KR101953604B1 - Decoration sheet and manufacturing method thereof - Google Patents
Decoration sheet and manufacturing method thereof Download PDFInfo
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- KR101953604B1 KR101953604B1 KR1020160114384A KR20160114384A KR101953604B1 KR 101953604 B1 KR101953604 B1 KR 101953604B1 KR 1020160114384 A KR1020160114384 A KR 1020160114384A KR 20160114384 A KR20160114384 A KR 20160114384A KR 101953604 B1 KR101953604 B1 KR 101953604B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/24—Organic non-macromolecular coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2317/00—Animal or vegetable based
- B32B2317/12—Paper, e.g. cardboard
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- Paints Or Removers (AREA)
Abstract
A release layer, a coating layer and a substrate layer, wherein the release layer has a peel force of 16 to 25 g / inch according to ASTM D903, and the coating layer has a silicone compound layer derived from the release layer on the surface thereof .
Description
Deco sheet and a method for manufacturing the same.
The design aspect is considered to be one of the important factors because the decorative sheet which can be applied to the surfaces of the interior and exterior materials of automobiles, household appliances, furniture, etc. can be continuously visually confirmed by the passenger or the user and can be physically contacted.
The decorative sheet has a coating layer, and the coating layer is required to have stain resistance and abrasion resistance. In particular, since the decor sheet is exposed to an environment vulnerable to a pollutant, such as curry or the like, which is colored by the food or ink, or whose surface is changed by the organic solvent, it is further required to improve the stain resistance.
An embodiment of the present invention provides a decorative sheet which is provided with high gloss to maintain the appearance quality of the product, and which has improved abrasion resistance and stain resistance.
In one embodiment of the present invention, the release layer comprises a release layer, a coating layer, and a substrate layer, wherein the release layer has a peel force of 16 to 25 g / inch according to ASTM D903, Layer is provided.
In another embodiment of the present invention, there is provided a method of forming a coating, comprising: coating a coating composition on a substrate layer; Laminating a release layer including a silicon compound layer on the coating composition to produce a laminate; And curing the laminate, wherein the release layer has a peeling strength of 16 to 25 g / inch according to ASTM D903.
The decor sheet can simultaneously achieve excellent abrasion resistance, low surface energy and improved stain resistance while maintaining excellent gloss.
1 is a schematic cross-sectional view of a decor sheet according to an embodiment of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which: These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art to which the invention pertains. Only. Like reference numerals refer to like elements throughout the specification.
In the drawings, the thickness is enlarged to clearly represent the layers and regions. In the drawings, for the convenience of explanation, the thicknesses of some layers and regions are exaggerated.
It will also be understood that when a layer, film, region, plate, or the like is referred to as being "on" or "over" another portion, . Conversely, when a part is "directly over" another part, it means that there is no other part in the middle. In addition, when a layer, film, region, plate, or the like is referred to as being "under" or "under" another portion, . Conversely, when a part is "directly underneath" another part, it means that there is no other part in the middle.
An embodiment of the present invention includes a release layer, a coating layer, and a substrate layer, wherein the release layer has a peeling strength of 16 to 25 g / inch according to ASTM D903, and the coating layer has a silicon compound layer And a decorative sheet.
Since the decorative sheet is exposed to an environment vulnerable to a pollutant which is colored by food or ink or whose surface is changed by an organic solvent, it is required to improve resistance to abrasion and stain resistance. It is possible to improve the stain resistance by increasing the content of the silicone compound in the coating composition for the coating layer of the decorative sheet. However, as the content of the silicone compound increases, the gloss of the decorative sheet is lowered, Lt; / RTI >
1, a
The
A primer layer (not shown) may be further formed on the upper or lower surface of the
The thickness of the substrate layer may be from about 50 [mu] m to about 1000 [mu] m. The base layer has a thickness in the above range, so that sufficient strength is given to the decor sheet to prevent unnecessary cost from being generated.
