KR20130078579A - Deco-sheet comprising foaming layer - Google Patents

Abstract

PURPOSE: A deco sheet is provided to smoothly form a curved part and an edge with a high reception rate. CONSTITUTION: A deco sheet in which a foaming layer is formed comprises a hard coating layer (130) and a base layer. A foaming layer is formed on the base layer. A PET-G material and a PET material are mixed and include pigment. The foaming layer is formed with a thermal disassembling foaming agent. The foaming agent is selected from azobis formamide, oxy benzene sulfonyl hydrazide, or palladium toluene sulfonyl hydrazide.

Description

Decor sheet with foam layer {Deco-sheet comprising foaming layer}

The present invention relates to a deco sheet formed with a foam layer, and more particularly, to a deco sheet capable of forming a membrane due to its good flexibility and excellent scratch resistance and fouling resistance by improving mechanical properties.

In general, a decoration sheet (hereinafter referred to as a "deco sheet") means a sheet for expressing various decorations on furniture such as dressers, desks, and sinks.

Conventionally, decor sheets have been used using polyvinyl chloride resins and combustible polypropylene resins. However, polyvinyl chloride material is excellent in physical properties and formability, but it is inferior in durability and emits a large amount of toxic gas when incinerated, which is classified as an environmentally harmful substance. There was a problem.

In addition, polyolefin-based resins have been used as a material for replacing them, which is difficult to mold and has a poor appearance quality. The olefin resin has excellent heat resistance and mechanical strength, excellent chemical resistance, electrical insulation, and the like, and is widely used in plastic films and sheets for non-toxicity. However, due to the inherent adhesive properties, the olefinic resin may stick to the roll surface during processing of a calender, and in particular, when ductility is imparted, such as polyvinyl chloride molded article for decor sheet, the adhesion becomes more difficult and the molding is difficult. The surface and appearance quality of the product is also degraded. In addition, due to the inherent elastic modulus of the olefin-based film there is a problem that the membrane molding is impossible.

Korean Patent Publication Nos. 2002-0011290 and 2002-0011289 disclose a decorating sheet composition capable of calendering by mixing an inorganic filler, an antiblocking agent, a lubricant and a stabilizer with polypropylene and polyethylene resin, but in this case, Using an inorganic filler, the compatibility with the base (Base Resin) is lowered, the mechanical properties of the decor sheet when molding into a product, there is a problem such as poor durability and flammable burning in combustion. In addition, there is a problem of membrane molding due to the high Tg temperature, which is an inherent physical property.

Accordingly, there is a demand for the development of a decor sheet capable of forming a membrane while the decor sheet secures high flexibility, scratch resistance, and contamination resistance.

In order to solve the above problems, an object of the present invention is to provide a decor sheet capable of forming a membrane while maintaining a suitable flexibility.

Another object of the present invention is to provide an environmentally friendly decor sheet excellent in pollution resistance.

In order to achieve the above object, the present invention is a decorative sheet having a base layer and a hard coating layer, the base layer is formed of a foam layer, PET-G and PBT is mixed, and a foam layer characterized in that it contains a pigment It provides the formed deco sheet.

In another aspect, the present invention is the foam layer is formed of a pyrolytic foaming agent, the blowing agent is azozyme carbon amido (ADCA), azobis formamide (azobis formamide), oxy benzene sulfonyl hydrazide (OBSH) ), Para-toluene sulfonyl hydrazide (palladium toluene sulfonyl hydrazide) to provide a decorative sheet formed foam layer, characterized in that at least one selected from the group consisting of.

In another aspect, the present invention provides a decorative sheet having a foam layer, characterized in that the content of the thermal decomposition foaming agent is contained 1 to 20 parts by weight based on 100 parts by weight of the base layer.

In another aspect, the present invention provides a foam sheet with a foam layer, characterized in that the foam layer may further include a foam aid, the content of the foam aid is 1 to 5 parts by weight based on 100 parts by weight of the base layer. .

In addition, the present invention may further include an inorganic filler in the foam layer, the inorganic filler is composed of calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide (antimon), zinc borate, molybdenum (molybdan) as an inorganic filler It provides a decorative sheet formed foam layer, characterized in that at least one selected from the group.

In another aspect, the present invention provides a decor sheet formed foam layer, characterized in that the mixing ratio of the PET-G and PBT is 5: 5 to 7: 3 molar ratio.

In another aspect, the present invention provides a deco sheet formed foam layer, characterized in that the base layer is further mixed with PCTG, the mixing ratio of PET-G, PBT and PCTG is 5: 4: 1 to 6: 3: 1 molar ratio. .

