WO2009082040A1

WO2009082040A1 - Transfer sheet comprising a fluororesin layer containing reflective particles,and exterior laminate sheet comprising a fluororesin layer containing reflective particles, and method for manufacturing the same

Info

Publication number: WO2009082040A1
Application number: PCT/KR2007/006666
Authority: WO
Inventors: Min Ho Lee; Young Sun An
Original assignee: Lg Chem, Ltd.
Priority date: 2007-12-20
Filing date: 2007-12-20
Publication date: 2009-07-02
Also published as: CN101557942A; CN101557942B

Abstract

The present invention relates to a transfer sheet characterized in that a fluororesin layer, wherein reflective particles such as pearl particles or glass particles for giving metal texture are dispersed, is formed on a carrier film and an adhesive layer is formed on said fluororesin layer, and an exterior laminate film characterized in that by transferring said transfer film on a synthetic resin film, the fluororesin layer containing reflective particles forms a surface layer, and an adhesive layer and a synthetic resin film are in turn laminated under said fluororesin layer. The exterior laminate sheet according to the present invention can easily give physical properties, such as excellent weather resistance, corrosion resistance and stain resistance, resulting from the fluororesin to windows/doors and panels, and it is so flexible that it has an effect of easily constructing curved surfaces. In addition, the exterior laminate sheet according to the present invention is allowed to use pearl particles or glass particles having large particle size by adopting formation of a fluororesin layer containing reflective particles as a coating method, whereby it has an effect that a decoration effect may be maximized.

Description

TRANSFER SHEET COMPRISING A FLUORORESIN LAYER

CONTAINING REFLECTIVE PARTICLES,AND EXTERIOR

LAMINATE SHEET COMPRISING A FLUORORESIN LAYER

CONTAINING REFLECTIVE PARTICLES, AND METHOD FOR

MANUFACTURING THE SAME Technical Field

[1] The present invention relates to a transfer sheet comprising a fluororesin layer containing reflective particles, an exterior laminate sheet comprising a fluororesin layer containing reflective particles and a process for preparing the same. More specifically, said transfer sheet according to the present invention is characterized in that a fluororesin layer, wherein reflective particles such as pearl particles or glass particles are dispersed for giving a metal texture, is formed on a carrier film and an adhesive layer is formed on said fluororesin layer, and said exterior laminate film according to the present invention is characterized in that by transferring said transfer film on a synthetic resin film, the fluororesin layer containing reflective particles forms a surface layer, and an adhesive layer and a synthetic resin film are laminated in turn under said fluororesin layer. Said exterior laminate sheet has not only excellent properties such as weather resistance, corrosion resistance and stain resistance, since its surface layer is composed of a fluororesin, but also it has excellent decoration effect, since reflective particles are dispersed therein.

[2]

Background Art

[3] Generally, exterior films have been used in aluminum windows, PVC windows, structural exterior panels and the like. Conventional exterior films were prepared by coating the coating solution that inorganic pigments or weather resistant pearl particles were dispersed in acrylic binder resin, in a manner of gravure, to form a print layer and a pearl coating layer, and laminating a PVDF (polyvinylidene fluoride) film thereon. Then, they were used as exterior films. However, the decoration effect of pearl was lowered due to lamination of the PVDF film. To maximize the decoration effect of pearl, pearl having large particle size should be used, but this method was also limited.

[4] Meanwhile, to form a fluororesin layer, the fluororesin had to be dissolved or melted. But, on account of characteristics of the fluororesin itself, there was a problem that dissolution or melt, as such, was very difficult. To form a fluororesin layer by using a fluororesin that polymerization was completed, there was a problem in processes of production and productivity that following coating a fluoro paint containing a fluororesin, a baking (meant sticking with partially burning by heating) process and a curing process had to be subjected.

[5]

Disclosure of Invention Technical Problem

[6] Therefore, the inventors identified advantages such that when a transfer film coated with a fluororesin on a carrier film is prepared and it is transferred to a synthetic resin film, pearl with large particle size is easily used, whereby the decoration effect may be maximized, and by forming the surface layer as the fluororesin layer, a process for further laminating a fluororesin layer, for example, a PVDF film, a baking process and a curing process and the like may be omitted, and accomplished the present invention.

