KR101453756B1 - the paste composition for thin film and method of manufacturing cover glass protecting film using therefrom - Google Patents

Abstract

The thin film paste composition according to the present invention and the cover glass protective film using the same can minimize the damage to the cover glass surface that may occur in the cutting and processing process of the cover glass used in electronic equipment and the like, It is suitable for use in eco-friendly products of the type. In addition, it is possible to minimize the difference in the refractive index difference and the contact angle of the glass by removing floating matters that may remain on the surface, such as foreign matter and unevenness on the surface of the glass. The inner planet is excellent here, and it is possible to easily remove the protective film from the processed cover glass, which can reduce the raw materials and reduce labor costs.

Description

TECHNICAL FIELD [0001] The present invention relates to a paste composition for a thin film and a method for manufacturing a cover glass protective film using the same,

TECHNICAL FIELD The present invention relates to a thin film paste composition for protecting a glass surface during a cutting process of a cover glass or an ITO coated glass substrate applicable to a smartphone for touch or a notebook computer, and a method for producing a cover glass protective film using the paste composition.

In portable mobile devices, cover glasses or ITO patterned glasses used in various mobile devices and electronic devices are widely used due to popularization of touch screens including advanced 3D screens. Accordingly, cutting and machining processes of coverglass by device are also important factors in the electronic device market. In order to prevent defects that may occur in such cutting and machining processes, it is common to attach a protective film using a screen printing technique to a cover glass and then perform a cutting process.

In order to protect the glass from contamination sources such as glass chips and foreign materials generated during cutting and side machining operations by size, it is necessary to take into account material leakage to cope with frequent model changes and precision of gap between patterns applied to commercialized protective film And additional costs such as personnel expenses are incurred. Also, when side grinding, the abrasive liquid including the abrasive particles is injected at a certain hydraulic pressure, so that a certain level of film strength and adhesion is required in the progressing process. In case of insufficient adhesion, product contamination and defective product due to removal of the protective layer are produced. If the adhesive strength is higher than a certain level, it takes time to remove paste after coating, do.

In order to solve this problem, Korean Patent Laid-Open No. 10-2008-0026376 discloses a method for producing a glass protective coating material which can be cured by heat treatment at a low temperature. More particularly, the present invention relates to a method for manufacturing a low-temperature curing type glass protective coating material which is prepared by dissolving existing oxides and carbonates in a solvent instead of melting them, synthesizing them into a solution, coating them, and heat- However, it has disadvantages such as the use of an organic solvent and the formation of a glass protective layer by glass frit.

Japanese Laid-Open Patent Publication No. 2001-335696 discloses a method of using a reducing agent in which a fatty acid ester having a specific carbon number or a polyalkylene glycol alkyl ether and a polyoxy alkylene alkyl ether are used in combination Paste resin composition. However, when such a scoring agent is used, a reduction effect is exhibited in a low share, but there is not a sufficient reduction effect in a high share, and the stability of the viscosity with time is insufficient. In addition, in order to obtain sufficient physical properties, the addition amount of the reducing agent is increased and the cost burden is increased.

Korean Patent Publication No. 10-2008-0026376 (Mar. 25, 2008) Japanese Patent Application Laid-Open No. 2001-335696 (December 04, 2001)

In order to solve the above-mentioned problems, the present invention is applied to polyvinyl chloride, which is a paste material, and an additive capable of adding main characteristics, and has properties such as screen printing workability, adhesiveness after heat curing, Which does not require a cleaning operation such as surface chemical treatment after cutting, and a method for producing a cover glass film using the same.

The present invention relates to a peelable paste composition and a method for producing a coverglass film using the peelable paste composition. One embodiment of the present invention relates to a peelable paste composition comprising polyvinyl chloride, a vinyl chloride vinyl acetate copolymer, lignin, bisphenol diglycidyl ether, a phosphate based compound, a primary plasticizer and a secondary plasticizer.

