KR20190088432A - The manufacturing method of thermoplastic polyurethane powder for powder slush molding, a thermoplastic polyurethane powder produced therefrom, and a skin material for automobile interior by using the thermoplastic polyurethane powder - Google Patents

Abstract

The present invention relates to: a method for manufacturing a thermoplastic polyurethane powder for powder slush molding; the thermoplastic polyurethane powder manufactured from the same; and a surface material for an automobile interior formed by using the same. Specifically, the present invention relates to: the method for manufacturing the thermoplastic polyurethane powder for powder slush molding; the thermoplastic polyurethane powder manufactured from the same; and the surface material for the automobile interior formed by using the same, wherein the powder manufactured by the method for manufacturing the powder has excellent moldability and the surface material for the automobile interior manufactured by using the same has excellent physical properties such as scratch resistance, tensile strength, elongation at break, weather resistance and the like.

Description

TECHNICAL FIELD The present invention relates to a method for producing a thermoplastic polyurethane powder for powder slush molding, a thermoplastic polyurethane powder prepared therefrom, and a skin material for an automobile interior material formed using the thermoplastic polyurethane powder and a thermoplastic polyurethane powder produced therefrom, and a skin material for automobile interior by using the thermoplastic polyurethane powder}

The present invention relates to a method for producing a thermoplastic polyurethane powder for powder slush molding, a thermoplastic polyurethane powder produced therefrom, and a skin material for an automobile interior material formed using the thermoplastic polyurethane powder, wherein the powder produced from the method for producing a powder of the present invention A method for producing a thermoplastic polyurethane powder for powder slush molding, which is excellent in moldability and is excellent in physical properties such as scratch resistance, tensile strength, elongation at break and weather resistance, And a skin material for an automobile interior material formed using the thermoplastic polyurethane powder.

Thermoplastic polyurethane (TPU) resin, which is widely used as an automobile interior material, is widely used because it can be molded in a variety of sizes compared to the price and has good mechanical properties and is particularly suitable for instrument panel, Door trim, etc.), automobile interior mat backing materials, and the like.

On the other hand, the skin material for automobile interior materials manufactured using the TPU resin is manufactured by a powder slush molding method having high design freedom and excellent emboss pattern maintenance as disclosed in Korean Patent Registration No. 10-1775199. The TPU resin , There is a problem that scratches are generated due to the hands of the operator when the skin material is demolded from the mold after the skin material has high adhesiveness compared to other thermoplastic elastomers.

In addition, since the scratch resistance of the TPU material is not good due to its inherent characteristics, it is not easy to satisfy the hardness or scratch resistance according to the level of the end user.

Conventionally, in order to solve this problem, silicone oil, paraffin oil or paraffin wax was added to improve the scratch resistance, but the weatherability of the skin material deteriorated and the oil or wax was excessively transferred to the surface of the skin material, , The oil or wax transferred to the surface is volatilized and the initial scratch resistance can not be maintained.

Accordingly, the thermoplastic polyurethane powder is excellent in moldability, the rate of change of gloss of the skin material for automobile interior materials formed using the thermoplastic polyurethane powder is low, and the thermoplastic resin for powder slush molding, which is excellent in physical properties such as scratch resistance, tensile strength, elongation at break, It is necessary to develop a polyurethane powder.

KR 10-1775199 B (Notice: 2017.08.30)

In order to solve the problems of the prior art as described above, it is an object of the present invention to provide a process for producing a thermoplastic polyurethane powder for powder slush molding and a thermoplastic polyurethane powder excellent in moldability produced therefrom.

Another object of the present invention is to provide a skin material for automobile interior materials which is formed by using the above thermoplastic polyurethane powder and has a low rate of change in gloss and is excellent in physical properties such as scratch resistance, tensile strength, elongation at break and weather resistance.

In order to achieve the above object,

The present invention relates to a method for producing a thermoplastic polyurethane resin composition, comprising: a first mixing step (S1) of mixing a thermoplastic polyurethane resin (A) and a silicone rubber (B) in a weight ratio of 90-50: 10-50; And

And a second mixing step (S3) in which 25-70 parts by weight of the mixture of the first mixing step (S1) is mixed with 100 parts by weight of the thermoplastic polyurethane resin (A), to prepare a thermoplastic polyurethane powder for powder slush molding ≪ / RTI >

The present invention also relates to the thermoplastic polyurethane powder produced by the process for producing the thermoplastic polyurethane powder for powder slush molding.

The present invention also relates to a skin material for an automobile interior material formed using the thermoplastic polyurethane powder.

The thermoplastic polyurethane powder produced from the process for producing a thermoplastic polyurethane powder for powder-slush molding of the present invention has an excellent dispersibility of silicone rubber in powder and is excellent in moldability in powder-slush molding.

In addition, the skin material for automobile interior materials formed using the powder has a small rate of change in gloss, and has excellent properties such as scratch resistance, tensile strength, elongation at break, and weather resistance.

