KR101806746B1 - Manufacturing method of fluorinated resin compounds for adhesive using display and fluorinated resin compounds using the same - Google Patents

Abstract

The present invention relates to a manufacturing method of a fluorinated resin compound for a display adhesive which is mixed with a reactive resin in which fluorine particles are introduced into a urethane acrylate reactive resin through a chemical reaction with a urethane acrylate reactive resin in which fluorine particles are disposed. Since fluorine is included in the present invention, the fluorinated resin compound which is excellent in water repellency and oil repellency, and has an environmental load less than that of a compound such as PFOS is provided.

Description

TECHNICAL FIELD The present invention relates to a fluorinated resin composition for a display adhesive, and a fluorinated resin composition using the fluorinated resin composition for a display adhesive. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorinated resin composition,

The present invention relates to a method for producing a fluorinated resin composition for a display adhesive and a fluorinated resin composition using the fluorinated resin composition for a display adhesive. More particularly, the present invention relates to a fluorinated resin composition for a display adhesive having a low environmental load and excellent oil repellency and water repellency against human body and cosmetics And a fluorinated resin composition using the same.

Portable displays equipped with touch panels typified by smartphones and smart pads are exposed directly to the human body due to their environmental characteristics, resulting in new reliability problems, particularly inferior reliability due to oils (sebum and cosmetics) Problems are emerging as new issues.

Most of the adhesives used in the packaging process of electronic products such as displays and semiconductors are made of polymer materials and some inorganic or metal fillers are selectively used to supplement their properties and functions. Most of the polymer materials used are thermally deformed , The shrinkage / expansion of the material due to the increase and decrease of the temperature is severe, so that there is a great restriction on securing the reliability. Therefore, intensive research is needed to solve the problem.

In the field of adhesives for displays, research on moisture and water repellency mainly using various silicone compounds has been mainly carried out so far. Researches using such silicones have not been able to secure oil resistance and oil repellency, And research into introducing oil-in-oil or oil-oil-specific adhesives into adhesives used in packaging has not been conducted at present.

When only the silicone compound is used alone, the crosslinking property of the inorganic oxide and the polymer is poor, so that the friction durability is poor, or the crosslinking is not performed sufficiently depending on the number of functional groups for forming the three-dimensional structure, , So that there is a problem that contaminants accumulate easily.

Therefore, in order to exhibit excellent performance as well as water repellency as well as water repellency, the present invention is intended to apply a fluorine compound, which is conventionally used in textiles and paper as a processing agent, to an adhesive composition.

U.S. Patent No. 5,247,008 discloses an aqueous dispersion of a copolymer of a perfluoroalkyl ester of acrylic acid or methacrylic acid with an alkyl ester of acrylic acid or methacrylic acid and an aminoalkyl ester of acrylic acid or methacrylic acid, , Finishing agents for paper and mineral substrates.

However, recently, in the case of fluorine compounds, some perfluoroalkyl-containing compounds having specific chemical structures such as perfluoro octanoic acid (PFOA) and perfluoro octantane sulfonic acid (PFOS) have been reported to be toxic and environmental risk. It is necessary to develop a fluorine compound which can replace PFOA and PFOS which are widely used at present and their similar compounds.

US 5247008 A

The present invention aims at solving all of the above problems.

Another object of the present invention is to provide a fluorinated resin composition for display adhesives having low surface energy and excellent water repellency and oil repellency.

Another object of the present invention is to provide a fluorinated resin composition for a display adhesive comprising an environmentally stable fluorine compound.

Another object of the present invention is to provide a method for producing the above fluororesin composition for a display adhesive.

Another object of the present invention is to provide a coating agent for electrode protection using the above fluororesin composition for a display adhesive.

In order to accomplish the objects of the present invention as described above and achieve the characteristic effects of the present invention described below, the characteristic structure of the present invention is as follows.

