then the mold heated to a high temperature and the box are shaken and rotated with each other to melt the powdery thermoplastic polyurethane-based resin composition in the mold, followed by cooling and solidifying. Molded articles can be produced by a so-called powder slush molding (PSM) process.

The powdery thermoplastic polyurethane-based composition

a) kneading and dispersing the resin composition with a kneader to prepare pellets; And

b) freezing and grinding the prepared pellets into powder;

. ≪ / RTI >

Step a) may use a known pellet manufacturing method or a single screw extruder, a twin screw extruder, a mixing roll, a balm mixer, a kneader, and the like, which are commonly used, and does not limit the size and shape of the pellet.

Step b) is a process of making the prepared pellets into a fine powder, to facilitate the powder slush molding process. To this end, the prepared pellets are quenched and then pulverized in a low temperature atmosphere to prepare them in powder form.

The powdery thermoplastic polyurethane-based composition prepared through step b) has an average particle diameter of 50 to 500 μm, preferably 100 to 400 μm, which is easy to process and may have an excellent skin texture.

In addition, the powdery thermoplastic polyurethane-based resin composition according to the present invention may further add inorganic particles to improve powder flowability and molding quality. Examples of the inorganic particles that can be added include talc, calcium carbonate, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, titanium oxide, alumina, mica, asbestos, zeolite, It may be any one or two or more selected from the group consisting of clay silicate, glass fiber and whiskers. The shape of the inorganic particles to be added may be in the form of a spherical shape, a plate shape, a needle shape, or the like, and the average particle diameter is preferably 1 to 10,000 nm, preferably 1 to 1,000 nm, and more preferably 1 to 500 nm.

The inorganic particles are preferably added in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the whole powdery thermoplastic polyurethane resin. If it is less than 0.05 parts by weight, it is difficult to obtain the desired powder flowability and molding quality improvement, and if it is more than 5 parts by weight, the surface may be roughened and the surface texture may be degraded.

The thermoplastic polyurethane-based resin composition according to the present invention may be manufactured into a molded article through a powder slush molding method after being prepared in powder form as described above, but a conventional molded article manufacturing method, for example, a powder or bulk thermoplastic polyurethane-based After melting the resin composition, it can be produced by extrusion or injection.

The thermoplastic polyurethane-based molded article according to the present invention may be included as a skin material of automobile interior materials such as an instrument panel, a door trim, a built-in trim through the above method.

The polyurethane-based resin composition and the molded article manufactured therefrom according to the present invention have good mechanical properties and soft touch, and have no fear of volatile emission, and have excellent scratch resistance and at the same time the surface of automobile interior parts having scratch self-healing properties. It is expected to be very useful for ashes.

Hereinafter, the polyurethane-based molded article and the automotive interior skin material according to the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples are only for the purpose of illustrating the present invention in detail, and the present invention is not limited to the following examples and comparative examples.

The physical properties of the polyurethane-based molded product specimens prepared in Examples and Comparative Examples were measured as follows.

(The tensile strength)

The specimens were taken from Dumbbell No. 1 molds in accordance with JIS K 6301, and tensile strengths were measured in a universal testing machine (Instron) according to ASTM D-790. The measurement standard is shown in Table 1 below.

[Table 1]

(Shore hardness)

The shore hardness was measured in accordance with ASTM D-2240 as a measure of the soft touch feeling of the molded article specimen. The evaluation criteria are shown in Table 2 below.

[Table 2]

(Permanent Compression Row)

The permanent compressive strain rate at 23 DEG C was measured according to ASTM D-395 as a measure of the durability of the soft touch on the molded article specimen. The evaluation criteria are shown in Table 3 below.

[Table 3]

(Scratch resistance)

After a specimen of 12 cm × 12 cm size was taken from the molded article, scratch resistance was measured according to MS 210-05. The evaluation criteria are shown in Table 4 below.

[Table 4]

(Scratch self-healing property)

After sampling the size of 12 ㎝ × 12 ㎝ from the molded product, each specimen was mounted in a scratch tester (manufactured by HEIDON) with a 3Φ sapphire tip, and 10 scratches (length 20 mm) were formed under a 500g load. Scratch conditions were photographed immediately after scratch occurrence and after 48 hours, and scratch self-healing was evaluated as the average percentage reduction of scratch width at the longitudinal midpoint for 10 scratches. The evaluation criteria are shown in Table 5 below.