[7]

Technical Solution

[8] One object of the present invention is to provide a transfer sheet comprising a fluororesin layer containing reflective particles.

[9] Another object of the present invention is to provide an exterior laminate sheet comprising a fluororesin layer containing reflective particles by transferring said transfer sheet on a synthetic resin film.

[10] The other object of the present invention is to provide a process for preparing a transfer sheet and an exterior laminate sheet, comprising a fluororesin layer containing reflective particles.

[H]

Advantageous Effects

[12] The exterior laminate sheet according to the present invention can be applied to aluminum windows, PVC windows, structural exterior panels and the like, can give to said windows/doors and panels and the like physical properties, such as excellent weather resistance, corrosion resistance and stain resistance, resulting from the fluororesin, by simply coating (wrapping) it on surfaces of these windows/doors and panels and the like, and it is so flexible that it has an effect of easily constructing curved surfaces.

[13] In addition, the exterior laminate sheet according to the present invention is allowed to use flake-shaped pearl particles or glass particles having large particle size by adopting formation of a fluororesin layer containing reflective particles as a coating method, whereby it has an effect that a decoration effect may be maximized.

[14] The transfer film and the exterior laminate sheet according to the present invention have an effect that a baking process and a curing process of conventional exterior laminate sheets, and a separate process for fiirther laminating a fluororesin film (PVDF film) and the like may be omitted

[15]

Brief Description of the Drawings

[16] Fig. 1 is a cross-section view of a transfer sheet according to one example of the present invention. [17] Fig. 2 is a cross-section view of an exterior laminate sheet according to one example of the present invention. [18]

Best Mode for Carrying Out the Invention [19] The transfer sheet comprising a fluororesin layer containing reflective particles, according to the present invention, is characterized by comprising, in turn, an adhesive layer, a fluororesin layer containing reflective particles and a carrier film from above. [D] Preferably, said fluororesin layer containing reflective particles comprises 30 to 50 parts by weight of a fluororesin and Q 1 to 5 parts by weight of reflective particles. [21] Said fluororesin layer may further contain Q 1 to 1 part by weight of an anti-settling agent.

[22] Preferably, said fluororesin layer is in a range of 5 to 50 μm.

[23] Said fluororesin layer may be formed by coating on a carrier film a fluororesin coating solution in which Q 1 to 5 parts by weight of reflective particles are homogeneously dispersed in a fluororesin solution that 30 to 50 parts by weight of a fluororesin is dissolved in 70 to 50 parts by weight of a solvent. [24] As a solvent for preparing said fluororesin solution, butyl acetate, toluene, acetone, xylene and benzene and the like may be used. [25] Said fluororesin is preferably fluoro polyisocyanate.

[26] Said reflective particles are in a flake ©shape, in which pearl particles, glass particles or a mixture thereof may be used. [27] The exterior laminate sheet according to the present invention is characterized in that a fluororesin layer containing reflective particles as a surface layer, an adhesive layer and a synthetic resin film are in turn laminated.

[28] In the exterior laminate sheet according to the present invention, a typical pressure sensitive adhesive layer and a releasing layer may be further formed on the back of said synthetic resin film.

[29] Said exterior laminate sheet according to the present invention may be prepared by transferring on a synthetic resin film said fluororesin layer containing reflective particles in said transfer sheet according to the present invention. Transfer herein includes usual transferring or laminating methods such as bond (or adhesive) transfer with only simple pressurization, bond transfer with heating and pressurization, or transfer with pressurization by a solvent. Especially, a method by heat transfer with heating and pressurization is most preferable. More specifically, it may be prepared via steps of dissolving a fluororesin (based on solid content) in a solvent to prepare a fluororesin solution; homogeneously dispersing reflective particles or reflective particles and an anti-settling agent in said fluororesin solution to prepare a fluororesin coating solution; coating said fluororesin coating solution on a carrier film to form and dry a fluororesin layer; coating an adhesive on said fluororesin layer to prepare a transfer sheet; and heat transferring said transfer sheet to the separately prepared synthetic resin film to laminate them. In the exterior laminate sheet according to the present invention, an exfoliate paper may be attached to the back of said synthetic resin film.