In another aspect, the present invention provides a decorative sheet is formed foam sheet, characterized in that the pigment using any one of TiO ₂ , Pigment Yellow and Pigment Blue.

In another aspect, the present invention provides a decorative sheet having a foam layer, characterized in that the hard coating layer is a polyurethane-based.

Decor sheet formed with a foam layer according to the present invention has an excellent elongation and high flexibility has the effect that the edges and curved portions are formed smoothly.

In addition, the decorative sheet formed foam layer according to the present invention is excellent in scratch resistance of the surface, there is an effect excellent in fouling resistance.

Figure 1 shows a cross-sectional view of the decorative sheet is formed foam layer according to an embodiment of the present invention.

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

The terms " about ", " substantially ", etc. used to the extent that they are used herein are intended to be taken to mean an approximation to or in the numerical value of the manufacturing and material tolerances inherent in the meanings mentioned, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The present invention relates to a decorative sheet having a base layer and a hard coating layer, wherein the base layer is a foam layer is formed on the base layer, PET-G and PBT is mixed, and comprises a pigment, the base layer has a thickness of 200 to It is characterized by a 400㎛.

Figure 1 shows a cross-sectional view of the decorative sheet is formed foam layer according to an embodiment of the present invention.

The decor sheet is composed of a hard coating layer 130 and a base layer 110, the base layer may be a foam layer 120 is formed in a portion. The foam layer 120 may be formed by a foaming agent, and the foaming agent may use a thermal decomposition type foaming agent. Examples of the thermally decomposable blowing agent include azo, azo, and oxy benzene sulfonyl hydrazide (OBSH), paratoluene sulfide, such as azozicarbonamido (ADCA) and azobis formamide. A hydrazide system, such as palladium toluene sulfonyl hydrazide, etc. can be used.

The content of the thermally decomposable foaming agent can be appropriately set in accordance with the type of the foaming agent, the expansion ratio (the ratio of the thickness of the foam layer to the thickness of the base layer containing the foaming agent), and the like. The foaming magnification is preferably 1.5 times or more, and preferably 3 to 8 times. The content of the thermally decomposable blowing agent may include 1 to 20 parts by weight of the blowing agent based on 100 parts by weight of the base layer.

Further, in order to further improve the foaming effect, a foaming assistant agent for accelerating the decomposition of the foaming agent can be added.

When the azo organic amido is used as the foaming agent, the foaming assistant agent may vary depending on the type of the foaming agent, but when the azo resin is used as the foaming assistant agent, a carboxylic acid hydrazide such as adipic acid hydrazide, (hydrazide), zinc oxide, lead sulfate, urea, zinc stearate, and the like. About 0.3-10 weight part is preferable with respect to 100 weight part of base layers, and, as for content of a foaming aid, about 1-5 weight part is more preferable.

In addition, an inorganic filler may be used in the foam layer 120, and the inorganic filler may be selected from the group consisting of calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, molybdenum compound, and the like. Can be.

By using the said inorganic filler, a snow-spacing effect, a surface characteristic improvement effect, etc. are obtained. It is preferable to use 0-100 weight part with respect to 100 weight part of resin components, and, as for content of the said inorganic filler, it is more preferable to use 20-70 weight part.

In addition, the bubble is preferably formed in the range of 10 to 50% of the total volume of the base layer 110.

In addition, the base layer 110 according to an embodiment of the present invention is composed of glycol-modified polyethylene terephthalate (PET-G) and polybutylene terephthalate (PBT).

Glycol modified polyethylene terephthalate (PET-G) resin included in the glycol-modified polyethylene terephthalate (PET-G) is a terephthalic acid (TPA) and ethylene glycol (Ethylene glycol: EG), cyclo It is an amorphous resin copolymerized with hexane dimethanol (CDM), which has excellent processability, moldability and printability, no deformation due to shrinkage, impact resistance, and no chlorine gas generated during incineration or fire. There is no harmful component such as hormones, and is suitable as the base layer resin included in the decor sheet according to the present invention.

The polybutylene terephthalate (PBT) has a property of improving solvent resistance when forming the base layer 110 as a crystalline polymer. That is, the hard coating layer 130 does not penetrate into the base layer 110 during coating with the hard coating layer 130. In addition, the solvent resistance is good and thereby the substrate is not damaged and the elongation is high. In addition, the PBT may be mixed with the base layer 110 to improve the turbidity of the decor sheet.

In addition, the PBT used in the present invention preferably has an intrinsic viscosity (IV) of 0.8 to 0.9 dl / g. It is well mixed with PET-G within the above range and improves the solvent resistance, thereby not damaging the substrate and high elongation.