The present invention relates to a method for producing a thermoplastic polyurethane resin composition, comprising: a first mixing step (S1) of mixing a thermoplastic polyurethane resin (A) and a silicone rubber (B) in a weight ratio of 90-50: 10-50; And

And a second mixing step (S3) in which 25-70 parts by weight of the mixture of the first mixing step (S1) is mixed with 100 parts by weight of the thermoplastic polyurethane resin (A), to prepare a thermoplastic polyurethane powder for powder slush molding ≪ / RTI >

Hereinafter, each step will be described in detail.

In the first mixing step (S1)

The first mixing step (S1) is a step of mixing the thermoplastic polyurethane resin (A) and the silicone rubber (B) in a weight ratio of 90-50: 10-50 or 85-55: 15-45, May be a step of masterbatching the silicone rubber (B) so that the dispersibility of the silicone rubber (B) is excellent.

The present inventors have found that when a small amount of the silicone rubber (B) is added to the thermoplastic polyurethane powder for powder slush molding, the dispersibility of the silicone rubber (B) is lowered and the physical properties of the skin material formed using the silicone rubber (Step S1) of master batching in which the thermoplastic polyurethane resin and the high-content silicon rubber (B) are preliminarily mixed as described above, so as to obtain a powder of the silicone rubber (B) in the powder It was possible to improve the acidity and to obtain an excellent effect of the physical properties of the skin material formed by using the powder with excellent moldability.

In order to improve the dispersibility of the additive in the polymer material, the master batch is prepared by first mixing a polymer material and a high-concentration additive in the form of a chip or a pellet when adding an additive to add functionality to a polymer material such as plastic And then adding it to the polymer material to use it.

If the content of the silicone rubber (B) is less than the above range, the tackiness and weatherability of the finished skin material may be deteriorated. If the content exceeds the above range, the dispersibility of the silicone rubber (B) And the mechanical properties such as the tensile strength and the elongation at break of the finished skin material deteriorate, so that they can be mixed at a weight ratio within the above range.

Also, the first mixing step (S1) may be performed at a temperature of 160-200 占 폚 or 170-190 占 폚. Wherein the thermoplastic polyurethane resin (A) and the silicone rubber (B) are not sufficiently melted when mixing is performed at a temperature lower than the temperature range in the first mixing step (S1) The dispersibility of the thermoplastic polyurethane resin (B) is lowered, the moldability of the powder is lowered, and the mechanical properties such as tensile strength and elongation at break of the finished skin material may be lowered. ) Is thermally decomposed to deteriorate physical properties such as tensile strength and elongation at break of the finished skin material.

Hereinafter, the thermoplastic polyurethane resin (A) and the silicone rubber (B) will be described in detail as follows.

Thermoplastic polyurethane resin (A)

The thermoplastic polyurethane resin (A) may be an aliphatic thermoplastic polyurethane resin excellent in discoloration and weatherability by ultraviolet rays.

Specifically, the thermoplastic polyurethane resin (A) can be produced by reacting an aliphatic diisocyanate with a polyol and a chain extender.

Examples of the aliphatic diisocyanate include isophorone diisocyanate, 1,6 hexamethylene diisocyanate, 4,4-dicyclomethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,4-cyclohexyl Diisocyanate, decane-1,10-diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate.

The polyol may be at least one selected from the group consisting of a polyether polyol, a polyester polyol, and a polycarbonate polyol, for example.

The polyether polyol is a diol or a polyol having 2-15 carbon atoms, specifically, an alkyldiol or a glycol and an alkylene oxide having 2-6 carbon atoms, specifically, ethylene oxide or propylene oxide Lt; / RTI >

The polyester polyol may be formed by esterifying one or more glycols with one or more dicarboxylic acids or anhydrides thereof. As a specific example, the glycol may be at least one selected from ethylene glycol, propylene glycol and glycerin, and the dicarboxylic acid may be at least one selected from adipic acid, phthalic acid and maleic acid.

Alternatively, the polyester polyol may be formed by subjecting a lactone or a derivative thereof to ring-opening polymerization using a small amount of a diol, a triol or an amine as an initiator.

A specific example of the polyester polyol may be polycaprolactone (PCL) synthesized by ring-opening polymerization using ε-caprolactone (CL) with diethylene glycol as an initiator.

The polycarbonate polyol may be derived from the reaction of a glycol and a carbonate.

The chain extender may be, for example, an aliphatic linear and branched chain diol having 2 to 10 carbon atoms in the chain, and specific examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, Hexanediol, cyclohexanediol, cyclohexanediol, diethylene glycol, dipropylene glycol monomethyl ether, cyclohexanedimethanol, cyclohexanediol, cyclohexanediol, cyclohexanediol, cyclohexanediol, Glycol, ethanolamine, and N-methyldiethanolamine.

The thermoplastic polyurethane resin (A) of the present invention may be at least one selected from the group consisting of a polyether-based polyurethane or a polycaprolactone-based polyurethane, and more specifically, a polyol having a hydrolyzable and heat- Caprolactone-based polyurethane.

