KR100896223B1 - Multi-layer sheet having pollution-resistance property and the method for processing thereof - Google Patents

Abstract

The present invention relates to a multilayer sheet having excellent light transmittance, and more particularly to a fluorocarbon compound and a rutile (TiO ₂ ) -introduced silane compound and rutile (TiO ₂ ) in order to improve pollution resistance and self-cleaning in a polycarbonate or acrylic sheet. The present invention relates to a multilayer sheet having excellent scratch resistance, environmental resistance and light resistance, and a method of manufacturing the same.

Skylight, Outdoor Lighting Sign, Silane Compound, Rutile-TiO2, Fluorine Resin, Polycarbonate

Description

Multi-layer sheet having pollution-resistance property and the method for processing

The present invention relates to a multilayer sheet having excellent light transmittance, and more particularly, a fluorine resin having a silane compound and rutile-TiO ₂ introduced therein to improve fouling resistance and self-cleaning in a polycarbonate or acrylic sheet. The present invention relates to a multilayer sheet and a method for producing the same, which are efficient in production efficiency and economical efficiency in a continuous process by transferring a coating and an adhesive onto a polycarbonate or an acrylic sheet, and having excellent scratch resistance, environmental resistance and light resistance.

Typically, coating several tens of micrometers thick on a thick sheet surface having a thickness of 100-1000 micrometers is inadequate due to the inefficiency of the continuous coating process due to the drying speed and thickness, so that the material to be coated with an adhesive or adhesive is applied to the film. It is desirable to make and laminate or laminate fusion. Looking at the prior art regarding such surface protection and multi-layered functionality, Korean Patent Laid-Open Publication No. 2005-0108125 "Method of Forming Furniture Multitone Film" is a process of providing a multitone film by heat fusion using an adhesive on a furniture surface. Korean Patent Publication No. 2003-0084757 discloses a protective tape for an optical member, a protective tape treatment layer forming agent for an optical member, an optical film with a protective tape, and an image display device with a protective tape. Is disclosed, and a protective tape for an optical member including a printing function on the opposite side thereof. Similarly, Korean Patent Laid-Open Publication No. 2002-0072653 “A protective tape for protecting the surface of an optical material” discloses a protective tape for an optical material by applying an acrylic adhesive having high cold resistance and high transmittance. However, the above known prior arts have limitations in imparting good self-cleaning, scratch resistance, light resistance and transmittance to the multilayer sheet.

In addition, skylight or outdoor lighting billboard sheets using these multi-layer sheets must be protected from scratches and damage during transportation, loading and processing, and from scratching and other injuries, and high transmittance and, above all, pollution and self-cleaning. ) Function is required. It has low adsorption of dust, partially absorbs the adsorbed organics or weakly interacts with hydrophobic particles, so it must be washed well in rainwater. Also, it must be yellowed or light resistant even if exposed to natural light for a long time. It must be inexpensive by mass continuous process. Currently, the development of a multilayer sheet that satisfies all these conditions is urgently required.

Accordingly, the present inventors have applied the silane-based compound and rutile-TiO ₂ fluorine resin and transfer-coated an adhesive to produce a multilayer sheet by laminating a polycarbonate or an acrylic sheet. The present invention was found to be able to produce a multilayer sheet that is not only very effective but also excellent in scratch resistance, environmental resistance and light resistance.

The present invention provides a multilayer sheet including a fluororesin layer containing a fluororesin, an acrylic resin, a rutile-TiO ₂ , a silane compound, a curing agent, toluene, xylene, ethyl acetate and butyl acetate.

The multi-layered sheet according to the present invention has excellent self-cleaning function and durability, and introduced a fluororesin layer having a desired physical property and thickness according to the use by using a low-cost fluororesin powder instead of an expensive processed fluororesin film. By introducing adhesive with tape and transfer laminating method, it manufactures a multi-layered sheet (protective tape + functional fluororesin layer + adhesive + release paper (protection)) to prevent contamination and protection during storage and transportation, and to be easily applied by users. The price is also affordable.