The
The coating layer is a cured product of the coating composition. The coating layer must have excellent abrasion resistance without cracking while maintaining excellent gloss, and should have stain resistance so as not to be colored by food or ink or to change its surface by organic solvent . The coating composition may include a monofunctional (meth) acrylic monomer, a bifunctional (meth) acrylic monomer and a bifunctional urethane (meth) acrylic oligomer. The coating layer formed by electron beam or ultraviolet ray hardening of the coating composition has a high degree of curing And an improved abrasion resistance, can have a low surface energy and an improved stain resistance, and at the same time a high gloss can be imparted to maintain a good quality of the appearance of the product.
The coating composition may include a monofunctional (meth) acrylic monomer to easily control the viscosity of the coating liquid, adjust the thickness of the coating layer, and facilitate formation of a coating layer having desired physical properties. For example, the monofunctional (meth) acrylic monomer may be (Meth) acrylic acid; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate such as stearyl (meth) acrylate; Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Glycidyl (meth) acrylates such as decanyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and nonylphenyl (meth) acrylate; Aralkyl (meth) acrylates such as benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; Alkane diol mono (meth) acrylate; Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and hexafluoroisopropyl (meth) acrylate; Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate; Aryloxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate and phenoxypropyl (meth) acrylate; (Meth) acrylate, nonylphenylcarbitol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate aryloxy (poly) alkoxyalkyl (meth) acrylate; Polyalkylene glycol mono (meth) acrylate such as polyethylene glycol mono (meth) acrylate; Acrylate such as 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, butylaminoethyl (meth) acrylate such as glycerin mono (Meth) acrylate having an amino group such as glycidyl (meth) acrylate, glycidyl (meth) acrylate, and combinations thereof. The monofunctional (meth) acrylic monomer may be included in an amount of about 5 to about 20 parts by weight based on 100 parts by weight of the coating composition.
Examples of the bifunctional (meth) acrylic monomer contained in the coating composition include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di ) Acrylate, polyethylene glycol di (meth) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxyl puivalic acid neopentyl glycol di (meth) acrylate, Dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (meth) acryloxyethyl isocyanurate, allyl allyl) cyclohexyl di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide modified hexahydrate Acrylate, neopentyl glycol-modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate, or 9,9- Bis [4- (2-acryloyloxyethoxy) phenyl] fluorine, and combinations thereof.
The bifunctional urethane (meth) acrylic oligomer may be selected from the group consisting of polyether urethane acrylate, polyester urethane acrylate, polycaprolactone urethane acrylate, polycarbonate urethane acrylate, polybutadiene urethane acrylate, and combinations thereof May be one selected compound.
The bifunctional urethane (meth) acrylic oligomer is formed by a polymerization reaction of a polyol compound and an isocyanate compound. The polyol compound is a polyether polyol, a polycaprolactone polyol, a polycarbonate polyol, a polybutadiene polyol, a polyester amide polyol, Polymeric polyols such as polymeric polyols and polymeric polyols. The isocyanate-based compounds may be aliphatic isocyanate compounds such as HDI (hexa-methylene-di-isocyanate), isophorone-di-isocyanate (IPDI), xylene- Aromatic diisocyanate compounds such as XDI, 2,4-toluene-di-isocyante (TDI), 4,4-di-phenyl-methane- -isocyanate), and a combination of these. By using a non-aromatic polyisocyanate or a derivative thereof, higher weather resistance and vulcanization resistance can be realized.
The weight average molecular weight (Mw) of the bifunctional urethane (meth) acrylic oligomer may be about 500 g / mol to about 10,000 g / mol. Wherein the coating composition comprises the bifunctional urethane (meth) acrylic oligomer in an amount of about 30 to about 70 parts by weight relative to 100 parts by weight of the total amount of the monofunctional (meth) acrylic monomer and the bifunctional (meth) acrylic monomer, Can provide a cured coating layer with appropriate flexibility together with an excellent degree of curing, and the coating layer has low surface energy, has excellent stain resistance, and can have excellent abrasion resistance
The coating composition may further comprise one additive selected from the group consisting of silicone acrylate oligomers, fluorine compounds, ultraviolet absorbers, hindered amine radical stabilizers, and combinations thereof.