The thermoplastic polyurethane resin (A) may have a Shore A hardness of 65-92 or 70-90. If it is less than the above range, the scratch resistance of the skin material for automobile interior material may be deteriorated. If it exceeds the above range, the soft touch of the skin material may be deteriorated, and Shore A hardness within the above range can be obtained.

The Shore A hardness of the present invention can be measured according to ISO 868.

The thermoplastic polyurethane resin (A) may have a tensile strength of 5-35 MPa, 10-30 MPa, or 20-30 MPa. If it is less than the above range, the tensile strength and elongation at break, which are required as the skin material for automobile interior materials, may not be satisfied. If it exceeds the above range, the air bag may not be torn along the incision line during deployment, Lt; / RTI >

The tensile strength can be measured according to ISO 527-2.

The thermoplastic polyurethane resin (A) may have a elongation at break of 300-520% or 350-480%. If it is less than the above range, the tensile strength and the elongation at break, which are required as the skin material for automobile interior materials, may not be satisfied. If it exceeds the above range, the air bag may not be torn along the incision line during deployment, It can be stretched.

The elongation at break can be measured in accordance with ISO 527-2.

The thermoplastic polyurethane resin (A) may have a Vicat softening point of 40-60 ° C or 45-55 ° C. If it is less than the above range, the temperature of the automobile room may rise, which may cause appearance change, cracking, etc. If the above range is exceeded, the skin softness may be deteriorated under low temperature conditions, .

The Vicat softening point of the present invention can be measured according to ISO 306.

The melt flow index (MFI) of the thermoplastic polyurethane resin (A) may be 50-100 g / 10 min (185 캜, 2.16 kg) or 60-90 g / 10 min (185 캜, 2.16 kg). If it is outside the above range, the processability may be deteriorated and the melt flow index within the above range may be obtained.

Silicone rubber (B)

The silicone rubber (B) of the present invention may be prepared from an organopolysiloxane or a mixture of an organopolysiloxane and a filler.

The organopolysiloxane may be a high consistency homopolymer or copolymer of di-organopolysiloxane gum (gum) containing two or more alkenyl groups of 2-20 carbon atoms in the molecule. The alkenyl group having 2-20 carbon atoms may be, for example, at least one member selected from the group consisting of vinyl, allyl, butenyl, pentenyl, hexenyl, propenyl and decenyl. The position of the alkenyl group is not critical, and it can be bonded at the molecular chain end, at the non-terminal position of the molecular chain, or at both of the above positions. In one embodiment, the alkenyl group is vinyl or hexenyl, and these groups may be included in the organopolysiloxane in an amount of 0.001-3 wt%, or 0.01-1 wt%.

The remaining (i.e., non-alkenyl) organic groups bonded to the silicon of the organopolysiloxane are independently selected from hydrocarbons or halogenated hydrocarbons that do not contain aliphatic unsaturation. Specifically, they may be an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.

The alkyl group having 1-20 carbon atoms includes, for example, methyl, ethyl, propyl, butyl, pentyl, and hexyl; The cycloalkyl group can be exemplified by, for example, cyclohexyl and cycloheptyl.

Examples of the aryl group having 6-12 carbon atoms include phenyl, tolyl and xylyl.

The aralkyl group having 7 to 20 carbon atoms may be, for example, benzyl and phenethyl.

Examples of the halogenated alkyl group having 1-20 carbon atoms include, for example, 3,3,3-trifluoropropyl and chloromethyl.

The viscosity of the organopolysiloxane at 25 ° C may be 100-90000 mPa · s or 300-7000 mPa · s.

The filler is a finely divided filler known to enhance the organopolysiloxane and is, for example, selected from the group consisting of fumed silica, precipitated silica, silica aerosol and titanium dioxide having a specific surface area of at least 50 m ² / g Fumed silica may be used as a specific example.

The filler may be used in an amount of 5-150 parts by weight or 20-100 parts by weight based on 100 parts by weight of the organopolysiloxane.

Meanwhile, in the first mixing step (S1), a curing agent and a catalyst may be further mixed in addition to the thermoplastic polyurethane resin (A) and the silicone rubber (B). In this case, in the first mixing step (S1) . ≪ / RTI >

In the present invention, the dynamic vulcanization process is a process in which a vulcanization process is carried out under the conditions of a high shear flow (for example, 150-300 rpm) and a high temperature (for example, 160-200 deg. C) Means a vulcanizing process in which a resin and at least one vulcanizable rubber are mixed. This dynamic vulcanization step can be carried out simultaneously with mixing in an extruder as an example.

The thermoplastic polyurethane resin (A) is present as a continuous matrix (B-1) through the dynamic vulcanization step and the silicone rubber (B) as a particle in the matrix is crosslinked (B-2) .

The cross-linked silicone rubber (B-2) means that it is cured, vulcanized and / or catalyzed, and has excellent mechanical properties such as strength, elasticity or heat resistance as compared with the silicone rubber (B) It is possible to impart an improved scratch resistance and weather resistance to a skin material for an automobile interior material.

In the present invention, the crosslinked silicone rubber (B-2) means a fully-crosslinked silicone rubber.