The present invention relates to a method for producing a display adhesive comprising the steps of dispersing fluorine particles of 0.1 to 20 mu m in a urethane acrylate type reactive resin and introducing fluorine into the urethane acrylate oligomer of the reactive resin through a chemical reaction A method for producing a fluorinated resin composition is provided.

The present invention also relates to a method of dispersing fluorine particles in a reactive resin, comprising the steps of adding the urethane acrylate-based reactive resin and fluorine particles to a paste mixer, mixing the paste mixer at 800 to 3000 rpm for 5 to 60 minutes And a step of defoaming the bubbles of the mixed solution. The present invention also provides a method for producing a fluororesin composition for a display adhesive.

In the step of introducing fluorine through a chemical reaction in the present invention, a step of preparing a fluorinated urethane acrylate oligomer, a step of preparing a fluorinated urethane acrylate oligomer, an adhesion imparting agent, an epoxy ester (meth) acrylate based compound and a photopolymerization initiator Wherein the fluorinated urethane acrylate oligomer is prepared by mixing a fluorine compound with an aqueous solvent to prepare a fluorine compound solution, adding a polyol compound to the polymerization reaction Adding the polymerized fluoropolyol copolymer and polymerization inhibitor to the reactor to remove water by reducing the pressure to 1 atm or lower for 10 minutes to 1 hour; adding a diisocyanate compound to the water-removed fluorinated polyol copolymer to obtain 200 To 300 rpm, Adding a condensation polymerization catalyst to the mixture, maintaining the mixture at 50 to 85 캜 for 2 to 3 hours, and adding an acrylate-based compound to raise the temperature to 60 to 90 캜 to prepare a fluorinated urethane acrylate oligomer Wherein the fluorinated urethane acrylate oligomer is used in an amount of 10 to 60 parts by weight per 100 parts by weight of the fluorinated resin composition, 30 to 70 parts by weight of an epoxy ester (meth) acrylate and 0.1 to 10 parts by weight of a photopolymerization initiator in an agitator, stirring at 300 to 500 rpm under an ultraviolet blocking lamp for 50 to 120 minutes at room temperature, After stirring, the mixture is filtered with a 200-mesh filter, and then filtrated at a temperature of 36 to 48 Removing step and the bubbles of the mixed liquid was allowed to stand for between completely and is achieved by including the step of producing the fluorinated resin composition.

The present invention also relates to a fluorinated urethane acrylate oligomer comprising 50 to 70 parts by weight of at least one fluorinated urethane acrylate oligomer prepared by the production method according to claim 4, hydroxyethyl methacrylate, caproic acid acrylate, trimethylolpropane triacrylate, 30 to 40 parts by weight of at least one acrylic monomer selected from the group consisting of tetrahydrofurfuryl acrylate, hydroxypropyl acrylate and phenoxyethyl acrylate, and 0.1 to 10 parts by weight of at least one photopolymerization initiator By weight based on the total weight of the coating composition.

The present invention maintains the surface energy of the fluorinated resin composition for display adhesives below the surface energy of general oil and the surface energy of water to reduce the wettability of water and oil, thereby inhibiting the penetration ability and having excellent water repellency and oil repellency.

Further, the present invention limits the number of CF ₃ groups in the fluorine compound to 1 to 6, so that the environmental load is small and it is environmentally stable.

In addition, since the dielectric constant is as low as 5 or less due to a low polarization ratio of fluorine, the present invention has excellent electrical characteristics as an adhesive for packaging electronic products.

The following detailed description of the invention refers to the accompanying drawings, which illustrate, by way of illustration, specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. It should be understood that the various embodiments of the present invention are different, but need not be mutually exclusive. For example, certain features, structures, and characteristics described herein may be implemented in other embodiments without departing from the spirit and scope of the invention in connection with an embodiment. It is also to be understood that the position or arrangement of the individual components within each disclosed embodiment may be varied without departing from the spirit and scope of the invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is to be limited only by the appended claims, along with the full scope of equivalents to which such claims are entitled, if properly explained. In the drawings, like reference numerals refer to the same or similar functions throughout the several views.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings, so that those skilled in the art can easily carry out the present invention.