Specifically, the coating composition may further include an ultraviolet absorber. The ultraviolet absorber may absorb ultraviolet rays irradiated to the coating layer to release heat energy, thereby preventing discoloration of the coating layer due to photooxidation. Examples of the ultraviolet absorber include ultraviolet absorbers such as triazine-based ultraviolet absorbers, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, salicylate ultraviolet absorbers, acrylonitrile ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, oxanilides Based ultraviolet absorber, and combinations thereof. Specifically, the coating composition further contains a triazine-based ultraviolet absorber and has a high ultraviolet absorption rate and may not be deteriorated by high energy such as ultraviolet rays. Wherein the ultraviolet absorber comprises about 0.5 to about 10 parts by weight of the ultraviolet absorbent relative to 100 parts by weight of the total amount of the monofunctional (meth) acrylic monomer, the bifunctional (meth) acrylic monomer and the bifunctional urethane (meth) .
Further, the coating composition may further include a hindered amine type radical stabilizer as a radical stabilizer, and can capture and stabilize radicals generated by ultraviolet rays. Specifically, 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2'-n-butylmalonic acid bis
(1,2,2,6,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis , 2,6,6-pentamethyl-
4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl- 4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), tetrakis (2,2,6,6,6-tetramethylpiperidin- 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-piperidinylmethacryl Rate; A hindered amine radical stabilizer having a reactive functional group such as 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, and a combination thereof. The coating composition may contain the hindered amine radical stabilizer in an amount of about 0.5 wt% based on 100 wt% of the total amount of the monofunctional (meth) acrylic monomers, the bifunctional (meth) acrylic monomers, and the bifunctional urethane (meth) To about 10 parts by weight.
The silicone acrylate oligomer, which is an additive further included in the coating composition, may have a weight average molecular weight of about 500 to about 200,000. Specifically, it may have a weight average molecular weight of about 1000 to about 100,000. The silicone acrylate oligomer may be used in an amount of about 0.5 to about 50 parts by weight based on 100 parts by weight of the total amount of monofunctional (meth) acrylic monomers, bifunctional (meth) acrylic monomers and bifunctional urethane (meth) . Specifically, it may be contained in an amount of about 1 to about 20 parts by weight. If the silicon acrylate is out of the above range, the gloss may be lowered and the stain resistance may be lowered. Particularly, when the amount is less than the above range, the stain resistance is remarkably poor. If the amount exceeds the above range, the gloss of the coating layer is lowered and the quality of the decor sheet may be deteriorated.
The silicone acrylate oligomer is crosslinked with a silicone compound derived from a monofunctional (meth) acrylic monomer, a bifunctional (meth) acrylic monomer and a bifunctional urethane (meth) acrylic oligomer and a release layer contained in the coating composition, The crosslinking density of the coating layer including the compound layer, and the like can be controlled. Thus, it is possible to impart high gloss to the decorative sheet including the decorative sheet to maintain the appearance quality of the product, and to impart excellent abrasion resistance, low surface energy, and improved stain resistance.
(Meth) acrylic monomer and the bifunctional urethane (meth) acryl-based oligomer in a total amount of 100 parts by weight, and the coating layer is an ultraviolet cured product of the coating composition, In an amount of about 1 part by weight to about 20 parts by weight, relative to the total weight of the composition. Specifically, it may be contained in an amount of about 1 to about 15 parts by weight. Examples of the photoinitiator include benzoin methyl ether, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide,?,? -Methoxy-? -Hydroxy Acetophenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4-morpholyl) phenyl] -1- butanone, 2,2- Dimethoxy-1,2-diphenylethan-1-one, 1 -hydroxy-cyclohexyl-phenyl ketone, 2-benzyl- 2- (dimethylamino) -1- [4- (4-morpholinyl) ] -1-butanone, and combinations thereof.