The curing agent for crosslinking the silicone rubber (B) may be an organopolysiloxane containing two or more hydrogen atoms bonded to silicon (Si) in a molecule, and the content thereof is preferably 0.2-2 wt% Or 0.5-1.7 wt%.

In addition, the curing agent may have a viscosity at 25 ° C of 0.5-1000 mPa · s or 2-500 mPa · s or 5-150 mPa · s.

The molar ratio of silicon-bonded hydrogen atoms of the curing agent to the silicon-bonded alkenyl of the organopolysiloxane may be 1 or more and less than 50, and may be 3 to 30 in one embodiment.

The curing agent may be contained in an amount of 0.5-10 parts by weight or 1-5 parts by weight based on 100 parts by weight of the total amount of the thermoplastic polyurethane resin (A) and the silicone rubber (B) Within the above range, crosslinking of the silicone rubber (B) is excellent, so that the skin material for automobile interior materials can be provided with improved scratch resistance, weather resistance and touch.

The catalyst may be a catalyst for promoting the crosslinking of the silicone rubber (B). In one embodiment, a hydrosilylation catalyst may be used. Examples of the hydrosilylation catalyst include platinum black, platinum supported on silica, carbon Platinum catalysts such as platinum, chloroplatinic acid, an alcohol solution of chloroplatinic acid, platinum / olefin complexes, platinum / alkenylsiloxane complexes, platinum / beta-diketone complexes, platinum / phosphine complexes and the like, rhodium chloride and rhodium chloride / Di (n-butyl) sulfide complexes and the like, and palladium catalysts such as palladium on carbon, palladium chloride and the like.

The catalyst may be contained in an amount of 0.05-10 parts by weight or 0.1-5 parts by weight based on 100 parts by weight of the total amount of the thermoplastic polyurethane resin (A) and the silicone rubber (B) ) Can be promoted and the production efficiency is excellent.

In addition, the first mixing step (S1) may further comprise the step of mixing the coupling agent, softening mineral oil, plasticizer, other mineral filler, pigment, dye, viscosity modifier, stabilizer, And one or more additives selected from the group consisting of a flexibilizer, and the kind and content thereof are not limited.

The Shore A hardness of the mixture of the first mixing step (S1) of the present invention may be 30-80 or 40-77. If it is less than the above range, the effect of improving the scratch resistance of the skin material for automobile interior materials may be insignificant. If it exceeds the above range, the feeling of soft touch as the skin material for automobile interior materials may be lowered.

The Shore A hardness can be measured according to ISO 868.

Also, the tensile strength at break of the mixture in the first mixing step (S1) may be 3-35 MPa, 4-30 MPa or 4-20 MPa, and the elongation at break may be 600-750%, 610-740%, or 620-730% Lt; / RTI > If it is less than the above range, the effect of improving the scratch resistance may be insignificant. If it exceeds the above range, the air bag may not be torn along the incision line when the air bag is deployed, so that it can have the tensile strength and elongation at break within the above range.

The tensile strength and elongation at break can be measured in accordance with ISO 37.

Also, the melt flow index (MFI) of the mixture in the first mixing step (S1) may be 40-100 g / 10 min (190 ° C, 10 kg) or 45-95 g / 10 min (190 ° C, 10 kg). If it is less than the above range, the moldability of the powder may be deteriorated. If it exceeds the above range, the powder may flow down without melting as a skin material after melting the powder, resulting in defective molding.

The melt index can be measured in accordance with ISO 1133. The method for producing a thermoplastic polyurethane powder for powder slush molding according to the present invention is characterized in that a first mixture of the thermoplastic polyurethane resin (A) and the silicone rubber (B) By including step (S1), the dispersibility of the silicone rubber (B) in the thermoplastic polyurethane powder is excellent and the moldability of the final thermoplastic polyurethane powder is excellent.

The second mixing step (S3)

The second mixing step (S3) comprises mixing 25-70 parts by weight, 30-60 parts by weight or 30-50 parts by weight of the mixture of the first mixing step (S1) with 100 parts by weight of the thermoplastic polyurethane resin (A) Lt; / RTI >

If the content of the mixture in the first mixing step (S1) is less than the above range, the slip property of the skin material for automobile interior material is lowered and the effect of improving the de-molding and improving the scratch resistance may be insignificant, When the amount of the silicone rubber (B) exceeds the above range, the dispersibility of the silicone rubber (B) in the powder is lowered and the moldability of the powder is lowered. In addition, the mechanical properties such as tensile strength and elongation at break of the finished skin material deteriorate, And can be included within the above range.

As a specific example of the second mixing step (S3), a mixture of the thermoplastic polyurethane resin (A) and the first mixing step (S1) is placed in a Banbury mixer and heated at 150-170 ° C or 155-165 ° C for 3 -10 minutes or 5-7 minutes at which time the temperature of the mixture in the second mixing step (S3) may rise to about 170-180 DEG C due to frictional heat.