As the base layer 110 is mixed with the PET-G and PBT, the decoration sheet of the present invention is secured flexibility is possible three-dimensional membrane molding.

In addition, the base layer 110 is preferably mixed polyethylene terephthalate (PET-G) and polybutylene terephthalate (PBT) in a molar ratio of 5: 5 to 7: 3. When mixed in the above range Tg for the mixture of PET-G and PBT is lowered, there is an advantage that can be processed at a low temperature during the post-process.

The base layer 110 may further include PCTG (poly (cyclohexylene dimethylene terephthalate), glycol). In order to mix the PET-G and PBT well, the PCTG may be mixed at the time of mixing to form the base layer 110. The mixing ratio of PCTG to the base layer 110 is preferably PET-G, PBT and PCTG in a 5: 4: 1 to 6: 3: 1 molar ratio. In the above range, the materials are mixed well, and the Tg is lowered, so that the processing is possible even at a low temperature during the post process.

In addition, the base layer 110 may include a pigment, the amount of the pigment depends on the color to be implemented, but may be used in the range of 0.2 ~ 1.0 mass% based on the base layer, if less than 0.2 mass% of the desired color If the base film is not obtained and used in excess of 1% by mass, the base film properties may be affected and the film workability may be impaired.

In addition, the pigment may be used any one of TiO ₂ , Pigment Yellow and Pigment Blue.

In addition, the thickness of the base layer 110 is preferably about 200 to 400㎛. If the base layer 110 is less than 200 ㎛ problem occurs that the base layer 110 is easily damaged when forming the membrane, if the base layer 110 exceeds 400 ㎛ there is a problem that the processing temperature rise and workability is lowered when forming the membrane.

On the other hand, the hard coating layer 130 may perform a hard drying of the thermal drying method. The heat-drying type hard coating has an advantage of being excellent in molding workability because it is more elastic than the UV curing type after curing. The hard coating layer 130 is preferably a polyurethane-based.

The polyurethane-based hard coating resin is a resin prepared by reacting a polyol and an isocyanate, and a polyol component such as polyether polyol, polyester polyol, polycaprolactone polyol, polybaconate polyol, polybutadiene polyol and toluene diisocyanate ( Aromatic isocyanates such as TDI; Toluene diisocyanate), diphenylmethane diisocyanate (MDI) or aliphatic isocyanates such as isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HMDI). An appropriate raw material having elasticity capable of three-dimensional molding and scratch resistance that can withstand external stimuli can be selected and used.

The hard coating layer 130 preferably has a thickness of about 3 to 10 μm. If the thickness of the hard coating layer 130 is less than 3㎛ may cause a change in the surface gloss of the base layer 110 when the membrane is formed, there is a problem that the pollution resistance is lowered, if the thickness exceeds 10㎛ when the surface treatment operation is reduced in speed and the membrane molding Cracks may occur in the hard coat layer 130.

In addition, the upper surface of the hard coating layer 130 may further include a protective film layer to protect the decor sheet. The material of the protective film layer is not particularly limited, and may be made of transparent PP, PC and PE. The protective film preferably has a thickness of about 5 to 10 μm.

The decor sheet of the present invention is suitable for thermoforming. Thermoforming is a method of heating / softening a sheet of a thermoplastic resin and forming a shape by vacuum or press. The term thermoforming is used in its broadest sense, including various sheet processing techniques, such as vacuum forming, pressure forming, matched mold forming, and combinations thereof. The thermoforming process is in the order of feeding, clamping, heating, shaping, cooling and trimming. When the sheet obtained mainly by extrusion or the like is fed to a molding machine, it is completely clamped to the mold, and heated to a molding temperature, followed by shaping by heating or vacuum. When the molding is completed, the molded product is obtained through appropriate cooling and trimming processes.

The thermoforming is performed at a pressure of about 1 to 10 atm lower than other competitive methods such as injection molding, blow molding and injection blow molding. Since it is possible to use a mold of a cheap material having a somewhat low strength, it can be molded at a minimum cost even in a large volume. In addition, parts with extremely thin sidewalls or sufficiently low thickness-to-area ratios have extremely short molding time and can efficiently mass-produce a large amount of parts, resulting in high molding satisfaction that is unlikely to be expected by other molding methods. There is an advantage that it can.

In addition, the decor sheet of the present invention is suitable for membrane molding. Membrane forming is a combination of press forming and vacuum forming. Press heating and vacuum forming occur simultaneously after heating.