The
At this time, the silicon compound layer may be derived from a release layer laminated on the surface of the coating layer. Generally, a silicon compound layer can be formed by a separate process such as coating a silicon compound on a coating composition, but in this case, the number of processes increases, which may be disadvantageous in terms of cost. The decor sheet is economical because it has a silicon compound layer derived from a release layer laminated on the surface of a coating layer.
Specifically, the silicone compound layer on the surface of the coating layer is formed by laminating and curing a release layer comprising a silicone compound layer on a coating composition, forming a coating layer, and transferring the silicone compound layer of the release layer onto the surface of the coating layer . That is, the decor sheet is economical because the silicon compound layer is formed on the entire surface or a part of the surface of the coating layer without a separate coating process.
The silicon compound layer may comprise one silicon compound selected from the group consisting of alkenyl polysiloxanes, hydrogen polysiloxanes, polysilicon containing vinyl groups, and combinations thereof. The silicone compound is derived from a release layer. As described above, when the coating composition is cured to form a coating layer, the silicone compound is transferred from the release layer to the surface of the coating layer while performing a crosslinking reaction with the coating composition.
The alkenyl polysiloxane may have a weight average molecular weight (Mw) of about 100,000 to about 500,000, which may be represented by the following formula (1), and has excellent abrasion resistance, low surface energy and improved stain resistance .
[Chemical Formula 1]
M is an integer of 20 to 5,000, n is an integer of 1 to 100, and m + n may be 30 to 5,000.
The hydrogelpolysiloxane can be represented by the following formula (2), which controls the cross-linking density of the silicone compound layer and can impart low surface energy and improved stain resistance to the coating layer including the same.
(2)
In the above, a is an integer of 3 to 200, and b is an integer of 1 to 120, and 5? A + b? 200.
The vinyl group-containing polysilicon forms a three-dimensional dendritic structure having a plurality of branches as compared with a linear silicon mixture such as the alkenyl polysiloxane or the hydrogen polysiloxane, The density of the polysilicon itself contained therein is high, and the crosslinking density of the silicon compound layer can be increased. Thus, it is possible to impart low surface energy and improved stain resistance to the coating layer including the coating layer, in addition to excellent abrasion resistance.
The surface energy of the surface of the coating layer may be about 10 to about 25 mN / m. The coating layer is a cured product of the coating composition, and the coating layer has a surface of a silicon compound derived from the release layer on the surface, and may have surface energy in the above range. As the coating layer has the surface energy in the above range, it can maintain an excellent laminated structure with the substrate layer, and the surface of the coating layer can have a low bonding force with respect to an organic substance or an inorganic substance and has excellent abrasion resistance, Can be implemented. In addition, it is possible to maintain a high gloss and maintain the quality of the decor sheet.
The degree of cure of the coating layer may be from about 80% to about 98%. Specifically, the degree of cure of the coating layer may be from about 90% to about 98%. The degree of curing can be measured by the following formula (1).
[Formula 1]
Hardening degree (GEL,%) = (Later mass / Initial mass) × 100
Specifically, the mass of the target hardened specimen to be measured is measured to obtain the " initial mass ". The initial weight of the cured specimen was immersed in an ethyl acetate solvent and allowed to stand at room temperature for 24 hours. The sample was filtered using a 200-mesh wire net and dried at 110 ° C for 2 hours to obtain a mass (dry weight) Can be measured as "later mass".
The decorative sheet includes the coating layer having the above-mentioned curability, so that it can exhibit excellent abrasion resistance and stain resistance while maintaining high transparency of the base layer. For example, when the degree of curing of the coating layer is less than the above range, the contaminants may be easily absorbed and the contamination resistance may be deteriorated. If the degree of curing exceeds the above range, cracks may occur in the coating layer.
The thickness of the coating layer 20 may be about 5 [mu] m to about 50 [mu] m. By maintaining the thickness of the coating layer in the above range, excellent abrasion resistance and stain resistance can be realized. For example, when the thickness of the coating layer 20 is less than the above range, it is difficult to ensure the uniformity of the thickness of the coating layer 20 due to the formation. When the thickness of the coating layer 20 exceeds the above range , The curability for forming the coating layer 20 may be lowered.