[Table 5]

(Example 1)

First, 1.25 g of sodium lauryl sulfate as an emulsifier and 125 g of distilled water were added to a beaker and stirred for 30 minutes to prepare an emulsified mixture, which was then fed into a reactor maintained at 60 ° C. Subsequently, 2.5 g of urea, 9.25 g of ammonium chloride and 0.25 g of resorcinol were added, and the mixture was stirred at a high speed of 500 rpm for 10 minutes at a high speed. Then, a 35% hydrochloric acid solution was slowly added thereto to adjust the pH to 3.5. Thereafter, the stirring speed was fixed at 850 rpm, 20 ml of vinyl-terminated polydimethylsiloxane (HSF40-100, Hansol E & C) as one of the vinyl group-containing silicone compounds and 7 g of formaldehyde were added and stirred for 10 minutes. The reaction was continued for 2 hours while injecting to obtain a microcapsule slurry. The resulting microcapsule slurry was dried through a spray drier to obtain a microcapsule (A-1) having an average particle diameter of 3.5 탆 in which the internal material was vinyl-terminated polydimethylsiloxane and the capsule wall material was a urea-formalin resin.

Next, in place of the vinyl-terminated polydimethylsiloxane to obtain the microcapsule (B-1), hydride-terminated polydimethylsiloxane (DMS-H03, Gelest), which is one of the hydride group- Microcapsules (B-1) having an average particle diameter of 3.5 mu m were obtained through the same manufacturing method as in (A-1).

Next, as a thermoplastic polyurethane resin, 100 parts by weight of aliphatic polyurethane resin (Desmopan DP 89085A, TPU (A), Bayer MaterialScience) of Shore hardness 86A, 3 parts by weight of microcapsules (A-1), and microcapsules (B-1) ) 3 parts by weight and a 0.002 parts by weight of platinum (Pt) catalyst were added to a twin screw extruder having a diameter of 70 mm and L / D 40, and melted and extruded at a cylinder temperature of 200 ° C. to obtain a final polyurethane resin composition. After preparing the obtained polyurethane-based resin composition as an injection specimen, the physical properties were measured and the results are shown in Table 7.

(Example 2)

Same as Example 1 except for using the composition which mixed 100 weight part of TPU (A), 5 weight part of microcapsules (A-1), 5 weight part of microcapsules (B-1), and 0.005 weight part of platinum (Pt) catalysts. To obtain a polyurethane-based resin composition. After preparing the obtained polyurethane-based resin composition as an injection specimen, the physical properties were measured and the results are shown in Table 7.

(Example 3)

The same as in Example 1 except that 100 parts by weight of the TPU (A), 15 parts by weight of the microcapsules (A-1), 15 parts by weight of the microcapsules (B-1) and 0.01 parts by weight of the platinum (Pt) catalyst were used. To obtain a polyurethane-based resin composition. After preparing the obtained polyurethane-based resin composition as an injection specimen, the physical properties were measured and the results are shown in Table 7.

(Example 4)

First, 1.5 g of sodium lauryl sulfate as an emulsifier and 130 g of distilled water were added to a beaker and stirred for 30 minutes to prepare an emulsified mixture, which was then fed into a reactor maintained at 60 ° C. Then, 3.0 g of urea, 11.1 g of ammonium chloride and 0.3 g of resorcinol were added, and the mixture was stirred at a high speed of 500 rpm for 10 minutes at a high speed, and a 35% hydrochloric acid solution was slowly added thereto to adjust the pH to 3.5. Thereafter, the stirring speed was fixed at 950 rpm, 20 ml of a vinyl-terminated polydimethylsiloxane-dimethylsiloxane copolymer (PDV-0325, Gelest), which is one of the vinyl group-containing silicone compounds, and 8 g of formaldehyde were added and stirred for 10 minutes Subsequently, the reaction was continued for 2 hours while injecting nitrogen to obtain a microcapsule slurry. The resulting microcapsule slurry was dried through a spray dryer to obtain a microcapsule (A-2) having an average particle diameter of 2.1 탆, which was a vinyl end-polydimethylsiloxane and the capsule wall material was a urea-formalin resin.

Next, Example 1 was used, except that 100 parts by weight of TPU (A), 10 parts by weight of microcapsules (A-2), 7 parts by weight of microcapsules (B-1) and 0.006 parts by weight of platinum (Pt) catalyst were used. The polyurethane resin composition was obtained in the same manner as the above. After preparing the obtained polyurethane-based resin composition as an injection specimen, the physical properties were measured and the results are shown in Table 7.