Deco sheet according to the present invention has the advantage of high flexibility, the edges and curved portions are formed smoothly and the elongation is excellent, the surface is excellent in scratch resistance, and also excellent in stain resistance.

Hereinafter, embodiments of the present invention will be described in detail.

Example  One

As a base layer, PET-G and PBT were mixed at a molar ratio of 5: 5, and the base layer was formed to have a thickness of 300 μm. A foam layer was formed on the base layer, and 10 parts by weight of azoji carbon amido (ADCA) was added to 100 parts by weight of the base layer, and zinc oxide (5 parts by weight based on 100 parts by weight of the base layer) was added as the foaming agent. And calcium carbonate (20 parts by weight based on 100 parts by weight of the base layer) as an inorganic filler to form a foamed layer. In addition, TiO ₂ was added as a pigment. The hard coating layer was made of a thermal drying method and was formed to a thickness of 10㎛ using a polyurethane-based to prepare a decorative sheet.

Example  2

In the same manner as in Example 1, PET-G and PBT were mixed in a molar ratio of 7: 3, and the thickness of the base layer was formed to 400㎛ to prepare a decor sheet.

Example  3

In the same manner as in Example 1, the base layer was further mixed with PCTG, and the mixing ratio of PET-G, PBT and PCTG was 5: 4: 1 to prepare a decor sheet.

Comparative example  One

The same procedure as in Example 1, but was formed by PET-G alone as a base layer to prepare a decor sheet.

Comparative example  2

The same procedure as in Example 1, except that the PET-G alone was formed as a base layer, the hard coating layer was prepared by UV curing method.

※ Test method

(1) elongation evaluation

The top layer films for decor sheets were cut into samples of 25 mm width x 100 mm length, respectively. The film was oriented along a direction using a 1 kg weight (9.8 N / 2.5 mm) and allowed to stand for 10 minutes, and then the elongation was measured.

(2) Scratchability test (pencil hardness test (high load evaluation))

The test was done by the pencil hardness tester. The test was conducted according to JIS K 5600-5-4 except that the tester was set so that the front part of the pencil gave a load of 750 g to the decor sheet when the tester was in the horizontal position.

(3) pollution resistance evaluation

The acid or alkali type (vinegar, coffee, soy sauce, etc.) was dropped on the deco sheet and wiped off after 24 hours.

1: No trace level

2: The level of traces can be seen in detail (can be identified at 0.30m)

3: level with traces (identifiable at 0.75m distance)

4: level of visible traces (identifiable at 1.5m)

division Elongation (%) Scratchability (pencil hardness) Pollution resistance evaluation Example 1 230 1H One Example 2 220 2H One Example 3 230 1H One Comparative Example 1 145 1B 4 Comparative Example 2 130 1B 4

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

Claims (9)

In the decor sheet having a base layer and a hard coating layer,
The base layer is formed with a foam layer, PET-G and PBT is mixed is composed, deco sheet formed foam layer, characterized in that it contains a pigment.
The method of claim 1,
The foam layer is formed of a pyrolytic foaming agent, wherein the foaming agent is azozycal carbon amido (ADCA), azobis formamide, oxy benzene sulfonyl hydrazide (OBSH), para toluene Deco sheet with a foam layer, characterized in that at least one selected from the group consisting of sulfonyl hydrazide (palladium toluene sulfonyl hydrazide).
The method of claim 2,
Deco sheet with a foam layer, characterized in that the content of the thermal decomposition foaming agent is contained 1 to 20 parts by weight based on 100 parts by weight of the base layer.
The method of claim 1,
The foaming layer may further include a foaming aid, the content of the foaming aid is a decor sheet formed foam layer, characterized in that containing 1 to 5 parts by weight based on 100 parts by weight of the base layer.
The method of claim 1,
Inorganic filler may be further included in the foam layer, wherein the inorganic filler is at least one of a group consisting of calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and molybdenum as an inorganic filler. Decor sheet formed with a foam layer, characterized in that selected.
The method of claim 1,
The PET-G and PBT mixing ratio is 5: 5 to 7: 3 mole ratio of the foam layer is formed decor sheet.
The method of claim 1,
The base layer is PCTG is further mixed, PET-G, PBT and PCTG is a decoration sheet formed foam layer, characterized in that the mixing ratio is 5: 4: 1 to 6: 3: 1 molar ratio.
The method of claim 1,
The pigment is a decoration sheet formed foam layer, characterized in that using any one of TiO ₂ , Pigment Yellow and Pigment Blue.
The method of claim 1,
The hard coating layer is a decorative sheet formed foam layer, characterized in that the polyurethane-based.

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