[30] Hereinafter, the present invention is explained in detail with reference to the attached drawings.

[31] In a preferred aspect, the transfer sheet comprising a fluororesin layer containing reflective particles, according to the present invention, consists of, in turn, an adhesive layer 3, a fluororesin layer 2 containing reflective particles 21 and a carrier film 3 from above, as shown in Fig. 1.

[32] The fluororesin forming said fluororesin layer 2, as a thermoplastic resin, must be easily coated on materials needed to be subjected to a coating process, has excellent solubility to a solvent, and has excellent heat resistance, film strength and water re- pellency after forming a film as well. A polymer, in which fluorine atoms are introduced in polymeric chains, such as trifluoroethylene polymer, vinylidene fluoride polymer, and perfluoroethylene polymer, has excellent heat resistance and chemical stability, but it has a disadvantage that solubility to an organic solvent is lowered. A polymer comprising a polymeric monomer with a perfluoroalkyl group in a branched chain, such as perfluoroalkyl acrylate or perfluoroalkyl methacrylate, or a polymer comprising perfluoroalkylstyrene has improved solubility to an organic solvent, but it has a disadvantage that long-term stability is lowered, because any deterioration reaction is occurred through ultraviolet absorption of aromatic groups. Therefore, an usable fluororesin herein is preferably a fluororesin which may form a film having good solubility to an organic solvent and excellent heat resistance and water re- pellency. Such a fluororesin is suitably a fluororesin such as fluoro polyisocyanate obtained by reacting an isocyante group (NCO group) in polyisocyanate with a fluoroalcohol. Such a fluororesin may include, for example, a fluororesin such as fluoro polyisocyante disclosed in KR Laid-Open Patent Publication No. D05-0068347.

[33] As said reflective particles 21, any one from pearl particles, glass particles or a mixture thereof may be used. Particles having good weather resistance as a flake- shaped are preferable. The pearl particles above are a kind cf organic pigments having pearl feeling, that is, pearled gloss. One skilled in this field can understand that pearl particles are known such that he may purchase and use those commercially provided by the foremost manufacturers at home and abroad. That is, pearl particles are known at home and abroad as a kind of pigments giving gloss such as pearl granule feeling. Pearl particles are intended to provide a visual difference, and the pearl effect varies due to difference of reflection depending on thickness of pearl particles. Said glass particles are alternatively called to glass flakes, and also increase the reflection effect due to high refractive index and give the effect of providing gloss.

[34] It is preferred that said reflective particles 21 are included in a ratio of Q 1 to 5 parts by weight relative to 30 to 50 parts by weight of a fluororesin (based on solid content).

[35] Said fluororesin layer may be formed by coating a fluororesin coating solution, in which Ql to 5 parts by weight of reflective particles are homogeneously dispersed in the fluororesin solution that 30 to 50 parts by weight of a fluororesin are dissolved in 70 to 50 parts by weight of a solvent, on a carrier film. If said reflective particles are used in an amount of less than Q 1 parts by weight, there can be a problem that the effect of increasing pearl feeling, that is, metal gloss or other reflection ratio is not sufficient. On the contrary, if the amount is in excess of 5 parts by weight, there can be a problem that the physical property of fluororesin layer is lowered and thus durability and the like is lowered.

[36] In addition, it is preferred that said reflective particles have a particle size distribution in a range of 2 μm to 60 μm. If the particle size of reflective particles is less than 2 μm, the decoration effect may be lowered. If it is in excess of 60 μm, the decoration effect may be increased, but there can be concerns about problems such as blocking development and need of a long time for drying, because the fluororesin layer with thick thickness has to be formed.

[37] As said carrier film, an usual synthetic resin film such as polyethyleneterephthalate film may be used, and considering economic efficiency, mechanical strength and adhesion and the like, polyethyleneterephthalate film is most suitable.

[38] The thickness of said carrier film is suitably in a range of 10 to 250 μm, but more preferably 12 to 75 μm. If the thickness is less than 10 μm, the mechanical strength is not sufficient and there can be a problem that after coating the fluororesin coating solution thereon, the thermal deformation may be occurred on drying. On the one hand, if it is in excess of 250 μm, flexibility of film is lowered, so that there is a problem that a coiling process of film is difficult and economic efficiency may be lowered.