(Example 5)

(A-1) was obtained in the same manner as in Example 1, except that trimethylsiloxy-terminated polymethylhydroxylsilane (TSF484, manufactured by Hansol E & C), which is one of the hydride group-containing silicone compounds, was used instead of the vinyl-terminated polydimethylsiloxane. Microcapsules (B-2) having an average particle size of 3.0 mu m were obtained through the manufacturing method. In addition, talc having an average particle size of 1.3 mu m was prepared as inorganic particles.

Next, it carried out similarly to Example 1 except having used the composition which mixed 100 weight part of TPU (A), 8 weight part of microcapsules (A-2), 7 weight part of microcapsules (B-2), and 5 weight part of talc. To obtain a polyurethane resin composition. After preparing the obtained polyurethane-based resin composition as an injection specimen, the physical properties were measured and the results are shown in Table 7.

(Example 6)

First, as a thermoplastic polyurethane resin, a mixture (TPU (B)) of 80 wt% of the TPU (A) resin and 20 wt% of ester-based polyurethane resin (Bayer MaterialScience, Desmopan DP 3070A) having a Shore hardness of 70A was prepared. Nickel (Ni) was also prepared as a metal catalyst.

Next, it carried out similarly to Example 1 except having used the composition which mixed 100 weight part of TPU (B), 11 weight part of microcapsules (A-2), 9 weight part of microcapsules (B-2), and 0.01 weight part of Ni. To obtain a polyurethane resin composition. After preparing the obtained polyurethane-based resin composition as an injection specimen, the physical properties were measured and the results are shown in Table 7.

(Example 7)

First, as a thermoplastic polyurethane resin, a mixture (TPU (C)) of 60 wt% of the TPU (A) resin and 40 wt% of an ester polyurethane resin (Bayer MaterialScience, Desmopan DP 3070A) having a Shore hardness of 70A was prepared. As inorganic particles, silica having an average particle diameter of 0.8 μm was prepared.

Next, an Example except using the composition which mixed 100 weight part of TPU (C), 13 weight part of microcapsules (A-3), 10 weight part of microcapsules (B-2), 0.015 weight part of Ni, and 3 weight part of silica was used. It carried out similarly to 1, and obtained the polyurethane-type resin composition. After preparing the obtained polyurethane-based resin composition as an injection specimen, the physical properties were measured and the results are shown in Table 7.

(Comparative Example 1)

An injection specimen was prepared using only TPU (A), and the results of the measurement were described in Table 7.

(Comparative Example 2)

A polyurethane-based resin composition was obtained in the same manner as in Example 1 except that a composition obtained by mixing 100 parts by weight of TPU (A) and 5 parts by weight of talc was used. After preparing the obtained polyurethane-based resin composition as an injection specimen, the physical properties were measured and the results are shown in Table 7.

TABLE 6

[Table 7]

As can be seen in Examples 1 to 7 it can be seen that the polyurethane-based resin composition according to the present invention has excellent scratch properties and scratch healing properties while maintaining excellent mechanical properties, soft touch feeling and soft touch durability. Compared with Comparative Examples 1 and 2, in which some simple polyurethane-based resins and inorganic substances are added, they are similar in terms of excellent mechanical properties, soft touch, and soft touch durability, but there are great differences in scratchability and scratch healing properties. Able to know.

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 (18)