The multilayer sheet according to the present invention may have the structure of FIGS. 1 to 4. Looking in more detail, the multilayer sheet consisting of a release paper, a pressure-sensitive adhesive, a fluororesin layer and a protective adhesive tape in order from the bottom (Fig. 1); A multilayer sheet consisting of a protective adhesive tape, a fluororesin layer and a protective adhesive tape in turn from below (FIG. 2); A multilayer sheet composed of a polycarbonate / polyacrylic sheet (PC / PA sheet), an adhesive, a fluororesin layer, and a protective adhesive tape (FIG. 3); Or a polycarbonate / polyacrylic sheet (PC / PA sheet), a fluororesin layer, and a protective adhesive tape (FIG. 4).

The release paper used in the present invention may use paper or PET (Polyethylene Terephthalate) film, but is not limited thereto.

Pressure Sensitive Adhesive used in the present invention is an acrylic adhesive, and various acrylic monomers were put in ethyl acetate, a solvent, and prepared by using an acrylic copolymer by adding an azo compound (AIBN) and a peroxide of Wako, a polymerization initiator. For example, 5 to 10% by weight of isobutyl acrylate monomer, 5 to 10% by weight of 2-ethylhexyl acrylate monomer, 5 to 10% by weight of vinyl acetate monomer, and 2-hydroxyhexylacryl based on the total weight of the pressure-sensitive adhesive composition 5-10% by weight of late monomer, 10-20% by weight of ethyl acrylate monomer, 3-8% by weight of acrylamide, 5-10% by weight of acrylic acid, 40-50% by weight of ethyl acetate as solvent, 2,2- as polymerization initiator 1-5% by weight of azobis (2,2-azobis (2,4-dimethyl valeronitrile); AIBN) and 1-5% by weight of benzoyl peroxide as peroxide High functionalized by polymerization Acrylic copolymers may be used, but are not limited thereto.

The fluorine resin layer used in the present invention is 20 to 50% by weight, 10 to 30% by weight of acrylic resin, 1 to 6% by weight of rutile-TiO ₂ , and silane compound 2 to 10% by weight based on the total weight of the fluorine resin layer. Wt%, curing agent 1-10 wt%, toluene 5-30 wt%, xylene 5-30 wt%, ethyl acetate 5-30 wt% and butyl acetate 5-30 wt%.

In addition, the fluorine resin layer used in the present invention is 10 to 30% by weight, 10 to 30% by weight of acrylic resin, 1 to 6% by weight of rutile (TiO ₂ ), silane compound 2 ~ to the total weight of the composition of the fluorine resin layer 10 wt%, 1-7 wt% of hardener, 5-30 wt% of toluene, 5-30 wt% of xylene, 5-30 wt% of ethyl acetate, 5-30 wt% of butyl acetate and methyl ethyl ketone (MEK) ) 5 to 30% by weight.

The fluorine resin used in the present invention can be used a variety of commercially available products, in the present invention is used, but not limited to K700 series (fluorine resin powder) manufactured by Kynal, Germany.

In the present invention, the silane-based compound used as a dirt pick-up inhibitor is a high cross-link material called sow T-resin or ladder polymer, and usability and coating film formation. It is excellent and has good binding property with TiO ₂ to exert synergy effect on various coating properties. For example, polymethylsilsesquioxane and polyphenyl propylsilsesquioxane Can be used in a 1: 1 weight ratio.

The curing agent used in the present invention is preferably a non-yellowing isocyanate (HMDI), but is not limited thereto.

The protective adhesive tape used in the present invention is prepared by the method described in Korean Patent Laid-Open No. 2002-0072653.