The fluororesin composition for a display adhesive according to an embodiment of the present invention may be first prepared by physically dispersing a fluorine compound in a reactive resin and introducing a fluorine compound into the reactive resin through a chemical reaction .

At this time, the dispersing step may be performed using a paste mixer, and the high speed mixing should be performed at a speed of at least 1000 rpm, and finally, a defoaming step may be included. At this time, the stirring speed is preferably 1000 to 3000 rpm, and the time may be 5 to 60 minutes.

The average particle diameter of the fluorine compound to be dispersed may be 0.1 to 20 占 퐉, preferably 1 to 10 占 퐉. If the average particle diameter of the fluorine compound is less than 0.1 탆, the fluorine compound is too small, and the interaction (reactivity) with the reactive resin is low, so that the effect of dispersing the fluorine compound is insignificant and the object of the present invention, especially, water repellency and oil repellency, If it is more than 20 탆, the interaction is high, but the fluorine compound is too large to disperse easily, and in particular, the particle size of the fluorine compound preferably satisfies the above-mentioned numerical range because of the problem that precipitation occurs during storage.

The content of the fluorine compound to be dispersed may be 40 to 100 parts by weight, preferably 70 to 100 parts by weight, based on 100 parts by weight of the reactive resin. Exceeding the above-mentioned numerical range, the dispersing effect may be insignificant as in the case of the average particle diameter, and precipitation may occur to a large extent.

The fluororesin composition for a display adhesive according to an embodiment of the present invention can introduce a fluorine compound into a reactive resin through a chemical reaction. In this case, a fluorine compound, a polyol compound, a diisocyanate compound, A fluorinated urethane acrylate oligomer containing an acrylate compound, a tackifier, an epoxy ester (meth) acrylate compound and a photopolymerization initiator.

The fluorinated urethane acrylate oligomer is an oligomer having fluorine introduced into a urethane acrylate oligomer by urethane reaction of a polyol compound and a diisocyanate compound to introduce a fluorine compound into the urethane compound in the process of producing the urethane compound, Capping method followed by reaction with a (meth) acrylate-based compound, and finally introducing an acrylate reactor into the terminal end-capping system.

As described above, since the fluorinated urethane acrylate oligomer is formed of urethane acrylate oligomer, there is an advantage that it can be easily applied to a flexible display such as a smart watch.

First, the fluorine compound containing one hydroxyl group (OH) is selected from 2,3,4,5,6-pentafluorobenzyl alcohol, 4- (trifluoromethyl) benzyl alcohol, [3,5- 2-methylethoxy) phenyl] methanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methylisopropanol, hexafluoro (P-tolyl) isopropanol, 4,5,5,6,6,6-hexafluoro-4- (trimethyl) -1-hexanol, 4,4,5,5,5-penta Fluoropentanol, pentafluoropropionaldehyde, 1H, 1H, 5H-octafluoro-1-pentanol, pentafluorobutan-2-ol, preferably 2,3,4,5 , 6-pentafluorobenzyl alcohol, 4- (trifluoromethyl) benzyl alcohol, [3,5-di (trifluoromethyl) phenyl] methanol or 1,1,1,3,3,3-hexafluoro 2-propanol. ≪ / RTI >

When a polyol compound and a diisocyanate compound are subjected to a urethane reaction, a fluorine compound containing one hydroxy group (hereinafter referred to as " fluoro monool ") does not enter the center of the urethane main chain. , The amount of fluorine monol may be influenced on the number of reactors and on the surface of the composition.

The reaction of introducing fluorine to the end of the fluorinated resin composition using the fluorine monool can be performed, for example, by the following mechanism.

The fluorine compound containing two hydroxyl groups (hereinafter referred to as "fluoro diol") is a fluorine compound containing a hydroxyl group is hexafluoro-2,3-bis (trifluoromethyl) 3-diol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8-octanediol, or 3,3,4,4,5, Octafluoro-1,6-hexanediol, preferably hexafluoro-2,3-bis (trifluoromethyl) butane-2,3-diol or 2, , 2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8-octanediol.