In another aspect of the present invention,

a) preparing a thin film paste composition by mixing polyvinyl chloride, a vinyl chloride vinyl acetate copolymer, lignin, bisphenol A diglycidyl ether, a phosphate-based compound, a primary plasticizer and a secondary plasticizer;

b) defoaming the thin film paste composition of step a);

c) applying the thin film paste composition of step b) to the substrate surface;

d) curing the applied thin film paste composition;

To a method for producing a cover glass protective film.

Hereinafter, a peelable paste composition according to the present invention and a method for producing a cover glass film using the peelable paste composition will be described in detail.

The peelable paste composition according to the present invention comprises 35 to 40 parts by weight of polyvinyl chloride, 20 to 25 parts by weight of a vinyl chloride vinyl acetate copolymer resin, 1.0 to 3.0 parts by weight of lignin having an average particle diameter of 0.05 to 2 占 퐉, 0.5 to 2.0 parts by weight of bisphenol A diglycidyl ether (BADGE), 0.05 to 4.0 parts by weight of a phosphate compound, and 20 to 50 parts by weight of a primary and secondary plasticizer.

First, the average degree of polymerization of the polyvinyl chloride that can be used in the present invention is 1,000 to 2,000, preferably 1,200 to 1,600. When the average degree of polymerization of the polyvinyl chloride is less than 1000, mechanical properties such as resistance to abrasion including film strength may decrease on the surface of the polyvinyl chloride paste composition after gelation, and when the average degree of polymerization exceeds 2,000, Printing stability is poor. Also, the average degree of polymerization of the vinyl chloride vinyl acetate copolymer resin is from 500 to 2,000, preferably from 800 to 1,000, wherein the ratio of the vinyl acetate monomer is 10% by weight to 20% by weight, It is advantageous to form an adhesive force of 0.4 N or more.

It is preferable that the polyvinyl chloride and the polyvinyl chloride vinyl acetate resin are used in an amount of 55 to 65 parts by weight in total of the two resins. If the content of the polyvinyl chloride / polyvinyl acetate copolymer resin is less than 55 parts by weight, the adhesion to the PVC film may be poor, and if it exceeds 65 parts by weight, the heat resistance may be poor. Particularly preferable polyvinyl chloride vinyl acetate copolymer resins are copolymers of 60 to 80% by weight of a vinyl chloride component and 20 to 40% by weight of a vinyl acetate component.

The vinyl chloride resin contained in the vinyl chloride vinyl acetate copolymer is a copolymer of a resin mainly composed of a polyvinylchloride (PVC) vinyl chloride monomer and a monomer copolymerizable with the vinyl chloride resin, and particularly preferably has a polymerization degree of 600 to 4,000 Is preferably a polyvinyl chloride or a vinyl chloride copolymer. Examples of the monomer copolymerizable with vinyl chloride include vinylidenechloride, ethylene, propylene, acrylonitrile, vinylacetate, maleic acid, (meth) acrylate, acrylic acid, (meth) acrylic ester, etc. may be used.

The lignin includes lignin in lignocellulose. The lignocellulosic material may be selected from the group consisting of agricultural wastes or industrial wastes accompanying wood resources such as woody materials, wood flour, waste materials, clay materials, . As the lignin-containing material, not only a material containing natural lignin but also a so-called black liquid obtained after pulping treatment of a lignocellulose material can be used.

As the lignin that can be used in the present invention, it is preferable to use kraft lignin which is obtained as a by-product in the pulp manufacturing process, and it is preferable to use kraft lignin such as p-coumaryl alcohol, It is preferable to use a lignin containing a hydrophenylpropane component such as a coniferyl alcohol, a cinafyl alcohol and the like, which are bonded to each other through an ether bond or a carbon-carbon bond.

[Chemical Formula 1]

The lignin that can be used in the present invention is preferably 0.01 to 5.0 parts by weight, and preferably 1.0 to 3.0 parts by weight based on the protective sheet to which the release type paste composition according to the present invention is applied. The number average molecular weight of lignin is 1,000 to 20,000, preferably 3,000 to 9,000, and the average particle size is 0.01 to 5.0 占 퐉, preferably 0.05 to 2.0 占 퐉.