The protective adhesive tape is 5 to 10% by weight of isobutyl acrylate monomer, 5 to 10% by weight of 2-ethylhexyl acrylate monomer, 5 to 10% by weight of vinyl acetate monomer, 10 to 20% to ethyl acrylate monomer on a highly transparent PE film. Wt%, 40-50% by weight ethyl acetate, 30-40% by weight solvent, 3-8% by weight acrylamide, 5-10% by weight acrylic acid, 5-10% by weight resin and 0-5% by weight curing agent After applying the pressure-sensitive adhesive made of a high functional acrylic copolymer, it is completed by drying and aging at an appropriate temperature and humidity conditions.

In this case, the curing agent may be an epoxy-based curing agent such as polyamine (PA) polyamido resin (PAR: Polyamido Resin) and polysulfide resin (Polysulfide Resin); Phosphate curing agents such as tri-basic sodium phosphate (TSP) and tri-sodium orthophosphate (Tri-sodium Orthophosphate); And dimethyl amino-ethyl methacrylate, 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,4,6-triisopropylphenyl diisocyanate, 4,4-diphenylmethane diisocyanate, tall Isocyanate-type hardeners, such as a ridine diisocyanate and a naphthalene diisocyanate; It can select and use 1 or more types from the group which consists of.

The process of manufacturing the multilayer sheet according to the present invention will be described in more detail through the detailed process diagram of FIG. 5 and the overall void diagram of FIG. 6.

<First step: Apply double sided wax>

First, the prepared 25 μm PET film 1 is hanged on an unwinding mounting table 2, and the prepared wax solution 3 is placed in a supporting container 43. At this time, a part of the coating drum 41 is partially submerged in the wax solution 3 in the supporting container 43, and the auxiliary drum 42 is in close contact with the coating drum 41. When the film 1 passes through the guide rod 44 and the guide rollers 5 through the guide to the next step, the surface of the film 1 is a wax solution is applied to a thickness of several μm. The coating thickness here depends on the microgrooves (tensions of meshes-hundreds of meshes) formed in the coating drum 41 and at the same time determined by the speed at which the film passes and the viscosity of the wax solution. The wax-coated film is artificially dried by passing through a drying device 6 consisting of a chamber 61 (FIG. 5). On the other side of the wax-coated film passed through the drying furnace, that is, the wax solution is applied to the back surface with a thickness of several micrometers in the same manner as the method of coating the back surface (FIG. 6). The wax used in the present invention may be used alone or in combination with Luwax A (CAS 9002-88-4), Luwax EAS (CAS 9010-77-9) and Luwax OA (CAS 68441-17-8) from BASF.

<Second Step: Adhesive Coating>

The double-sided wax-coated film passed through the back drying device is a sheet of 10 μm thick coated and dried acrylic adhesive on one side of the wax-coated film, similar to the first process, through a guide rod and guide rolls in a so-called gravure coating. Is wound on the winder mounting table 7 to complete the adhesive transfer sheet. The finished sheet roll is mounted on a laminated winder base for transferring lamination (FIG. 6).

<3rd process: release agent coating>

Prepared similarly to the first process, a wax solution prepared using paper or PET film, which requires some heat resistance instead of PE film, is applied to a thickness of several micrometers. The wax applied here is applied to the use of a release agent for transferring the fluororesin layer applied in the next step.

<Fourth Step: Fluoropolymer Coating>

The waxed paper (or PET film) that has passed through the drying device 6 is required to apply the fluororesin in a manner similar to the first process, on a waxed surface, in what is called a gravure coating via guide rods and guide rolls. Depending on the coating thickness in the range of 10-100㎛ is possible, in this embodiment, the fluororesin coating thickness was prepared to 25㎛ in the dry state.

The fluororesin coated paper is passed through seven high temperature (up to 150 ° C.) chambers (chambers 3-chambers 9) to form a completely dry / cured and transparent fluororesin layer.