In addition, the decor sheet includes a release layer, and the release layer prevents contact with oxygen in the air during the curing process of the coating composition forming the coating layer, so that the curing can be efficiently performed. Thus, the coating layer, which is a cured product of the coating composition, can exhibit excellent abrasion resistance and stain resistance while maintaining transparency.
The release layer has a peel force of about 16 to about 25 g / inch at room temperature of about 23 to about 27 DEG C according to ASTM D903. For example, the release layer has a peel force of about 16 g / inch to about 25 g / inch when the TESA 7475 tape is bonded on top and peeled at 180 degrees at a rate of 300 mm / min according to ASTM D903.
The releasing layer has a peeling force in the above range, so that an appropriate releasing force can be maintained, and at the same time, the surface energy of the surface of the coating layer to which the releasing layer is abutted can be lowered. For example, when the releasing force of the releasing layer is less than the above range, the surface energy of the surface of the coating layer becomes high, so that it has a high binding force to an organic substance or an inorganic substance and exhibits very low stain resistance. Specifically, when a line is drawn on the decor sheet with contaminants such as stamps, oil-based magic, mustard, etc., and wiped off immediately, unevenness may remain and the coating layer may be damaged.
When the releasing force of the releasing layer exceeds the above range, defective peeling property may be exhibited at the step of releasing the releasing layer, and the degree of gloss may be lowered.
Wherein the releasing layer is a cured product of a releasing composition comprising one silicone compound selected from the group consisting of alkenyl polysiloxane, hydrogen polysiloxane, vinyl group-containing polysilicon, and combinations thereof, wherein the content of the silicone compound It can have a peel force of about 16 to about 25 g / inch according to ASTM D903.
As described above, the alkenyl polysiloxane may have a structure represented by the following formula (1) and have a weight average molecular weight (Mw) of about 100,000 to about 500,000. In addition, the hydrogen polysiloxane may have the structure of the above-described formula (2), and the vinyl group-containing polysilicon may be a compound forming a three-dimensional dendritic structure.
The releasing layer may have a releasing force in the above range by having a cured product of the releasing composition containing the silicone compound in a thickness of about 100 to about 200 nm on one side of the polyester film.
In another embodiment of the present invention, there is provided a method of forming a coating, comprising: coating a coating composition on a substrate layer; Laminating a release layer including a silicon compound layer on the coating composition to produce a laminate; And curing the laminate, wherein the release layer provides a release strength of 16 to 25 g / inch according to ASTM D903 at room temperature.
The above-mentioned decor sheet can be produced by the above-mentioned method for producing a decor sheet. That is, by the method for producing the decorative sheet, a decorative sheet having excellent abrasion resistance, low surface energy, and improved stain resistance can be economically and efficiently manufactured while maintaining high transparency.
The method for producing the decorative sheet is a step of coating the coating composition on the base layer, and the composition and characteristics of the base layer and the coating composition are as described above.
The coating may be applied to a substrate such as a bar coating, a roll coating, a curtain coating, a gravure coating, a micro-gravure coating, a slot-die coating, , And is preferably, but not exclusively, carried out by a bar coating method. At this time, the bar coating method is advantageous in that a thin coating is formed using a bar coater, and a coating layer of a precise and constant thickness can be formed on the surface of the substrate with paints and coating agents.
The coating composition may be coated on the substrate layer to a thickness of about 5 탆 to about 50 탆. At this time, the thickness can be adjusted by controlling the interval between the rolls when the roll coating is performed.
Then, a release layer containing a silicone compound layer may be laminated on the coating composition to form a laminate.
At this time, the laminate may be prepared by laminating a silicone compound layer so as to contact with the coating composition, and by contacting the release layer at the same time as coating, contact with air can be minimized.
The releasing layer is formed by applying and curing a releasing composition comprising a silicone compound on one side of a polyester film, wherein the releasing layer comprises a silicon compound layer. Examples of the polyester film include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), and the like. For example, the polyester film may be polyethylene terephthalate and may exhibit an appropriate peel force.