[39] Said adhesive layer may include preferably an adhesive layer formed by coating an acrylic resin solution. It is preferred in said adhesive layer that an acrylic resin is coated in a manner of gravure coating and its thickness is 1 to 10 μm, and more preferably 2 to 5 μm. If the thickness of adhesive layer is less than 1 μm, there can be a problem that on further bonding it to a synthetic resin film, bonding strength is lowered. If it is in excess of 10 μm, there can be a problem that roll coiling and processing are difficult due to occurrence of blocking.

[40] Said fluororesin coating solution may further comprise an anti-settling agent in an amount of Q 1 to 1 part by weight. Said anti-settling agent serves to prevent reflective particles contained in the fluororesin coating solution from settling and is known to those skilled in this field, such that they can purchase and use commercially available anti-settling agents. For example, a commercially available anti-settling agent such as the trade name 'BYK 410' (manufactured by ALTANA Chemie, Germany) may be used.

[41] It is preferred that the thickness of said fluororesin layer after dryness is in a range of

5 to 50 μm. If said fluororesin layer is formed in a thickness of less than 5 μm, stability in coating work of the resin layer containing reflective particles with large particle size is lowered. On the contrary, if it is formed in a thickness exceeding 50 μm, there can be a problem that blocking is occurred, since sufficient dryness is not performed.

[42] As a preferred aspect, the exterior laminate sheet comprising a fluororesin layer containing reflective particles, according to the present invention, has a structure that a fluororesin layer containing reflective particles as a surface layer, an adhesive layer and a synthetic resin film are laminated in turn, as shown in Fig. 2. The exterior laminate sheet according to the present invention is a sheet that said transfer sheet is transferred to one side of the synthetic resin film, and the fluororesin, reflective particles and adhesive layer constituting the fluororesin layer are the same as the fluororesin, reflective particles and adhesive layer constituting the transfer sheet as explained above.

[43] Said synthetic resin film 4 is an usual synthetic resin film and may be transparent or color (opaque, semi-transparent, colored or printed). When it consists of a color film, its colors or printing designs and the like may be suitably designed as optional colors or printing designs, considering colors, shapes, sizes and the like of products to which the exterior laminate sheet to be obtained according to the present invention is applied. The present invention is not limited to its colors or kinds of synthetic resins in the synthetic resin films, but in order to be preferably able to construct curved surfaces, a polyvinyl chloride resin film (PVC film) or an acrylic resin film with good flexibility and excellent weather resistance is preferable.

[44] The exterior laminate sheet comprising a fluororesin layer containing reflective particles, according to the present invention, may be prepared by preparing a fluororesin solution of 30 to 50 % by weight of a fluororesin, homogeneously dispersing Q 1 to 5 parts by weight of reflective particles or Q 1 to 5 parts by weight of reflective particles and Q 1 to 1 part by weight of an anti-settling agent in 100 parts by weight of said fluororesin solution to prepare a fluororesin coating solution, coating said fluororesin coating solution on a carrier film to form and dry a fluororesin layer, applying an adhesive on said fluororesin layer to prepare a transfer sheet, and attaching an adhesive layer of said transfer sheet to be in contact with a surface of the separately prepared synthetic resin film and transferring (or laminating) them with heating. The exterior laminate sheet according to the present invention is made to a product by attaching a release paper to back of said synthetic resin film, and when it is practically used, it may be attached to an adherend with releasing said release paper or after releasing it. When said carrier film is removed prior to or after making a product or after allowing to be attached to an adherend, the fluororesin layer containing reflective particles consists of a surface layer of the adherend, and thus the excellent decoration effect and the excellent effects such as weather resistance, corrosion resistance and stain resistance can be obtained.

[45] Mode for the Invention

[46] The present invention is specifically explained as preferred examples below.