The bisphenol A diglycidyl ether (BADGE) resin used in the present invention has reactivity with an epoxy functional group and a secondary alcoholic hydroxyl group present in the BADGE resin, and a curing reaction by an epoxy functional group or a hydroxyl group occurs . Generally, the bisphenol A epoxy resin is excellent in heat resistance because the free rotation of the benzene nucleus of bisphenol A is difficult, and has an ether group in the molecule, which is characteristic of chemical resistance and plasticity. In addition, since hydrophilic hydroxyl groups and hydrophobic hydrocarbon groups are regularly arranged, they are excellent in adhesiveness and excellent electrical properties such as electrical insulation and dielectric constant after curing. The BADGE resin preferably has an average epoxy resin equivalent of 100 to 400. When the average epoxy resin equivalent weight is less than 100, it is difficult to exhibit desired physical properties. When the average epoxy resin equivalent weight is more than 400, the compatibility with the plasticizer is decreased and the melting point becomes too high, which makes control difficult. The bisphenol A type epoxy resin may be contained in an amount of 0.5 to 5 wt% of 100 wt% of the composite epoxy resin. If the content is less than 0.5% by weight, the properties required in the present invention can not be obtained. If the content is more than 5% by weight, cracks due to brittleness are undesirable.

The primary plasticizer included in the present invention improves physical properties such as processability, flexibility, electrical insulation and the like. Representative types include phthalates such as dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dibutyl phthalate (DBP) Such as di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisooctyl adipate (DIOA) (2-ethylhexyl) trimellitate (TOTM), triisooctyl trimellitate (TIOTM), triisononyl trimellitate (TINTM), triisooctyl trimellitate It is preferable to use a trimellitate plasticizer such as triisodecyl trimellitate (TIDTM) or the like, and it is most preferable to use TOTM.

The secondary plasticizer used in the present invention improves the moisture resistance of the thin film paste composition according to the present invention and is preferably an epoxidized soybean oil (ESO), an epoxidized linseed oil (ELO), etc. Epoxy-based, fatty acid ester-based or the like. More preferably, epoxidized soybean oil is used.

The epoxidized soybean oil is used as a secondary plasticizer and a costabilizer, and can affect the strength of the membrane in terms of low-migration and plays a role in improving the processability. The epoxidized soybean oil is not particularly limited, but it is preferable to use one having a weight average molecular weight of 1,000 to 3,000.

The amount of the secondary plasticizer is preferably 1.0 to 5.0 parts by weight based on 100 parts by weight of the polyvinyl chloride / vinyl chloride vinyl acetate resin. Preferably 1.0 part by weight to 3.0 parts by weight. When the content of the secondary plasticizer is less than 1.0 part by weight, sufficient workability can not be imparted. When the amount is more than 5.0 parts by weight, the anti-rusting property, abrasion resistance and adhesion force after curing are deteriorated.

The primary plasticizer and the secondary plasticizer may be used alone or in combination of two or more kinds of primary and secondary plasticizers. 20 to 50 parts by weight of the primary and secondary plasticizers are preferably added. If it is added in an amount of less than 20 parts by weight, the processability of the polymer resin is deteriorated. If it exceeds 50 parts by weight, migration from the polymer resin increases, and the physical properties may be deteriorated.

The phosphate compound acts as a curing accelerator of an antioxidant and an epoxy resin. As the phosphate compound, triphenyl phosphite, tri (monylphenyl) phosphite, Triisodecyl phosphite, diphenyl-iso-octyl-phosphite and the like can be used. 0.05 part by weight to 4.0 part by weight of the phosphate compound is preferably added. When the amount is less than 0.05 part by weight, it is difficult to obtain a sufficient thermal stability effect. When the amount is more than 4.0 parts by weight, a gas generating factor is not preferable.

The present invention may further comprise one or more additives of an inorganic filler, a thermoplastic resin, a stabilizer, a colorant, a foaming agent, an antioxidant, a flame retardant, an ultraviolet absorber, a releasing agent and an antifoaming agent in the peelable paste composition.