As described above, since the number of carbon atoms substituted with fluorine is 1 to 6 and the number of carbon atoms is smaller than that of perfluorocarbon having 8 or more carbon atoms, which is presently a problem of toxicity, the fluoride compound has a low environmental load and is environmentally stable. Can be prepared. Accordingly, it is clear that the fluorinated resin composition according to the embodiment of the present invention is a very excellent composition as a water-repellent / oil repellent agent that can replace perfluorocarbon which is a current problem.

Unlike the fluorine monool, the fluorine diol can be inserted into the urethane compound and has the effect of forming a more stable fluorinated resin composition.

In addition, the fluorine compound may further include a carbonate group as well as a hydroxyl group, and may preferably include a polyethylene carbonate diol.

The fluorine compound further comprising a carbonate group exhibits an effect of significantly improving the water permeability and the oxygen permeability blocking effect in the production of the resin composition for an adhesive. In comparison with the urethane compound to which a fluorine compound not containing a carbonate group is applied, It exhibits an excellent adhesion to the adherend, and thus has an effect of having excellent water repellency and adhesion even when the content of the fluorine compound is lower than that of the conventional fluorine compound.

In addition, by designing the molecular structure so that the fluorinated alkyl group and the carbonate group intersect, there is a characteristic that weather resistance, light resistance and the like are superior to those of conventional urethane compounds, and resistance to corrosion is strong. In producing a fluorinated polycarbonate diol, The reaction proceeds in-situ through the intermediates of the carbonate of the present invention.

The polyol compound in the fluorinated resin composition for an adhesive according to the embodiment of the present invention is a polyether polyol including polyethylene glycol, polypropylene glycol, polytetramethylene glycol and copolymers thereof; A polyester polyol including a polycondensation product of adipic acid and polyhydric alcohol, a polycondensation product of sebacic acid and polyhydric alcohol, a polycondensation product of phthalic acid and polyhydric alcohol, and a polycondensation product of lactones and polyhydric alcohol; Polycarbonate polyols obtained by reacting a diol containing 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and cyclohexanedimethanol with phosgene; And a polyolefin polyol including a polybutadiene diol and a hydrogenated polybutadiene polyol, and may preferably include a polybutadiene diol or a hydrogenated polybutadiene diol.

The polybutadiene diol and the hydrogenated polybutadiene diol exhibit a low glass transition temperature and are excellent in mechanical properties such as tensile properties and 300% modulus due to their high stereoregularity. Therefore, when these compounds are provided as copolymerization monomers of urethane compounds, The fluorine compound can be uniformly mixed with regularity and excellent mechanical properties such as tensile properties can be obtained when an adhesive for display is formed.

The diisocyanate compound in the resin composition for an adhesive according to an embodiment of the present invention may be at least one selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 5-naphthalene diisocyanate, 2,4-trilene diisocyanate, 2,6-trilene diisocyanate, 1,3-xylene diisocyanate, diphenylmethane-4,4-diisocyanate, 3- , Methylene diphenyl diisocyanate (MDI), 1,6-hexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane or 1,4-bis (isocyanatomethyl) cyclohexane, and preferably 1,6-hexane diisocyanate, isophorone diisocyanate, dicyclohexyl Diisocyanate and may include aliphatic diisocyanates hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclo hexane, or 1,4-bis (isocyanatomethyl) cyclo hexane. The aliphatic diisocyanate does not contain a benzene ring structure and can have a low viscosity when an adhesive is formed. Therefore, the aliphatic diisocyanate has an advantage of being easy to process, and can have high adhesion and excellent durability.

Containing isocyanurate-containing polyisocyanate derived from at least one of the above-mentioned diisocyanate compounds in an amount of 5 to 45% by weight based on the total weight of the diisocyanate compound.