[47]

[48] <Preparation Examples of Transfer Sheet>

[49] <Example 1>

[50] The transfer sheet according to the present invention was prepared by dissolving 300 g of fluoro polyisocyanate resin as a fluororesin in 700 g of toluene to prepare a fluororesin solution, mixing 50 g of glass particles having an average particle size of 2) μm with 1 kg of this fluororesin solution and homogeneously dispersing the mixture therein to prepare a fluororesin coating solution, and then, coating this fluororesin coating solution on one side of polyethyleneterephthalate film with a thickness of 75 μm as a carrier film 1, such that a film thickness after dryness is 1 μm, to form a fluororesin layer 2, drying it at a temperature of 100⁰C, and coating an acrylic adhesive in a thickness of 2 μm on the top of fluororesin layer to form an adhesive layer 3.

[51]

[52] <Example 2>

[53] The transfer sheet according to the present invention was prepared by the same conditions and methods as those of Example 1 except that 500 g of fluoro polyisocyanate resin as a fluororesin was dissolved in 500 g of toluene to prepare a fluororesin solution, 1 g of pearl particles having an average particle size of D μm were mixed with 1 kg cf this fluororesin solution and were homogeneously dispersed therein to prepare a fluororesin coating solution, and this fluororesin coating solution was coated on one side of polyethyleneterephthalate film with a thickness of 75 μm as a carrier film 1, such that a film thickness after dryness is 5 μm, to form a fluororesin layer 2.

[54]

[55] <Preparation Examples of Exterior Laminate Sheet>

[56] <Example 3>

[57] The exterior laminate sheet according to the present invention was prepared by thermal transferring the transfer sheet prepared in Example 1 above on a synthetic resin film of vinyl chloride resin having a thickness of 100 μm as a colored synthetic resin film 4, attaching the transfer sheet to the synthetic resin film, such that the adhesive layer 3 of said transfer sheet is in contact with said synthetic resin film 4, heating and laminating them, and removing the carrier film. [59] <Example 4>

[60] The exterior sheet according to the present invention was prepared by the same method as Example 3 except that the transfer sheet prepared in Example 2 above was thermal transferred on an acrylic resin film having a thickness of 100 μm as a transparent synthetic resin film 4.

[61]

[62] <Gomparative Example 1>

[63] The transfer sheet was prepared by dissolving 300 g of fluoro polyisocyanate as a fluororesin in 7)0 g of toluene to prepare a fluororesin solution, mixing 60 g of glass particles having an average particle size of D μm with 1 kg of this fluororesin solution and homogeneously dispersing the mixture therein to prepare a fluororesin coating solution, and then, coating this fluororesin coating solution on one side of polyethylen- eterephthalate film with a thickness of 75 /an as a carrier film 1, such that a film thickness after dryness is D μm, to form a fluororesin layer 2, drying it at a temperature of 100⁰C, and coating an acrylic adhesive in a thickness of 2 μm on the top of fluororesin layer to form an adhesive layer.

[64]

[65] <Comparative Example 2>

[66] The transfer sheet was prepared by the same conditions and methods as those of

Comparative Example 1 except that 500 g of fluoro polyisocyanate resin as a fluororesin was dissolved in 500 g of toluene to prepare a fluororesin solution, Q9 g of pearl particles having an average particle size of D μm were mixed with 1 kg of this fluororesin solution and were homogeneously dispersed therein to prepare a fluororesin coating solution.

[67]

[68] <Comparative Example 3>

[69] The transfer sheet was prepared by the same conditions and methods as those of

Comparative Example 1 except that 300 g of fluoro polyisocyanate resin as a fluororesin was dissolved in 700 g of toluene to prepare a fluororesin solution, 25 g of glass particles and 25 g of pearl particles, having an average particle size of D μm, were mixed with 1 kg of this fluororesin solution and were homogeneously dispersed therein to prepare a fluororesin coating solution, and this fluororesin coating solution was coated on one side of polyethyleneterephthalate film with a thickness of 75 μm as a carrier film 1, such that a film thickness after dryness is 4 μm.

[70] [71] <Gomparative Example 4>

[72] The transfer sheet was prepared by the same conditions and methods as those of

Comparative Example 1 except that DO g of fluoro polyisocyanate resin as a fluororesin was dissolved in 800 g of toluene to prepare a fluororesin solution, 30 g of glass particles having an average particle size of D μm were mixed with 1 kg of this fluororesin solution and were homogeneously dispersed therein to prepare a fluororesin coating solution.