As the inorganic filler, calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, aluminum silicate, hydrotalcite, Magnesium silicate, calcium silicate, zeolite, and the like.

As the thermoplastic resin, polyethylene, polypropylene, vinyl chloride, vinyl acetate resin, polystyrene, acrylonitrile butadiene styrene, acrylic resin and the like can be used, and any one or two or more of them can be added.

As the stabilizer, it is preferable to use one or more of tribasic lead sulphate (TLS), dibasic lead phosphite (DLP), dibasic lead stearate (DBL) and calcium oleate.

One or two or more additives may be mixed for each additive, and the additive may be omitted depending on the physical properties, but the present invention is not limited thereto unless the object of the present invention is not impaired.

 The cover glass protective film using the thin film paste composition according to the present invention is produced through the following process.

a) preparing a thin film paste composition by mixing polyvinyl chloride, a vinyl chloride vinyl acetate copolymer, lignin, bisphenol A diglycidyl ether, a phosphate-based compound, a primary plasticizer and a secondary plasticizer;

b) defoaming the thin film paste composition of step a);

c) applying the thin film paste composition of step b) to the substrate surface;

d) curing the applied thin film paste composition;

First, the paste composition for the cover glass protective film comprises 35 to 40 parts by weight of the polyvinyl chloride, 20 to 25 parts by weight of a vinyl chloride vinyl acetate copolymer resin, 1.0 to 3.0 parts by weight of lignin having an average particle diameter of 0.05 to 2 μm 0.5 to 2.0 parts by weight of bisphenol A diglycidyl ether (BADGE), 0.05 to 4.0 parts by weight of a phosphate compound, and 20 to 50 parts by weight of a primary and secondary plasticizer, Lt; / RTI > The mixer may be a commonly used ribbon mixer, mixer or dissolver, and it is preferable to mix and mix the subcomponent in sequence with a liquid plasticizer, a solid raw material and polyvinyl chloride, for smooth dissolution.

When mixed with a mixer, it is preferable to use a planetary ball mill, a universal stirrer, a thin film swirling type high speed stirrer, or the like to perform defoaming. The degassing is preferably performed two to three times.

At the end of the defoaming process, the thin film paste composition is applied to a cover glass. In this case, the application method is not limited to the kind but the screen printing method is preferable. In the case of applying the screen printing method, a screen composition (stencil) is fixed to the equipment, and the paste composition is supplied thereon. At this time, plate design according to the thickness should be preceded by drying after setting the thickness of the rope and the emulsion. Once the plate is completed, the hardness of the film can be checked by considering the curing conditions after installation on the screen printing machine.

In addition, a screen printer is equipped with a squeezee and a scraper, and the speed is controlled according to the viscosity. It is desirable to lower the speed when the viscosity of the paste composition is high and to increase the speed when the viscosity is low. Specifically, the squeegee speed is set to 10.0 to 15.0 cm / sec, and in the case of the scraper, the squeegee speed can be adjusted to 25.0 to 30.0 cm / sec.

After the printing operation is completed on the surface of the glass substrate, the curing operation is performed using a dryer of infrared or medium wave infrared type. In the case of an infrared drier, drying is preferably performed at 160 to 180 ° C for 6 to 8 minutes, and when infrared is used, drying is preferably performed at 180 to 230 ° C for 1 to 2 minutes. The paste applied on the surface of the glass substrate has a larger effect on the drying time and temperature during the curing reaction and the adhesion to the glass surface also increases as the temperature increases. Also, if the temperature inside the curing and drying zone is 240 ° C or higher, yellowing or cracking may occur during the operation and carbonization of lignin may occur. The thickness of the paste composition after curing reaction is preferably 15 to 400 탆.

The present invention relates to a paste composition capable of protecting the surface of a cover glass when processing a cover glass, and a cover glass protective film using the paste composition, which has advantages of adhesiveness and frictional resistance. In addition, it can minimize the damage that may occur on the glass surface during cutting and machining of coverglass, and is also suitable for use in environmentally friendly products of solvent-free type. It also has the advantage of minimizing heating loss and minimizing heating loss, minimizing the amount of suspended particles remaining on the surface of the protective film after the processing of the cover glass, and eliminating the need for a chemical detergent, thus reducing raw material costs and labor costs .