Also, the mixture in the second mixing step (S3) may optionally contain one kind selected from flame retardants, light stabilizers, high heat stabilizers, lubricants, antioxidants, heat resisting agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, The above additives can be further mixed, and the kind and content thereof are not limited as long as they do not impair the desired effects of the present invention.

The method for producing a thermoplastic polyurethane powder for powder slush molding according to the present invention may further comprise: a pellet production step (S5) of producing a mixture of the second mixing step (S3) with a pellet; And a powder preparation step (S7) of pulverizing the pellet to produce a powder; As shown in FIG.

Pellet production step (S5)

The pellet preparation step (S5) may be a step of putting the mixture of the second mixing step (S3) into an extruder and extruding the mixture at 160-190 ° C or 170-185 ° C to form pellets.

If the temperature is lower than the above temperature range, the mixture in the second mixing step (S3) is not sufficiently melted and the mechanical properties such as tensile strength and elongation at break of the finished skin material deteriorate, (A) is thermally decomposed to deteriorate physical properties such as tensile strength and elongation at break of the finished skin material.

Powder production step (S7)

The powder preparation step (S7) may be a step of freezing the pellet produced in the pellet production step (S5) using liquid nitrogen and then pulverizing or pulverizing the powder through hydro-grinding to produce a thermoplastic polyurethane powder.

The thermoplastic polyurethane powder of the present invention may have an average particle size of 150 to 250 占 퐉 or 170 to 200 占 퐉, and has an average particle size within the above range, thereby being excellent in moldability in powder slush molding.

The average particle size can be measured using a mesh.

In addition, the dropping performance of the thermoplastic polyurethane powder of the present invention is 10-15 seconds or 12-13 seconds, and has the dropping property within the above range, so that the moldability in powder slush molding can be excellent.

100 ml of the thermoplastic polyurethane powder is poured into an apparent specific gravity measuring device funnel according to KS M 3002, and the time taken for 100 ml of powder to fully escape from the funnel can be measured.

The thermoplastic polyurethane powder of the present invention produced from the above-described method for producing a thermoplastic polyurethane powder for powder slush molding has an excellent dispersibility of the silicone rubber in the powder and is excellent in the powder-slush molding molding property.

The present invention also relates to a skin material for an automobile interior material formed using the thermoplastic polyurethane powder.

Specifically, the skin material of the present invention can be produced through a powder slush molding process using the powder described above.

The powder slush molding process may be performed at about 200-250 ° C, 210-240 ° C, or 220-230 ° C to provide excellent skin moldability.

The automotive interiors may be instrument panel, door trim, door trim, console box, arm rest, head rest, filler trim, seat buckle, head liner, glove box trunk cover trim, airbag cover or steering wheel cover.

The skin material for an automobile interior material of the present invention may contain 80-92% by weight or 82-90% by weight of the thermoplastic polyurethane resin, and 5-15% by weight or 6-12% by weight of the silicone rubber.

Since the thermoplastic polyurethane resin is contained within the above range, mechanical properties can be satisfied as a skin material for automobile interior materials, and silicone rubber is contained within the above range, so that the dispersibility in powder is excellent, and the scratch resistance, tensile strength, And has excellent properties such as elongation at break and the like.

The skin material for automobile interior materials of the present invention has an scratch resistance (JIS K 6718, g) of 300 g or more or 400 g or more, and has excellent scratch resistance within the above range. The upper limit thereof is not limited, but may be 1500 g or less or 1300 g or less, for example.

The surface scratch resistance was evaluated by scratching the surface of the surface of the skin with a Heidon scratch tester (SHINTO Co., HEIDON type 14FW) under a load of 100 mm / s at a speed of 100 mm / s in accordance with JIS K 6718, Lt; 2 > m, the load was measured.

The larger the load, the better the scratch resistance.

In addition, the skin material for automobile interior materials of the present invention may have a tensile strength (ISO 5207-3) of 85-150 MPa, 90-140 MPa or 90-120 MPa, and is advantageous in expanding the airbag with excellent mechanical properties within the above range .

The tensile strength may be measured using a universal testing machine (UTM) according to ISO 5207-3.

In addition, the skin material for automobile interior materials of the present invention may have a breaking elongation (ISO 5207-3) of 350-500%, 350-450%, or 400-450% There is an advantageous effect of expanding the airbag even though the mechanical properties are excellent within the above range.

The elongation at break may be measured using a universal testing machine (UTM) according to ISO 5207-3.

The skin material for an automobile interior material of the present invention may have a gloss change rate of -40% to + 40%, -20% to + 20%, or -7% to + 7% It is possible to satisfy the required gloss change rate.

The gloss change rate was measured using a gloss meter (BYK Gardner GLOSS master 60) using a gloss meter (BYK Gardner GLOSS master 60) after irradiating ultraviolet ray (Xenon arc specified in ISO 105) with an incident angle of 60 degrees in accordance with ASTM D563 in an amount of 126 MJ The degree of gloss before and after the ultraviolet ray irradiation can be measured and the rate of change thereof can be calculated.

