KR101961517B1 - Polyurethane coating agent with enhanced touchness and anti scratch and coted members with thereof - Google Patents

Abstract

The present invention relates to a polyurethane coating agent having excellent touch feeling and scratch resistance and a coated member using the same. More particularly, the present invention relates to a novel polyurethane coating agent which is resistant to scratches and has a soft touch feeling, .
The matting member according to the present invention is a matting agent for paper or film, which comprises 100 parts by weight of the water-dispersed polyurethane dispersion and 1 to 20 parts by weight of silica powder having a diameter of 0.5 to 5 탆.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyurethane coating agent having excellent touch sensation and scratch resistance, and a coating member coated with the coating member. [0002]

The present invention relates to a polyurethane coating agent having excellent touch feeling and scratch resistance and a coated member using the same. More particularly, the present invention relates to a novel polyurethane coating agent which is resistant to scratches and has a soft touch feeling, .

The matte coating agent is suitable for manufacturing a luxurious product because there is no reflected light, but scratched easily occurs when scratched, and tends to be easily visible because of a small scratched surface.

Accordingly, in order to prevent the occurrence of scratches, a polyurethane based matting coating agent is prepared by curing a rigid organic solvent-based polyurethane base resin through heat or ultraviolet rays and modifying the silica used as a quencher to use the coating It is mainly used to strengthen the rigidity to prevent the occurrence of scratches.

For example, Korean Patent No. 1231508 issued to LG Houses discloses a matte coating composition for a decorative sheet comprising a heat or ultraviolet curable polyurethane binder resin, silica particles surface treated with fluorosilane, and a solvent.

For example, Korean Patent Laid-Open Publication No. 1020130118913, filed by BASF Coatings GmbH, discloses a matte coating composition for automobile repairing surface modified with wax.

In this way, the polyurethane-based matte coating is superior in appearance and is strong against scratches. However, because of the stiff, sticky touch feeling inherent in polyurethane, it can be used for direct contact with human hands, There is a problem that it is not suitable for coating application.

A problem to be solved by the present invention is to provide a novel polyurethane-based matting coating composition having excellent touch feeling and good scratch resistance.

Another problem to be solved by the present invention is to provide a new paper or film member having a polyurethane based matte coating layer having excellent touch feeling and good scratch resistance.

In order to solve the above problems, the matting agent for paper or film according to the present invention is characterized in that 1 to 20 parts by weight of silica powder having a diameter of 0.5 to 5 탆 is contained in 100 parts by weight of the water-dispersed polyurethane dispersion .

In the present invention, the water-dispersed polyurethane is prepared by reacting a polyol and a polyisocyanate to prepare a prepolymer and water-dispersing the prepared prepolymer.

In the practice of the present invention, the polyol may be a conventional polyol used for producing polyurethane, and may be a polyether polyol, a polyester polyol, a polyamide polyol, a polyester amide polyol, a polythioether polyol, Polyol polyols, polysiloxane polyols, acrylic polyols, rolls, and silicone polyols, and the like. The polyether polyols which can be used are alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran, in the presence of a polyfunctional initiator containing from 2 to 8 active hydrogen atoms per molecule, ≪ / RTI > furan. Suitable initiator compounds contain a plurality of active hydrogen atoms and are selected from the group consisting of water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl But are not limited to, toluene diamine, phenylenediamine, toluenediamine, diphenylmethanediamine, ethylenediamine, cyclohexanediamine, cyclohexanedimethanol, resorcinol, bisphenol A, glycerol, trimethylolpropane, 1,2,6- , Pentaerythritol, sorbitol and sucrose. Mixtures of initiators and / or cyclic oxides may be used. Particularly useful polyether polyols are polyoxypropylene diols and triols and poly (oxyethylene-oxypropylene) polyols obtained by the simultaneous or sequential addition of ethylene and propylene oxide to a bi- or tri-functional initiator as fully described in the prior art, Diols and triols. Other particularly useful and preferred polyether polyols include polytetramethylene glycols obtained by the polymerization of tetrahydrofuran. Polyester polyols which can be used include but are not limited to ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, glycerol, trimethylolpropane, pentaerythritol or poly Terminal reaction products of polyhydric alcohols such as polyhydric alcohols, ether polyols, or mixtures of said polyhydric alcohols, and polycarboxylic acids, especially dicarboxylic acids or ester-forming derivatives thereof, such as succinic acid, glutaric acid, Dicarboxylic acid, dicarboxylic acid, dicarboxylic acid, dicarboxylic acid, dicarboxylic acid, dicarboxylic acid, dicarboxylic acid, dicarboxylic acid, dicarboxylic acid or dicarboxylic acid.