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The examples of the present invention are merely illustrative examples for the concrete implementation of the present invention, and thus the scope of the present invention is not limited by the following examples.

The physical properties and test conditions measured in the following examples are described below.

(Exam conditions)

The following tests were carried out at a temperature of 23 ± 1 ° C and a relative humidity of 50 ± 5%.

(Dispersibility)

The resin composition was poured into a mold (10 cm x 10 cm) with a thickness of 0.2 mm and heated at 180 DEG C for 5 minutes to prepare a sheet. The surface of the sample was visually observed, ?: dispersion failure at less than 10% of the total area,?: dispersion failure at less than 50% of the entire area, and x: dispersion failure at less than 100% of the total area.

(Printing workability)

The paste composition was printed on the glass surface so that the adhesion amount was 170 mg / cm < ² >, and dried to form a predetermined pattern having a thickness of 30 mu m. A case in which a void pattern pinned layer formed on the surface was obscured or the occurrence of a handgun and pin hole was visually observed and a handgun pin hole was not observed was evaluated as? And the case X is shown.

(Abrasion resistance)

The paste composition was applied to a glass of 10 x 20 cm, coated with a 200-neck SUS screen mesh, and cured for 6 minutes in a 180 ° C convection oven. A friction material was placed on a sliding piece (25.4 mm × 50.8 mm, rubber thickness: 8 mm, 500 g), and the specimen was horizontally reciprocated on the circular arc, A distance of 55 1 mm and an arc turning radius of 180 mm was applied and a load of 500 g / cm ² was applied. The test piece was repeated 500 times at a speed of 45 times / min to visually observe the degree of frictional resistance of the specimen. , And when the scratches were generated at a depth of less than the depth of occurrence, ⊚ was indicated as ⊚.

(adhesiveness)

After applying paste to an 80 mm × 80 mm glass, the glass coated with a 200-neck SUS screen mesh is cured in an oven at 180 ° C. for 6 minutes, and then a transparent box tape is attached to a size of 50 mm × 40 mm. Leave the part to be fixed to the adhesion tester 60 mm x 25 mm and remove the remaining glass. After that, 50 mm x 40 mm parts fixed with a transparent box tape were connected at an angle of 90 degrees, and then an adhesive force measuring instrument SWU-10M (thickness of 1 mm, width of 50 mm, length of 20 mm and test speed of 100 mm / ). The peel strength of the coated film was measured twice per the same specimen to prepare an average value.

(Inner planet)

The release paper coated with the release paper and coated with the 80 占 퐉 hand quota was cured in the 180 占 폚 oven for 6 minutes, cut into 80 mm 占 80 mm size, and then the paste was peeled off. The initial weight (Wi) was measured to the four decimal places of the weight of the peeled paste. The sheet was placed between the ABS resin plates in an oven at 80 DEG C and left for 48 hours under a load of 1 kg. (Wo) was measured and calculated by the formula (1).

[Formula 1]

(% By weight) = {(Wi - Wo) / Wi} x 100

(Where Wi is the initial weight of the paste composition and Wi is the weight of the specimen under load for 48 hours).

(Contact angle)

After the paste was applied to an 80 mm 80 mm glass, the glass coated with 200 mesh SUS screen mesh was cured in an oven at 180 ° C for 6 minutes and the paste was completely peeled off. A total of 30 contact angles of 80 mm × 80 mm bare glass were measured with a contact angle meter (Dropmaster 300, FAMAS) at 5 locations in each of 5 horizontal, vertical and diagonal directions. The contact angles of the contact angle test specimens were measured up, 10 measurements were made and the average value was recorded.

(Refractive index)

 A prism coupler method was used according to ASTM D 542 standard. A contact area between the sample and the prism was prepared to be 8 mm x 8 mm by using a refractive index device (Prism Coupler 2010 / M (Metricon)) with a cured paste sample of the paste (width 50 mm x length 50 mm, thickness 30 m) The measurement spot size was 1 mm in diameter.