The silicone compound included in the mold-releasing composition may include one silicone compound selected from the group consisting of alkenyl polysiloxane, hydrogen polysiloxane, polysilicon containing vinyl groups, and combinations thereof. The silicone compound is as described above and may be dispersed in an organic solvent.
When the coating composition is cured to form a coating layer, the silicone compound is transferred to the surface of the coating layer while performing a cross-linking reaction with the coating composition, thereby imparting excellent abrasion resistance, low surface energy and improved stain resistance to the coating layer.
The decor sheet can be produced by curing the laminate. The curing may be performed by irradiating an electron beam having an acceleration voltage of about 80 to about 250 keV and an electron beam of about 30 to about 150 kGy depending on the thickness of the coating layer. Or it may be carried out by irradiating the ultraviolet energy of about 100 mJ / cm 2 to about 10,000 mJ / cm 2. The silicone compound layer is transferred from the release layer to the coating composition, and at the same time, the coating composition is cured to form a coating layer. By irradiating the above-mentioned laminate with energy in the above range, the silicone compound of the release layer is transferred in an appropriate amount, and the crosslinking density with the coating composition can be controlled. Further, the degree of curing of the coating layer of the decor sheet can be controlled.
The thus-produced decor sheet can be directly used to remove the release layer or can be used for interior and exterior materials of automobiles to be used after removing the release layer immediately before use.
Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.
Example One
9.5 parts by weight of isobornyl acrylate, 45.5 parts by weight of tricyclodecane dimethanol acrylate and 45.5 parts by weight of bifunctional urethane (meth) acrylic oligomer (Mw = 1400) were prepared. The coating composition is coated on the top of a base layer made of polyethylene terephthalate glycol to a thickness of 10 to 30 占 퐉 by a roll coating method and a release layer including a silicone compound layer is laminated on the coating composition, . At this time, the release layer was peeled off at 180 ° under a condition of a speed of 300 mm / min according to ASTM D903 by adhering a TESA7475 tape on the tape and having a peeling force of 16 g / inch.
Then, the laminate was irradiated with an electron beam at a voltage of 150 keV and an electron beam of 30 to 50 kGy, followed by curing to produce a decor sheet.
Example 2
A decor sheet was prepared in the same manner as in Example 1, except that a release layer having a peel force of 20 g / inch was used.
Example 3
A decor sheet was prepared in the same manner as in Example 1, except that a release layer having a peel force of 25 g / inch was used.
Example 4
A photoinitiator (Irgacure 184) was added to the coating composition. In this case, the photoinitiator is not 1-functional (meth) acrylic monomer, a bifunctional (meth) acrylic monomer and a bifunctional urethane (meth) contains an amount acrylic oligomer a total content of 10 parts by weight of 100 parts by weight of the preparation, the electron beam 500mJ / cm 2 To 1500 mJ / cm < 2 >, and then cured.
Example 5
Silicone acrylate (Mw = 6,000) was added to the coating composition. The silicone acrylate was prepared in the same manner as in Example 2 except that the silicone acrylate was used in an amount of 5 parts by weight based on 100 parts by weight of the total amount of the monofunctional (meth) acrylic monomer, the bifunctional (meth) acrylic monomer and the bifunctional urethane To prepare a decor sheet.
Comparative Example One
A deco sheet was prepared in the same manner as in Example 1 except that a release layer having a peel force of 12 g / inch was used.
Comparative Example 2
A decor sheet was prepared in the same manner as in Example 1, except that a release layer having a peel force of 30 g / inch was used.
Comparative Example 3
A photoinitiator (Irgacure 184) was added to the coating composition. In this case, the photoinitiator is not 1-functional (meth) acrylic monomer, a bifunctional (meth) acrylic monomer and a bifunctional urethane (meth) contains an amount acrylic oligomer a total content of 10 parts by weight of 100 parts by weight of the preparation, the electron beam 500mJ / cm 2 To 1500 mJ / cm < 2 >, respectively, to prepare a decorative sheet.