In the present invention, the polyisocyanate includes any of those known in the art for the production of polyurethanes and can be selected from aromatic, aliphatic, cycloaliphatic and aromatic polyisocyanates. In a preferred embodiment of the invention said organic isocyanate is selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3- Di (aminocyclohexyl) methane hexamethylene diisocyanate, 1,4 phenylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylene diisocyanate, 1,5 naphthalene diisocyanate, trimethylhexamethylene diisocyanate, Norbornane diisocyanate, and the like.

As a method of forming the prepolymer, a usual aqueous dispersion polyurethane production method can be used. In a preferred embodiment of the present invention, the polyurethane prepolymer of the present invention can be prepared by mixing a polyol and a polyisocyanate with an organic solvent and catalyzed by a catalyst, for example, a tin catalyst, such as a dibutyl tin dilaurator. The organic solvent used in the preparation of the polyurethane prepolymer may be any conventional organic solvent known in the art, for example, benzene, toluene, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, Methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, tetrachlorethylene, N-methylpyrrolidone, etc. These solvents may be used alone or in combination .

The water-dispersible polyurethane according to the present invention is obtained by dispersing a polyurethane prepolymer in water according to a conventional method. In a preferred embodiment of the invention, the polyurethane prepolymer is prepared by reacting with triethylamine and then being water-dispersed, chain-extended with a chain extender such as ethylenediamine and dispersed.

In the present invention, it is preferable that the water-dispersed polyurethane exhibits a soft touch feeling and is made of soft polyurethane having high elongation so as to prevent peeling in the state of being bonded to paper or film exposed to bending, folding or the like .

The soft polyurethane preferably has an elongation of 100 to 2000%, preferably 300 to 500%, and most preferably 500 to 1200%. When the elongation is low, the coating member is difficult to exhibit a soft touch, and is easily peeled off in the state of being bonded to paper or film exposed to bending, folding, or the like. On the other hand, if the elongation is too high, the strength of the surface is lowered and scratched easily occurs. More preferably, the polyurethane has a Tg of -20 to 60 占 폚, preferably -10 to 40 占 폚, and most preferably 0 to 20 占 폚, so that the polyurethane of the seasons can have an anti- .

In the present invention, as the silica powder, a silica powder having an unmodified diameter in the range of 0.5 to 5 mu m is used. Though not to be limited theoretically, the small silica powder of the above range has a good dispersibility in water due to the polarity of the silica powder, and is capable of ensuring the scratch resistance even when the particles are not modified in the coating on paper or film do.

In the present invention, when the size of the silica powder is as small as 0.5 micron or less, it is difficult to produce particles in a powder form, and most of the silica powder is completely embedded in the coating layer, thereby reducing the matte effect.

In the practice of the present invention, it is more preferable to use spherical silica particles in the range of 1 to 3 mu m as the silica powder. In a preferred embodiment of the present invention, the matting coating agent is commercially available and can be used, for example, 220A product of Tohso Silica.

In the practice of the present invention, the matting coating agent is preferably a silica powder in an amount of 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the water-dispersed polyurethane (based on dry weight) To 10 parts by weight of silica powder. When the content of the silica powder is small, it is difficult to obtain a sufficient matte effect. When the content of the silica powder is large, the silica powder is exposed to the coating surface excessively and the scratch resistance is deteriorated.

In the present invention, the coating agent may include a defoaming agent to prevent the generation of bubbles. The antifoaming agent is commercially available and can be used, for example, Tego 810 manufactured by Tego Corporation is suitable. The antifoaming agent may be used in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight based on 100 parts by weight of the water-dispersed polyurethane.

In the present invention, the coating agent may include a thickener so that the coating liquid has a viscosity suitable for coating. The thickener may be purchased commercially and used, for example, Tego 3030 manufactured by Tego Corporation. The thickener is preferably used in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight based on 100 parts by weight of the water-dispersed polyurethane.

In the present invention, the coating agent may be a leveling agent in order to increase the surface dispersibility of the coating liquid and make the height of the coating uniform. The leveling agent is commercially available and can be used. For example, BYK-333 manufactured by BYK is suitable. The leveling agent is preferably used in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight based on 100 parts by weight of the water-dispersed polyurethane.

In the present invention, the coating agent may be a drying agent to control the drying rate of the coating solution. The drying regulator may be commercially available from isopropyl alcohol. The drying regulator is preferably used in an amount of 1 to 20 parts by weight, preferably 5 to 10 parts by weight based on 100 parts by weight of the water-dispersed polyurethane.

In the present invention, the above-mentioned coating agent can additionally use a silicone additive to enhance scratch resistance. The silicone additive is commercially available and can be used, for example, Dow 51 from Dow is used. The silicone additive may be used in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the water-dispersed polyurethane.