(Example 1)

, 32.0 parts by weight of tri-2-ethylhexyl trimellitate (TOTM), 2.0 parts by weight of epoxidized soybean oil (ESO), and 100 parts by weight of a polypropylene resin were placed in a stirrer equipped with a turbine- 2.0 parts by weight of Triphenyl Phosphite (TPP) was added and a liquid mixture at 30 占 폚 was prepared using a heating mantle. 2.0 parts by weight of lignin, 1.0 part by weight of bisphenol A diglycidyl ether (BADGE), 1.2 parts by weight of stabilizer calcium oleate, 0.3 part by weight of copper phthalocyanine blue, 37.0 parts by weight of polyvinyl chloride, and 22.5 parts by weight of a vinyl chloride vinyl acetate copolymer were sequentially added and stirred in this order to prepare a mixture phosphor paste. At this time, the internal temperature of the container was stirred at 25 ° C for 3 hours to prevent impurities from mixing. The resulting mixture was slowly stirred with a vacuum mixer under reduced pressure of 40 hPa / mbar and subjected to vacuum defoaming. The prepared paste composition was formed into a film according to the physical property measurement method described above. The composition ratios of the paste composition are shown in Table 1, and the dispersibility, printability, abrasion resistance, adhesive strength, anti-fogging property, contact angle difference and refractive index difference of the produced films are shown in Table 3.

(Examples 2 to 5)

 A paste composition was prepared in the same manner as in Example 1, except that the amount of the paste composition added was changed as shown in Table 1. The prepared paste composition was formed into a film according to the physical property measurement method described above. The composition ratios of the paste composition are shown in Table 1, and the dispersibility, printability, abrasion resistance, adhesive strength, anti-fogging property, contact angle difference and refractive index difference of the produced films are shown in Table 3.

[Table 1]

Lignin: Kraft lignin, BADGE: Bisphenol A diglycidyl ether, TOTM: Tri-2-ethylhexyl trimellitate, ESO: Epoxidized soybean oil, Stabilizer: calcium oleate, pigment: copper phthalocyanine

(Comparative Example 1)

 32.0 parts by weight of Tris (2-Ethylhexyl) trimellitate (TOTM), 2.0 parts by weight of epoxidized soybean oil (ESO), and 10 parts by weight of polyvinyl alcohol were placed in a stirrer equipped with a turbine- And triphenylphosphite (TPP) (2.0 parts by weight) were melted in a liquid state at a temperature of 25 ° C using a heating mantle, and maintained at room temperature to prepare a liquid mixture. , 1.0 part by weight of bisphenol A diglycidyl ether (BADGE), 4.0 parts by weight of a filler heavy calcium carbonate (average particle size of 1-5 mu m), 1.2 parts by weight of stabilizer calcium oleate (Calcium Oleate) 0.3 parts by weight of phthalocyanine (Copper phthalocyanine blue), 35.75 parts by weight of polyvinyl chloride, and 21.75 parts by weight of a vinyl chloride vinyl acetate copolymer are sequentially added and stirred in order to prepare a paste of the mixture. At this time, the internal temperature of the vessel was stirred at 25 ° C for 3 hours to prevent impurities from entering. The resulting mixture was slowly stirred with a vacuum mixer under reduced pressure of 40 hPa / mbar and vacuum degassed. The prepared paste composition was formed into a film according to the physical property measurement method described above. Table 3 shows the composition ratios of the paste composition, and Table 3 shows the dispersibility, printability, abrasion resistance, adhesive strength, anti-fogging property, contact angle difference and refractive index difference of the produced films.

(Comparative Examples 2 to 10)

 The procedure of Comparative Example 1 was repeated except that the amount of the paste composition to be added was changed as shown in Table 2 below. The prepared paste composition was formed into a film according to the physical property measurement method described above. Table 3 shows the composition ratios of the paste composition, and Table 3 shows the dispersibility, printability, abrasion resistance, adhesive strength, anti-fogging property, contact angle difference and refractive index difference of the produced films.