<Process 5: double sided laminating>

In the fourth process, after passing through the drying furnace, double-sided lamination, that is, two laminating processes, are continuously performed in line. First, the first lamination is performed by laminating the pressure-sensitive adhesive coated sheet prepared in the second process. The first lamination removes the release paper or film introduced in the fourth step in the first lamination state, and the protective adhesive tape is laminated on the fluororesin coating film to complete the multilayer sheet of FIG. 1 in the winder.

The multilayer sheet of FIG. 1 has a structure composed of a release paper, an adhesive, a fluororesin layer, and a protective adhesive tape in order from the bottom, and removes the release paper from the multilayer sheet of FIG. 1, and the adhesive and the polycarbonate / polyacryl sheet ( PC / PA sheet) can be laminated in order to produce a multilayer sheet having a structure as shown in FIG. 3.

In addition, the multilayer sheet of FIG. 2 is completed by laminating two protective adhesive tapes on both sides instead of the adhesive transfer laminating in the fifth process, and the multilayer sheet of FIG. 4 is peeled off the protective adhesive tape attached to one side of the multilayer sheet of FIG. It can be produced by laminating a polycarbonate polyacrylic sheet (PC / PA sheet) in a semi-dry state on the back surface of the fluororesin layer.

The multilayer sheet according to the present invention can be used as a skylight plate, an advertising board or an illumination sheet.

Hereinafter, an Example is given and this invention is demonstrated in detail. The following examples are intended to illustrate the present invention in detail, and the scope of the present invention is not limited by the following examples.

[Examples 1-3]

A multilayer sheet having the structure shown in FIG. 1 was prepared through a five step process (FIGS. 5 and 6) consisting of double-sided wax coating, pressure-sensitive adhesive coating, release agent coating, fluororesin coating, and double-side laminating described above.

At this time, the adhesive is 7% by weight of isobutyl acrylate monomer, 7% by weight of 2-ethylhexyl acrylate monomer, 7% by weight of vinyl acetate monomer, 7% by weight of 2-hydroxyhexyl acrylate monomer, ethylacryl 15% by weight of late monomer, 5% by weight of acrylamide, 7% by weight of acrylic acid, 40% by weight of ethyl acetate, 2,2-azobis (2,4-dimethyl valeronitrile (2,2-azobis (2,4-dimethyl) valeronitrile); 2.5 wt% AIBN) and 2.5 wt% benzoyl peroxide were used.

In addition, the fluororesin layer was prepared by using the fluororesin layer composition to be prepared in Examples 1 to 3 according to the composition shown in Table 1 below. In Example 1, a molecular weight of 70,000 was used in the K700 series manufactured by Kynal, Germany. In Example 2, a molecular weight of 50,000 was used in the K700 series manufactured by Kynal, Germany. It was used by mixing in 1 weight ratio.

The fluororesin powder was dissolved in toluene and butyl acetate, rutile-TiO ₂ (photodegradable) was added and dispersed, and then the silane compound, ethyl acetate, and xylene were added to make the final solution viscosities at 700 cps and 50% solids. It was. The hardener used was a yellowed isocyanate (HMDI) in accordance with the fluororesin OH value, and the solvent used was ethyl acetate, toluene and methyl ethyl ketone without OH groups and residual moisture. At this time, 5-10% by weight of the curing agent was used in comparison with the main material, and the silane-based compound was polymethylsilsesquioxane (CAS 68554-70-1) and polyphenylpropylsilsesquioxane (Dow Chemical). Polyphenyl propylsilsesquioxane; 4 OH group average 30% propyl (CAS 68037-90-1)) was used by mixing 50:50 by weight.