In a preferred embodiment of the present invention, the coating agent comprises 1 to 20 parts by weight of silica powder having a diameter in the range of 0.5 to 5 mu m, 0.1 to 5 parts by weight of a defoaming agent, 0.1 to 5 parts by weight of a thickener, 0.1 to 5 parts by weight of a leveling agent, 5 to 10 parts by weight of a drying control agent and 0.2 to 2 parts by weight of a silicone additive.

The present invention, in one aspect,

Paper or film substrate; And

And a water-dispersed polyurethane coating layer in which a silica powder having a diameter of 0.5 to 5 탆 coated on the paper or film substrate is dispersed.

In the present invention, the film may be a polyethylene terephthalate film, an OPP film, a polypropylene film, or a PVC film.

According to the present invention, a water-dispersible polyurethane-based matte coating agent and a matte paper and a matte film coated thereon are provided.

The matte paper or matte film according to the present invention is excellent in texture, is matt and very strong against scratches (scratches). In addition, it has excellent post-processability, and is excellent in offset printing, UV printing, gold and silver foil after coating, and various coating methods can be used. Thus, coating of microgravure, gravure, comma, spray and the like is possible. Also, water-dispersed polyurethane is environmentally friendly, has little fire hazard, and is harmless to human body.

1 shows the nail scraping test result of the matte sheet. (b) is a result of a scratched test of a matte film according to Example 6, and (c) shows a result of a scratch test of a matte film according to Comparative Example 1, It is the result of the crunch test.

Hereinafter, the present invention will be described in detail with reference to examples. The following examples are intended to illustrate the present invention, but are not to be construed as limiting the invention.

Example 1

a. Preparation of water-dispersed polyurethane 1

602 g of PTMEG (Mw 1000), 192 g of NMP and 136 g of DMBA were placed in a 2 L four-necked flask equipped with a stirrer, a mantle, a cooling tube and a thermometer. The mixture was heated to 110 캜 and dehydrated for 30 minutes. 465 g of diisocyanate and 320 g of NMP were charged and 0.35 g of DBTDL was added and reacted at 85 ° C for 4 hours to prepare a polyurethane prepolymer having a solid content of 70% and an NCO content of 2.0%. Thereafter, a stirrer and a pedestal were mounted in a separate container, 890 g of ion-exchanged water and 41 g of triethylamine were mixed, and 856 g of a prepolymer was added with vigorous stirring to perform water dispersion.

Thereafter, 9.2 g of ethylenediamine and 120 g of ion-exchanged water were mixed and added with stirring to prepare a water-dispersed polyurethane having a solid content of 32.5%, a pH of 8.9, a viscosity of 250 cps, a softening point of 120 ° C, a particle size of 32.5 nm and a molecular weight of 100,000 .

b. Preparation of water-dispersed polyurethane 2

(Mw 1000), 301 g of polycarbonate polyol, 192 g of NMP and 136 g of DMBA were placed in a 2-liter four-necked flask equipped with a stirrer, a mantle, a cooling tube and a thermometer and dehydrated for 30 minutes 409g of isophorone diisocyanate and 320g of NMP were added and 0.35g of DBTDL was added and reacted at 85 ° C for 4 hours to prepare a terminal prepolymer having a solid content of 69% and an NCO content of 1.57%. Thereafter, a stirrer and a pedestal were mounted in a separate container, 890 g of ion-exchanged water and 41 g of triethylamine were mixed, and 856 g of prepolymer was added with vigorous stirring to perform water dispersion. Thereafter, 8.3 g of ethylenediamine and 120 g of ion-exchanged water were mixed and stirred to prepare a water-dispersed polyurethane having a solid content of 31%, a pH of 8.2 and a viscosity of 180 cps, a softening point of 85 ° C and a particle size of 43 nm.

c. Preparation of water-dispersed polyurethane 3

465 g of a polyester polyol (Mw1000) and 120 g of an acrylic polyol (MW 900) (Soken AS-300), 192 g of NMP and 136 g of DMBA were charged into a 2 L four-necked flask equipped with a stirrer, a mantle, a cooling tube and a thermometer. After dehydration for 30 minutes, 560 g of isophorone diisocyanate and 320 g of NMP were added, and 0.35 g of DBTDL was added and reacted at 85 ° C for 4 hours to prepare a terminal prepolymer having a solid content of 71.5% and NCO content of 4.62%. Thereafter, a stirrer and a pedestal were mounted in a separate container, and 890 g of ion-exchanged water and 41 g of triethylamine were mixed, and 856 g of a prepolymer was added with vigorous stirring to effect water dispersion. Thereafter, 10.5 g of ethylenediamine, 120 g of water were added thereto under agitation, and then a water-dispersed polyurethane having a solid content of 32%, a pH of 7.8, a viscosity of 175 cps, a softening point of 125 ° C and a particle size of 52.6 nm was prepared.

d. Preparation of water-dispersed polyurethane 4

492 g of PTMEG (Mw1000), and 110 g of ES-100 (number average MW of 21,000), 192 g of NMP and 148 g of DMBA were charged into a 2 L four-necked flask equipped with a stirrer, a mantle, , And then 465 g of isophorone diisocyanate and 320 g of NMP were added and 0.35 g of DBTDL was added and reacted at 85 ° C. for 4 hours to prepare a terminal prepolymer having a solid content of 70% and an NCO content of 2.86%.