The skin material for automobile interior materials of the present invention may have weatherability of -30% to + 30%, -25% to + 25%, or -20% to + 20% There is an effect that the required weather resistance can be satisfied.

The weathering resistance can be calculated by measuring the tensile strength and / or the elongation at break before and after aging using a universal testing machine (UTM) after irradiating ultraviolet ray (UV, Xenon arc specified in ISO 105) in an amount of 126 MJ have.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

The components used in the following examples are as follows.

- Thermoplastic polyurethane resin (TPU): Shore A hardness (ISO 868) of 70-88, tensile strength (ISO 527-2) of 26 Mpa, elongation at break (ISO 527-2) of 415%, Vicat softening point (ISO 306) , A thermoplastic polyurethane resin having a melt flow index (MFI) of 48 g / 10 min (185 DEG C, 2.16 kg)

Silicone rubber: Silicone-containing organopolysiloxane having a viscosity of 300-70000 mPa 占 퐏 (25 占 폚)

- Hardener: an organopolysiloxane containing silicon (Si) -bonded hydrogen atoms with a viscosity of 29 mPa.s

Catalyst: a hydrosilylation catalyst comprising 1.5% by weight of a platinum complex of 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane

Paraffin oil: Kukdong Oil & Oil Co., Ltd. Having a weight average molecular weight of 400 g / mole, LP500

- High heat stabilizer: BASF, Irganox 1010

- Light stabilizer: BASF, Tinuvin PUR 866

1. Thermoplastic polyurethane Powder manufacturing

≪ Example 1 >

(1) First mixing step (S1)

Thermoplastic polyurethane resin 70 parts by weight Silicone rubber 30 parts by weight, curing agent 2.5 parts by weight and catalyst 0.1 part by weight were fed into a twin-screw extruder (BAUTEK, BA-19) to perform dynamic vulcanization and mixing at 150-300 rpm and 180 ° C .

(2) the second mixing step (S3)

Subsequently, 40 parts by weight of the mixture of the first mixing step (S1), 6 parts by weight of the high heat stabilizer and 0.3 part by weight of the light stabilizer were added to a thermosetting polyurethane resin at a temperature of 160 DEG C for 5 minutes Mix.

(3) Pellet production step (S5)

Then, the mixture is extruded at a temperature of 180 캜 in an extruder to form a pellet.

(4) Powder production step (S7)

The pellet is pulverized to prepare a thermoplastic polyurethane powder having a particle size of 150 to 250 占 퐉 and a flowability of 10 to 15 seconds.

≪ Example 2 >

(1) First mixing step (S1)

60 parts by weight of a thermoplastic polyurethane resin, 40 parts by weight of a silicone rubber, 2.5 parts by weight of a curing agent and 0.1 part by weight of a catalyst were put into a twin-screw extruder and subjected to dynamic vulcanization and mixing at 150-300 rpm and 180 캜.

(2) - (4): The same procedure as in Example 1 is carried out.

≪ Comparative Example 1 &

(1) First Mixing Step (S1): None

(2) the second mixing step (S3)

5 parts by weight of paraffin oil, 6 parts by weight of a high heat-resistant stabilizer and 0.3 parts by weight of a light stabilizer are added to a Banbury mixer at a temperature of 160 캜 for 5 minutes with respect to 100 parts by weight of a thermoplastic polyurethane resin.

(3) - (4): The procedure of Example 1 is repeated.

≪ Reference Example 1 &

(1) First mixing step (S1)

95 parts by weight of a thermoplastic polyurethane resin, 5 parts by weight of a silicone rubber, 2.5 parts by weight of a curing agent and 0.1 part by weight of a catalyst were put into a twin-screw extruder and subjected to dynamic vulcanization and mixing at 150-300 rpm and 180 캜.

(2) - (4): The same procedure as in Example 1 is carried out.

≪ Reference Example 2 &

(1) First mixing step (S1)

40 parts by weight of a thermoplastic polyurethane resin, 60 parts by weight of a silicone rubber, 2.5 parts by weight of a curing agent and 0.1 part by weight of a catalyst were charged into a twin-screw extruder and subjected to dynamic vulcanization and mixing at 150-300 rpm and 180 캜.

(2) - (4): The same procedure as in Example 1 is carried out.

Reference Example 3:

(1): The same procedure as in Example 2 is carried out.

(2) the second mixing step (S3)

10 parts by weight of the mixture of the first mixing step (S1), 6 parts by weight of the high heat-resistant stabilizer and 0.3 part by weight of the light stabilizer were mixed into a Banbury mixer at a temperature of 160 캜 for 5 minutes to 100 parts by weight of the thermoplastic polyurethane resin .

(3) - (4): The procedure of Example 1 is repeated.

≪ Reference Example 4 &

(1): The same procedure as in Example 2 is carried out.

(2) the second mixing step (S3)

80 parts by weight of the mixture in the first mixing step (S1), 6 parts by weight of the high heat-resistant stabilizer and 0.3 part by weight of the light stabilizer were mixed into a Banbury mixer at a temperature of 160 DEG C for 5 minutes to 100 parts by weight of the thermoplastic polyurethane resin .