Comparative Example 4
Silicone acrylate (Mw = 6,000) was added to the coating composition. The silicone acrylate was prepared in the same manner as in Comparative Example 1 except that the silicone acrylate was used in an amount of 5 parts by weight based on 100 parts by weight of the total amount of monofunctional (meth) acrylic monomers, bifunctional (meth) acrylic monomers and bifunctional urethane In the same manner as in the above.
<Evaluation>
1. Surface energy measurement
Water and diiodomethane were placed on the surfaces of the coating layers of Examples and Comparative Examples and contact angles were measured with a contact angle meter (
2. Evaluation of stain resistance
The decorative sheet of the examples and comparative examples was drawn with a stamp (Monami Co., Ltd.), Yusung Magic (Monami Co., Ltd.) or mustard to the coating layer from which the release layer had been removed, left for 16 hours and wiped off with ethanol The samples were visually observed and graded according to the following evaluation criteria, and the results are shown in Table 1 below. The above evaluation criteria are based on the following 1) to 5). 3) Grade 3: The coating layer is not damaged, but a lot of stains remain. 4) Grade 2: The coating layer is not damaged and the stain is completely removed. 4) Grade: The coating layer is not damaged, The coating layer is damaged and a lot of stains remain. 5) Class 1: The coating layer is damaged much, and a lot of stains are left.
3. Polarity measurement
The decor sheets prepared in the above Examples and Comparative Examples were measured using a 60 degree gloss meter (AG-4460, BYK-Gardner, Inc.). Specifically, the decor sheet was placed on a 60-degree gloss system so that the coating layer of the decor sheet was directed upward, light was radiated at an incident angle of 60 degrees, and the amount of light reflected at a reflection angle of 60 degrees was measured to measure gloss , Are shown in Table 1 below.
Contact angle (°)
(Stamped / oiled magic / mustard)
As shown in Table 1, it can be seen that the decorative sheet of the embodiment gives high gloss to maintain the appearance quality of the decorative sheet, while simultaneously realizing excellent abrasion resistance, low surface energy and improved stain resistance. Specifically, the decor sheet may have a gloss of from about 90 to about 95, with low surface energy and significantly improved stain resistance.
10: Deco Sheet
100: substrate layer
200:
300: Coating layer
Claims (14)
The releasing layer has a peeling strength according to ASTM D903 of 16 to 25 g / inch,
Wherein the coating layer comprises a cured product of a coating composition comprising a monofunctional (meth) acrylic monomer, a bifunctional (meth) acrylic monomer and a bifunctional urethane (meth) acrylic oligomer,
Wherein the silicon compound layer is a transfer material derived from the release layer,
Wherein the bifunctional urethane (meth) acrylic oligomer has a weight average molecular weight (Mw) of 500 g / mol to 10,000 g / mol,
Wherein the silicon compound layer comprises one silicon compound selected from the group consisting of alkenyl polysiloxanes, hydrogen polysiloxanes, polysilicon containing vinyl groups, and combinations thereof,
Wherein the coating layer has a surface energy of 10 to 25 mN / m
Deco sheet.
Wherein the coating composition further comprises a silicone acrylate oligomer
Deco sheet.
Wherein the coating layer has a curing degree of 80% to 98%
Deco sheet.
The base layer may be formed of a material selected from the group consisting of translucent PVC, polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polyethylene naphthalate (PEN), polycarbonate (PC) , Cyclic olefin polymers or copolymers, methylene diphenyl diisocyanate (MDI), and combinations thereof. The term " polymer "
Deco sheet.
Wherein the thickness of the coating layer is 5 [micro] m to 50 [micro] m
Deco sheet.
Wherein the base layer has a thickness of 50 mu m to 1000 mu m
Deco sheet.