Thereafter, a stirrer and a pedestal were mounted in a separate container, 890 g of ion-exchanged water and 67 g of triethylamine were mixed, and 856 g of a prepolymer was added with vigorous stirring to perform water dispersion. Then, 9.2 g of ethylenediamine and 120 g of ion-exchanged water were mixed and stirred to prepare a water-dispersed polyurethane having a solid content of 31%, a pH of 8.7, a viscosity of 218 cps, a softening point of 98 ° C and a particle size of 38 nm.

Example 2. Preparation of coating liquid

(Tego 810), a leveling agent (BYK-333), a thickener (Tego 3030), a drying regulator (IPA: Isopropyl Alcohol) and a silica having an average particle diameter of 1.5 μm Tohso Silica 220A), and a silicon additive (Dow51) were charged and stirred vigorously to prepare a coating solution.

Example 3. Preparation of matte paper using coating agent coating

The coating solution prepared according to Example 2.a was coated on paper to prepare a matte-coated paper. A scratch-resistant, matte-coated paper was produced.

Example 4. Preparation of matte film using coating agent coating

The coating solution prepared in Example 2.b was coated on a PET film to prepare a matte coating film. The manufactured matt film was subjected to a scratch test. 1.

Example 5. Preparation of matte film using coating coating

The coating solution prepared in Example 2.c was coated on a PP film to prepare a matte PP film.

Example 6 A coating liquid having different silica diameters

A coating solution was prepared in the same manner as in Example 2.a except that the average particle size of silica was changed to 5 탆, and coated paper and film were prepared as in Examples 3 to 5 to prepare a matte paper and a film.

Comparative Example 1 A coating solution having a large particle size of silica

A coating solution was prepared in the same manner as in Example 2.b except that the average particle diameter of silica was changed to 12 탆, and a coating film was coated thereon to prepare a matte film.

Comparative Example 2. A coating solution having a large particle size of silica

A coating solution was prepared in the same manner as in Example 2.b except that the average particle size of silica was changed to 20 탆, and a coating film was coated on the film to prepare a matte film.

Example 7. Scratch test

The matt films prepared in Example 4 and Comparative Examples 1 and 2 were scratched. The scratch test was conducted by using a nail scraper test to check the occurrence of scratches on the film using a nail. The results are shown in Fig. Scratches were improved in the film according to Example 1.

Claims (8)

100 parts by weight of water-dispersed polyurethane having a chain extension and 1 to 20 parts by weight of a silica powder having a diameter of 500 nm to 5 탆. The composition is excellent in touch feeling and scratch resistance, and can be subjected to offset printing, UV printing, A matte coating for surface coating of an excellent paper or film. The matting coating composition for surface coating of paper or film according to claim 1, wherein the water-dispersed polyurethane dispersion is a water-dispersed polyurethane having an elongation of 100 to 2000%. The matting coating composition of claim 1 or 2, wherein the coating agent further comprises a defoaming agent, a thickener, a leveling agent, a drying regulator, and a silicone additive. The coating agent according to claim 3, wherein the coating agent comprises 1 to 20 parts by weight of a silica powder having a diameter in the range of 0.5 to 5 mu m, 0.1 to 5 parts by weight of a defoaming agent, 0.1 to 5 parts by weight of a thickener, 0.1 to 5 parts by weight, 5 to 10 parts by weight of a drying control agent and 0.2 to 2 parts by weight of a silicone additive. Paper or film substrate; And
And a matte coating layer coated on the surface of the paper or film substrate,
Here, the matte coating layer comprises 100 parts by weight of water-dispersed polyurethane having a chain extension and 1 to 20 parts by weight of a silica powder having a diameter of 500 nm to 5 μm,
The non-light-fastening member is excellent in touch feeling and scratch resistance, and is excellent in offset printing, UV printing, or gold / silver foil. delete The luminescent member according to claim 5, wherein the film is a polyethylene terephthalate film, an OPP film, a polypropylene film, or a PVC film. 6. The mat member according to claim 5, wherein the coating layer has a Tg of from -20 deg. C to 60 deg.

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