Composition and Properties of Fluoropolymer Solution Example 1 Example 2 Example 3 Fluorine content (% by weight) 24 24 12 OH value 4.8 4.8 2.4 Tg (℃) 40 35 6 Solid content (% by weight) 50 50 50 Viscosity (cps) 700 600 500 Rutile-TiO ₂ (% by weight) 5 5 5 Silane compound 3 3 3 solvent EA, BA, Toluene, Xylene EA, BA, Toluene, Xylene EA, BA, Toluene, MEK Light resistance test (KS R 0021) No discoloration (yellowing) No discoloration (yellowing) No discoloration (yellowing) Pollution Resistance Test (KS M 3803) clear clear clear Coating strength 3H 3H 2H

A protective adhesive tape disclosed in Korean Laid-Open Patent Publication No. 2002-0072653 was used.

Light resistance, fouling resistance and coating film strength of the multilayer sheets prepared in Examples 1 to 3 were measured, respectively, and the results are shown in Table 1 together.

As described above, it was confirmed that the multilayer sheets of Examples 1 to 3 according to the present invention had excellent light resistance, stain resistance, and coating strength.

1 to 4 are exemplary cross-sectional views of the skylight plate sheet according to the present invention.

Figure 5 is a detailed process diagram showing a manufacturing process of the light plate sheet according to the present invention.

6 is a general process diagram showing the manufacturing process of the light-emitting plate sheet according to the present invention.

<Explanation of Signs of Major Parts of Drawings>

1: PET film 2: Unwinding stand

3: wax solution 5: guide roller

6: drying apparatus 7: winding mounting table

8: aging room 41: coating drum

42: auxiliary drum 43: container

44: guide rod 61: chamber

Claims (6)

A multilayer sheet composed of a release paper, an adhesive, a fluororesin layer, and a protective adhesive tape in order from the bottom, The fluorine resin layer is 20 to 50% by weight, 10 to 30% by weight of acrylic resin, 1 to 6% by weight of rutile (TiO ₂ ), 2 to 10% by weight of silane compound, based on the total weight of the fluorine resin layer. A multilayer sheet comprising 1 to 10% by weight of a curing agent, 5 to 30% by weight of toluene, 5 to 30% by weight of xylene, 5 to 30% by weight of ethyl acetate, and 5 to 30% by weight of butyl acetate. A multilayer sheet composed of a release paper, an adhesive, a fluororesin layer, and a protective adhesive tape in order from the bottom, The fluorine resin layer is 10 to 30% by weight, 10 to 30% by weight of acrylic resin, 1 to 6% by weight of rutile (TiO ₂ ), 2 to 10% by weight of silane compound, and a curing agent, based on the total weight of the fluorine resin layer. 1 to 7% by weight, 5 to 30% by weight of toluene, 5 to 30% by weight of xylene, 5 to 30% by weight of ethyl acetate, 5 to 30% by weight of butyl acetate and 5 to 30% by weight of methyl ethyl ketone The multilayer sheet characterized by containing. The multilayer sheet according to claim 1 or 2, wherein the silane compound is a 1: 1 weight ratio of polymethylsilsesquioxane and polyphenyl propylsilsesquioxane. . The multilayer sheet according to claim 1 or 2, wherein the curing agent is a yellowed isocyanate (HMDI). According to claim 1 or 2, wherein the pressure-sensitive adhesive is 5 to 10% by weight of isobutyl acrylate monomer, 5 to 10% by weight 2-ethylhexyl acrylate monomer, 5 to 10 weight of vinyl acetate monomer based on the total weight of the pressure-sensitive adhesive composition %, 2-hydroxyhexyl acrylate monomer 5-10 wt%, ethyl acrylate monomer 10-20 wt%, acrylamide 3-8 wt%, acrylic acid 5-10 wt%, ethyl acetate 40-50 wt%, 2 1 to 5% by weight of 2,2-azobis (2,4-dimethyl valeronitrile; AIBN) and 1 to 5% by weight of benzoyl peroxide. Multi-layer sheet, characterized in that consisting of a mixed high functional acrylic copolymer. The multi-layered sheet of claim 1 or 2, wherein the multi-layered sheet is a skylight, an advertisement board, or an illumination sheet.

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