Laminating a release layer including a silicon compound layer on the coating composition to produce a laminate; And
And curing the laminate,
Wherein the coating composition comprises a monofunctional (meth) acrylic monomer, a bifunctional (meth) acrylic monomer and a bifunctional urethane (meth) acrylic oligomer,
Wherein the bifunctional urethane (meth) acrylic oligomer has a weight average molecular weight (Mw) of 500 g / mol to 10,000 g / mol,
Wherein the silicon compound layer comprises one silicon compound selected from the group consisting of alkenyl polysiloxanes, hydrogen polysiloxanes, polysilicon containing vinyl groups, and combinations thereof,
Wherein the laminate is produced by laminating the silicon compound layer so as to contact with the coating composition,
In the step of curing the laminate,
The silicone compound layer is transferred from the release layer to the coating composition, and at the same time, the coating composition is cured to form a coating layer,
A surface energy of the surface of the coating layer is 10 to 25 mN / m,
The releasing layer has a peeling strength according to ASTM D903 of 16 to 25 g / inch
A method of manufacturing a decorative sheet.
The curing is carried out by irradiating an electron beam of 30 to 150 kGy
A method of manufacturing a decorative sheet.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160114384A KR101953604B1 (en) | 2016-09-06 | 2016-09-06 | Decoration sheet and manufacturing method thereof |
| PCT/KR2017/009635 WO2018048147A1 (en) | 2016-09-06 | 2017-09-04 | Decoration sheet and method for manufacturing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160114384A KR101953604B1 (en) | 2016-09-06 | 2016-09-06 | Decoration sheet and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20180027151A KR20180027151A (en) | 2018-03-14 |
| KR101953604B1 true KR101953604B1 (en) | 2019-05-17 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020160114384A KR101953604B1 (en) | 2016-09-06 | 2016-09-06 | Decoration sheet and manufacturing method thereof |
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| Country | Link |
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| KR (1) | KR101953604B1 (en) |
| WO (1) | WO2018048147A1 (en) |
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| CN111117508B (en) * | 2019-12-27 | 2021-10-26 | 无锡达美新材料有限公司 | Polyethylene protective film with ultralow surface energy and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001225420A (en) | 2000-02-18 | 2001-08-21 | Dainippon Printing Co Ltd | Decorative sheet |
| JP2012056237A (en) * | 2010-09-10 | 2012-03-22 | Dainippon Printing Co Ltd | Three-dimensional molding decorative sheet and decorative molded product using the same |
| KR101538447B1 (en) * | 2014-02-17 | 2015-07-22 | 도레이첨단소재 주식회사 | Release sheet |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100757016B1 (en) * | 2006-05-29 | 2007-09-11 | (주)아이디어 스틱스 코리아 | Fabric sheet for decoration or interior and manufacture method of it |
| KR100882719B1 (en) * | 2007-08-16 | 2009-02-06 | 도레이새한 주식회사 | Polyester film with excellent stability in peeling force over time and manufacturing method threrof |
| KR101964094B1 (en) * | 2014-09-30 | 2019-04-02 | (주)엘지하우시스 | Matt coating composition, matt coating sheet and the manufacturing method of the same |
| KR102016954B1 (en) * | 2014-10-24 | 2019-09-03 | (주)엘지하우시스 | Uv curing type matt paint composition, a decoration sheet applied the same and methods for manufacturing the decoration sheet |
-
2016
- 2016-09-06 KR KR1020160114384A patent/KR101953604B1/en active IP Right Grant
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2017
- 2017-09-04 WO PCT/KR2017/009635 patent/WO2018048147A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001225420A (en) | 2000-02-18 | 2001-08-21 | Dainippon Printing Co Ltd | Decorative sheet |
| US20010046594A1 (en) | 2000-02-18 | 2001-11-29 | Masataka Takemoto | Decorative sheet |
| JP2012056237A (en) * | 2010-09-10 | 2012-03-22 | Dainippon Printing Co Ltd | Three-dimensional molding decorative sheet and decorative molded product using the same |
| KR101538447B1 (en) * | 2014-02-17 | 2015-07-22 | 도레이첨단소재 주식회사 | Release sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018048147A1 (en) | 2018-03-15 |
| KR20180027151A (en) | 2018-03-14 |
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