[73]

[74] <Comparative Example 5>

[75] The transfer sheet was prepared by the same conditions and methods as those of

Comparative Example 4 except that 600 g cf fluoro polyisocyanate resin as a fluororesin was dissolved in 400 g of toluene to prepare a fluororesin solution.

[76]

[77] <Evaluation>

[78] Examples 1 and 2 and Examples 3 and 4, according to the present invention, were easily subjected to the coating work, and had also excellent state after coating and decoration effect (pearl effect).

[79] However, the transfer sheet of Comparative Example 1 had so large quantity of reflective particles that coating processability and color uniformity were lowered. It could be visually observed that the transfer sheet of Comparative Example 2 had so small quantity of reflective particles that the decoration effect (pearl effect) was lowered. In case of Comparative Example 3, since the space of coater had to be reduced for coating a film in a thin thickness, the coating work was difficult due to coating lines. In case of Comparative Example 4, since the solvent was excessively used, the drying time was so long that productivity was lowered and slight thermal contraction was developed. In case of Comparative Example 5, the viscosity was so high that coating stability was lowered, and slight bubbles were developed on drying.

[80]

[81]

[82]

Claims

[I] A transfer sheet characterized by comprising, in turn, an adhesive layer, a fluororesin layer containing reflective particles and a carrier film from above.

[2] The transfer sheet of claim 1, characterized in that said fluororesin layer, containing reflective particles, comprises 30 to 50 parts by weight of a fluororesin and Ql to 5 parts by weight of reflective particles.

[3] The transfer sheet of claim 2, characterized in that said fluororesin layer containing reflective particles further comprises an anti- settling agent.

[4] The transfer sheet of claim 2, characterized in that said fluororesin is fluoro poly- isocyanate.

[5] The transfer sheet of claim 2, characterized in that said reflective particles are any one from pearl particles, glass particles or a mixture thereof.

[6] The transfer sheet of any one of claims 1 to 5, characterized in that said fluororesin layer containing reflective particles is 5 to 50 micrometer (βm).

[7] A process for preparing the transfer sheet as described in any one of claims 1 to

6, characterized in that it comprises steps of dissolving a fluororesin in a solvent to prepare a fluororesin solution; homogeneously dispersing reflective particles or reflective particles and an anti-settling agent in said fluororesin solution to prepare a fluororesin coating solution; coating said fluororesin coating solution on a carrier film to form and dry a fluororesin layer; coating an adhesive on said fluororesin layer to prepare a transfer sheet.

[8] An exterior laminate sheet, characterized in that a fluororesin layer containing reflective particles as a surface layer, an adhesive layer and a synthetic resin film is in turn laminated from above.

[9] The exterior laminate sheet of claim 8, characterized in that said exterior laminate sheet is one obtained by transferring the transfer sheet as described in any one of claims 1 to 6 on the synthetic resin film.

[10] The exterior laminate sheet of claim 8, characterized in that said fluororesin layer containing reflective particles comprises 30 to 50 parts by weight cf a fluororesin and Q 1 to 5 parts by weight of reflective particles.

[I I] The exterior laminate sheet of claim 8, characterized in that said fluororesin layer containing reflective particles further comprises an anti- settling agent.

[12] The exterior laminate sheet of claim 8, characterized in that said fluororesin is fluoro polyisocyanate.

[13] The exterior laminate sheet of claim 8, characterized in that said reflective particles are any one from pearl particles, glass particles or a mixture thereof.

[14] The exterior laminate sheet of any one of claims 8 to 13, characterized in that said fluororesin layer containing reflective particles is 5 to 50 micrometer (μm).

[15] The exterior laminate sheet of claim 14, characterized in that said synthetic resin film is a transparent or colored film.

[16] A process for preparing an exterior laminate sheet, characterized in that it comprises steps of dissolving a fluororesin in a solvent to prepare a fluororesin solution; homogeneously dispersing reflective particles or reflective particles and an anti-settling agent in said fluororesin solution to prepare a fluororesin coating solution; coating said fluororesin coating solution on a carrier film to form and dry a fluororesin layer; coating an adhesive on said fluororesin layer to prepare a transfer sheet; and transferring said transfer sheet to the separately prepared synthetic resin film to laminate them.