[Table 2]

BOTGE: Bisphenol A diglycidyl ether, TOTM: tri-2-ethylhexyltrimellitate, DOA: di (2-methylphenyl) Ethylhexyl) adipate, DOP: dioctyl phthalate, PDGAP: poly-di (2-ethylhexyl) glycol adipate, AAP: adipic acid polyester, TPP: triphenylphosphate, ESO: epoxidized soybean oil, stabilizer: calcium oleate, pigment: copper phthalocyanine

[Table 3]

In Table 3, surface dispersions of less than about half were generated in the samples of Comparative Examples 4 to 9, and in Comparative Examples 1 and 4 to 7, the blank pattern layer was exuded, or a pin- But in the Examples, surface dispersion did not occur and printing workability was also excellent.

The scratches were not found or the incidence was low in Examples 1 to 5 and Comparative Examples 8 to 10. In Comparative Examples 4 to 7 in which the polymer plasticizer was applied, lignin, which is one of the important constituents of the present invention, was included The effect of frictional resistance is not shown. Therefore, it has been confirmed that a desirable property can be obtained in the present invention by adding a melitate plasticizer together with the mixing of lignin.

As for the adhesive strength, Examples 1 to 5 exhibited a stickiness of 0.4 N or more, while Comparative Examples showed a range of less than 0.2 to 0.3. From the viewpoint of the inner ear performance, the average anti-icing property of the examples was 0.03%, indicating that the transition and migration properties were very low on the glass surface. Thus, it was confirmed that the anti-

In addition, the difference in contact angle and refractive index difference between the cured pastes of each paste composition can be checked to confirm the optimum range and reference of the sensor on the semi-automatic conveyor belt. As in Comparative Examples 1 to 3, when the filler was added except for lignin, the difference in the refractive indexes was observed to increase. In Comparative Examples 4 to 7 in which a polymer plasticizer was applied, the refractive index difference was similar to those of Examples 1 to 3 in Comparative Example 6 in which PDGAP, which is a polymer plasticizer, was added, but the dispersibility, It was confirmed that the value of the frictional resistance was low. In addition, it was confirmed that there is a large difference in the refractive index depending on the presence or absence of epoxidized soybean oil or triphenylphosphoric acid as a secondary plasticizer.

Claims (9)

Polyvinyl chloride, vinyl chloride vinyl acetate copolymer, lignin having a number average molecular weight of 1,000 to 20,000 and an average diameter of 0.01 to 5 占 퐉, bisphenol A diglycidyl ether, a phosphate compound, a primary plasticizer and a secondary plasticizer ≪ / RTI > The method according to claim 1,
Wherein the polyvinyl chloride has an average degree of polymerization of 1,200 to 1,600. The method according to claim 1,
Wherein the vinyl chloride vinyl acetate copolymer has an average polymerization degree of 800 to 1,000 and the vinyl acetate monomer is 10 to 15% by weight of 100% by weight of the total vinyl chloride vinyl acetate copolymer. delete The method according to claim 1,
Wherein the primary plasticizer is one or two or more selected from the group consisting of phthalate, adipate and trimellate. The method according to claim 1,
Wherein the secondary plasticizer is any one or two or more selected from the group consisting of polyester series, epoxy series and fatty acid ester series. a) a polyvinyl chloride, a vinyl chloride vinyl acetate copolymer, lignin having a number average molecular weight of 1,000 to 20,000 and an average diameter of 0.01 to 5 m, a bisphenol A diglycidyl ether, a phosphate compound, a primary plasticizer and a secondary Mixing a plasticizer to prepare a thin film paste composition;
b) defoaming the thin film paste composition of step a);
c) applying the thin film paste composition of step b) to the substrate surface;
d) curing the applied thin film paste composition;
≪ / RTI > 8. The method of claim 7,
Wherein the thickness after curing of the thin film paste composition is 15 to 400 mu m. 8. The method of claim 7,
Wherein the curing is performed at a temperature of 160 to 230 DEG C for 1 to 8 minutes.