Thermoplastic polyurethane resins;
Microcapsules (A) containing a vinyl group-containing silicone compound as a core;
(B) a microcapsule containing a hydride group-containing silicone compound as a core; And
Metal catalyst;
Scratch self-healing polyurethane-based resin composition comprising a. The method of claim 1,
The thermoplastic polyurethane-based resin is one or two or more scratch self-healing polyurethane-based resin composition selected from the group consisting of ether-based thermoplastic polyurethane, ester-based thermoplastic polyurethane and carbonate-based thermoplastic polyurethane. The method of claim 1,
The thermoplastic polyurethane resin is a scratch self-healing polyurethane resin composition is an aliphatic polyurethane resin obtained by reaction with a polyol, aliphatic isocyanates and chain extenders. The method of claim 1,
The vinyl group-containing silicone compound is a vinyl terminal polydimethylsiloxane, vinyl terminal polydiethylsiloxane, vinyl terminal polydiphenylsiloxane, vinyl terminal diethylsiloxane-dimethylsiloxane copolymer, vinyl terminal diphenylsiloxane-dimethylsiloxane copolymer, vinyl Terminal trifluoropropylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy terminal vinylmethylsiloxane-dimethylsiloxane copolymer, silanol terminal vinylmethylsiloxane-dimethylsiloxane copolymer, vinyl terminal vinylmethylsiloxane-dimethylsiloxane copolymer, vinyl Methylsiloxane homopolymer, vinylmethylsiloxane-octylmethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-phenylmethylsiloxane-dimethylsiloxane copolymer, vinylmethoxysiloxane homopolymer, vinylethoxysiloxane homopolymer and vinylethoxysiloxane- Selected from the group consisting of propylethoxysiloxane copolymers Any one or more than one self-healing scratch property polyurethane-based resin composition. The method of claim 1,
The hydride group-containing silicone compound is a hydride-terminated polydimethylsiloxane, a hydride-terminated polydiethylsiloxane, a hydride-terminated polydiphenylsiloxane, a hydride-terminated polyphenylmethylsiloxane, a trimethylsiloxy-terminated methylhydrosiloxane-dimethylsiloxane air Copolymer, hydride terminal methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxy terminal polymethylhydrosiloxane, triethylsiloxy terminal polyethylhydrosiloxane, hydride terminal polyphenyl- (dimethylhydrosiloxy) silane, hydride terminal A scratch self-healing polyurethane resin composition comprising at least one selected from the group consisting of a methylhydrosiloxane-phenylmethylsiloxane copolymer and a methylhydrosiloxane-octylmethylsiloxane copolymer. The method of claim 1,
Scratch self-healing polyurethane-based resin composition of the fine capsule is any one or more selected from the group consisting of melamine-formalin resin, urea-formalin resin, polyurethane resin and inorganic. The method of claim 1,
Scratch self-healing polyurethane-based resin composition having an average particle diameter of the fine capsule is 0.01 to 100 ㎛. The method of claim 1,
The metal catalyst is any one or two or more selected from the group consisting of platinum, nickel, palladium, titanium, rhodium, ruthenium, platinum complex, nickel complex, palladium complex, titanium complex, rhodium complex and ruthenium complex. Scratch self-healing polyurethane-based resin composition. The method of claim 1,
The polyurethane composition includes 1 to 20 parts by weight of the microcapsules (A), 1 to 20 parts by weight of the microcapsules (B) and 0.0001 to 0.5 parts by weight of the metal catalyst, based on 100 parts by weight of the thermoplastic polyurethane resin. A scratch self-healing polyurethane resin composition having (A) / microcapsules (B) of 0.5 to 2.0. The method of claim 1,
Scratch self-healing polyurethane-based resin composition further comprises any one or two or more additives selected from the group consisting of a sunscreen, antioxidants, heat-resistant agents, pigments, dyes, lubricants and blowing agents in the polyurethane-based resin composition. A powdered scratch self-healing polyurethane-based resin composition obtained by pulverizing pellets prepared from the polyurethane-based resin composition according to any one of claims 1 to 10 in powder form. 12. The method of claim 11,
Powdered scratch self-healing polyurethane-based resin composition having an average particle diameter of 50 to 500㎛. 12. The method of claim 11,
Talc, calcium carbonate, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, titanium oxide, alumina, mica, asbestos, in the powdered scratch self-healing polyurethane resin composition Scratch self-healing polyurethane-based resin composition further comprises any one or two or more inorganic particles selected from the group consisting of zeolite, clay silicate, glass fiber and whiskers. A powder to which the powdered scratch self-healing polyurethane-based resin composition according to claim 11 is put into a box, the mold heated to a high temperature and the box are shaken and rotated to melt the polyurethane-based resin composition in the mold, and then cooled and solidified. Scratch self-healing polyurethane-based molded article obtained by the slush molding method. The scratch self-healing polyurethane-based molded article obtained by extrusion or injection process after melting the scratch self-healing polyurethane-based resin composition according to any one of claims 1 to 10. A scratch self-healing polyurethane-based molded product obtained by extrusion or injection process after melting the powdered scratch self-healing polyurethane-based resin composition according to claim 11. Scratch self-healing skin material comprising the molded article according to claim 15. A scratch self-healing skin material comprising the shaped article according to claim 16.