(3) - (4): The procedure of Example 1 is repeated.

Reference Example 5:

(1) First Mixing Step (S1): None

(2) the second mixing step (S3)

12 parts by weight of a silicone rubber, 6 parts by weight of a high heat-resistant stabilizer and 0.3 parts by weight of a light stabilizer were added to a Banbury mixer at a temperature of 160 캜 for 5 minutes to 100 parts by weight of a thermoplastic polyurethane resin.

(3) - (4): The procedure of Example 1 is repeated.

2. Manufacture of skin materials for automobile interior materials

The thermoplastic polyurethane powder of Example 1-2, Comparative Example 1 and Reference Example 1-5 prepared above was subjected to a powder slush molding process at a temperature of 220-230 ° C to prepare a skin material for an automobile interior material.

The content of each component in the skin material is summarized in Table 1 below.

Example 1 Example 2 Comparative Example 1 Reference Example 1 Reference Example 2 Reference Example 3 Reference Example 4 Reference Example 5 Skin material
(weight%) TPU 87 84.3 90 93.6 79 91 78.8 84.7 Si rubber 8 10.6 - 1.4 16 3.3 16.8 10 Hardener 0.7 0.7 0.7 0.7 0.2 1.0 - Paraffin oil - - 4.3 - - - - - High heat stabilizer 4.1 4.1 5.4 4.1 4.1 5.2 3.2 5 Light stabilizer 0.2 0.3 0.3 0.2 0.2 0.3 0.2 0.3

[Experimental Example]

1. Formability measurement of powder

Using the thermoplastic polyurethane powder of Example 1-2, Comparative Example 1 and Reference Example 1-5 prepared above, the powder slush molding process was carried out at a temperature of 220-230 ° C. And the results are shown in Table 2 below.

(O: powder was well melted and moldability was excellent, powder type powder could not be seen, and the thickness of the skin material made of the powder was uniform.

X: Powder was poorly melted and moldability was deteriorated, powdery powder was present, and the thickness of the skin material made of the powder was large.

2. Measurement of physical properties of skin materials for automobile interior materials

The scratch resistance, tensile strength, elongation at break, gloss change rate, and weather resistance of the skin materials for automobile interior materials of Examples 1-2, Comparative Examples 1 and 1-5 prepared above were measured and the results are shown in Table 2 below .

(1) Scratch resistance: The surface of a skin sample for automobile interior material having a width of 5 cm and a length of 20 cm or more was subjected to a load of 100 mm / min using a Heidon scratch tester (SHINTO, HEIDON) according to JIS K 6718, After scratching 100 mm at a speed of s, the load was measured when the scratch width on the surface exceeded 200 탆.

The larger the load, the better the scratch resistance.

(2) Tensile Strength: The skin material for automobile interior materials with a width of 5 cm and a length of 20 cm or more was measured using Universal Testing Machine (UTM) according to ISO 5207-3.

(3) Elongation at break: The surface roughness of 5cm width and 20cm length was measured using universal testing machine (UTM) according to ISO 5207-3.

(4) Gloss change rate: Using a skin test piece for automobile interior materials having a width of 5 cm and a length of 20 cm or more, ultraviolet rays (Xenon arc specified in ISO 105) were irradiated at an incident angle of 60 degrees according to ASTM D563 at 126 MJ And then the glossiness before and after the UV irradiation was measured using a gloss meter (BYK Gardner GLOSS master 60), and the rate of change thereof was calculated.

(5) Weatherability: Using a universal testing machine (UTM) after irradiation of ultraviolet rays (Xenon arc specified in ISO 105, ISO 105) in an amount of 126MJ using a skin test piece for a car interior material having a width of 5 cm and a length of 20 cm or more And the tensile strength and / or elongation at break before and after aging were measured and the rate of change thereof was calculated.

3. Sensibility measurement of skin material for automobile interior material

Texture: The inner softness of the skin material was evaluated by touching with the hand, and the relative softness was evaluated. The results are shown in Table 2 below.

(?: Smooth feeling,?: Normal, X: excessive slip property and firm feeling)

Example 1 Example 2 Comparative Example 1 Reference Example 1 Reference Example 2 Reference Example 3 Reference Example 4 Reference Example 5 First mixing
step
(Parts by weight) TPU 70 60 - 95 40 60 60 - Si rubber 30 40 5 60 40 40 Second mixing
step
(Parts by weight) TPU 100 100 100 100 100 100 100 100 The first mixing step
mixture 40 40 - 40 40 10 80 - Si rubber - - - - - - - 12 Paraffin oil - - 5 - - - - - Si rubber content in the skin material (% by weight) 8 10.6 - 1.4 16 3.3 16.8 10 powder Formability ○ ○ ○ ○ X ○ X X Skin material Scratch resistance
(g) 400 600 300 300 600 250 600 100 The tensile strength
(Mpa) 120 100 160 140 80 125 80 65 Elongation at break (%) 400 450 550 500 350 500 350 300 Polish
Rate of change
(%) 5 3 70 8 2 8 2 30 Weatherability
(%) Tensile strength change rate -15 -10 -35 -25 -5 -25 -5 -30 Rate of elongation at break -20 -20 -10 -50 -35 -20 -50 -50 touch ○ ○ ○ △ X △ X △

As can be seen in Table 2, the powders of Examples 1 and 2 prepared by the method of the present invention are superior to those of the powder of Reference Example 5, which is not subjected to the first mixing step (S1) It was confirmed that the dispersibility was excellent and the powder was excellent in moldability.

It was also confirmed that the skin materials produced using the powders of Examples 1 and 2 were excellent in scratch resistance, tensile strength, elongation at break, change in gloss, weatherability, and touch.

On the other hand, the powder of Comparative Example 1 containing paraffin oil in the prior art was excellent in the formability of the powder even though the first mixing step (S1) was not carried out, but the weatherability deteriorated, and as time elapsed, And it is buried in the hands of the user and the initial scratch resistance can not be maintained.

In addition, the skin material of Comparative Example 1 has higher tensile strength and elongation at break than those of the skin materials of Examples 1 and 2, and it is confirmed that the skin material of Comparative Example 1 is not suitable for deploying the air bag.

On the other hand, in Reference Example 1 where a small amount of silicone rubber was used in the first mixing step (S1) and Reference Example 3 where a small amount of the mixture of the first mixing step was used in the second mixing step (S3) It was confirmed that the weatherability and touch were lowered compared with the skin materials of Examples 1 and 2.

Further, in Reference Example 2 where an excessive amount of silicone rubber was used in the first mixing step (S1) and Reference Example 4 where the mixture of the first mixing step was excessively used in the second mixing step (S3), the dispersibility of the silicone rubber in the powder It was confirmed that the formability of the powder was lowered and the mechanical properties such as the tensile strength and elongation at break of the skin material and the feel of the skin deteriorated.

Further, in Reference Example 5 including the silicone rubber but not in the first mixing step (S1), the dispersibility of the silicone rubber in the powder was lowered and the formability of the powder was lowered. Compared to the skin materials of Examples 1 and 2 The scratch resistance, the tensile strength, the elongation at break, the rate of change in gloss, the weather resistance, and the feel were both lowered.

Claims (15)

A first mixing step (Sl) of mixing the thermoplastic polyurethane resin (A) and the silicone rubber (B) in a weight ratio of 90: 50: 10-50; And
And a second mixing step (S3) in which 25-70 parts by weight of the mixture of the first mixing step (S1) is mixed with 100 parts by weight of the thermoplastic polyurethane resin (A), to prepare a thermoplastic polyurethane powder for powder slush molding Way. The method according to claim 1,
Wherein the first mixing step (S1) is a step of mixing the thermoplastic polyurethane resin (A) and the silicone rubber (B) in a weight ratio of 85-55: 15-45, wherein the thermoplastic polyurethane resin . The method according to claim 1,
Wherein the first mixing step (S1) is performed at a temperature of 160-200 占 폚. The method according to claim 1,
Wherein the first mixing step (S1) further comprises mixing a curing agent and a catalyst followed by a dynamic vulcanization step. 5. The method of claim 4,
Wherein the first mixing step (S1) is performed in an extruder. The method according to claim 1,
Wherein the second mixing step (S3) is a step of mixing 30-60 parts by weight of the mixture of the first mixing step (S1) with 100 parts by weight of the thermoplastic polyurethane resin (A). The thermoplastic polyurethane for powder slush molding Gt; The method according to claim 1,
Wherein the second mixing step (S3) is performed at 150-170 DEG C for 3-10 minutes. The method according to claim 1,
The method for producing a thermoplastic polyurethane powder for powder slush molding according to the present invention comprises a pellet production step (S5) of producing a mixture of the second mixing step (S3) as a pellet; And
A powder preparation step (S7) of pulverizing the pellet to produce a powder; Wherein the thermosetting polyurethane powder further comprises a thermoplastic polyurethane powder. 9. The method of claim 8,
Wherein the pelletizing step (S5) is carried out at 160-190 占 폚. A thermoplastic polyurethane powder produced by the process for producing a thermoplastic polyurethane powder according to any one of claims 1 to 9. 11. The method of claim 10,
A skin material for automobile interior materials, which is produced through a powder slush molding process using the thermoplastic polyurethane powder. 12. The method of claim 11,
Wherein the skin material for automobile interior materials comprises 80-92 wt% of a thermoplastic polyurethane resin and 5-15 wt% of a silicone rubber. 12. The method of claim 11,
Wherein the skin material for automobile interior materials has an scratch resistance (JIS K 6718, g) of 300 to 1500 g. 12. The method of claim 11,
Wherein the skin material for automobile interior materials has a tensile strength (ISO 5207-3) of 85-150 MPa and a elongation at break (ISO 5207-3) of 350-500%. 12. The method of claim 11,
Wherein the skin material for automobile interior materials has a gloss change rate (ASTM D563) of -40% to + 40% and a weather resistance of -30% to + 30%.