Isocyanurate can form a ring structure containing an NCO group, and has an effect of improving the impact resistance by excellent physical and chemical stability as compared with an isocyanate compound having a linear structure. In addition, due to its ring structure, it has excellent thermal stability and is less deformed by heat.

If the content of isocyanurate is less than 5% by weight, the content of the isocyanurate can not contribute to impact resistance and heat resistance. If the content of isocyanurate exceeds 45% by weight, the ratio of the ring structure increases, . Therefore, it is desirable to satisfy the numerical value range of 5 to 45% by weight which is easy to handle while achieving excellent impact resistance and heat resistance.

Of the fluorinated resin compositions according to the embodiments of the present invention, the acrylate-based compound may be selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2- Hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, 2-hydroxy-3-phenoxy Propyl acrylate, propyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, pentaerythritol triacrylate, trishydroxyethyl isocyanurate diacrylate, trishydroxyethyl isocyanurate dimethacrylate , Pentaerythritol diacrylate monostearate or pentaerythritol dimethacrylate Relat monostearate may be included and preferably includes 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate or 2-hydroxybutyl acrylate .

At this time, in the acrylate compound, the reactor is introduced into the end of the fluorine-introduced urethane compound in an end capping manner.

In the production of the fluorinated urethane acrylate oligomer among the constituents of the fluorinated resin composition according to the embodiment of the present invention, the condensation polymerization catalyst and the polymerization inhibitor may be contained in an amount of 0.01 to 1% by weight based on the weight of the whole fluorinated urethane acrylate oligomer, And a diluent capable of controlling the amount of the diluent.

The polycondensation catalyst comprises a tertiary amine, an aprotic salt and an organometallic compound, the aprotic salt is a quaternary ammonium and a carboxylic acid salt of an alkali metal, and the organometallic compound includes, for example, copper naphthenate, cobalt naphtate , Zinc naphthate, n-dibutyl tin dilaurate, tristyl amine, dibutyl tin diacetate, and dibutyl tin dim mercutide. Specific examples of the tertiary amine compound include 2-methyltriethylene diamide, 1,4 - diazabicyclic [2,2,2] octane, bis (2-dimethylaminoethyl) ether, trimethylaminoethylethanolamine, N, N, N ¹ , N ¹ , N ² -pentamethyldiethylenetriamine, N , N ¹ -dimethylethanolamine, dimethylaminopropylamine, N-ethylmorpholine, N, N-dimethylaminoethylmorpholine, N, N-dimethylcyclohexylamine, 2-methyl- But is not limited to .

In particular, when a diisocyanate compound containing isocyanurate is applied, an aprotic magnetic salt which promotes the ring-forming reaction can be used.

The polymerization inhibitor may include butylhydroxytoluene, hydroquinone, hydroquinone monomethyl ether, parabenzoquinone or phenothiazine.

The diluent may include a (meth) acrylate-based monomer containing a hydrocarbon or fluorocarbon group having 4 to 12 carbon atoms. The diluent may include 0.01 to 1% by weight based on the weight of the whole fluorinated urethane acrylate oligomer. The higher the ratio of the diluent, the lower the viscosity of the oligomer, and the handling of the fluorinated resin composition can be facilitated.

 The molecular weight of the fluorinated urethane acrylate oligomer according to an embodiment of the present invention may be 1000 to 10,000 g / mol, preferably 2000 to 8000 g / mol. When the molecular weight is less than 1000 g / mol, there is a problem that the adhesive force of the urethane acrylate having adhesiveness is low. When the molecular weight exceeds 10,000 g / mol, the viscosity is high and handling of the pressure sensitive adhesive is difficult.

In addition, the average number of functional groups of the fluorinated urethane acrylate oligomer according to an embodiment of the present invention is at least 1.5, preferably 1.8 to 6. The average number of functional groups of the oligomer is a number that indicates how many average acryloyl groups are present in one fluorinated urethane acrylate oligomer molecule. When the oligomer is synthesized, the average number of functional groups can be controlled by controlling the reaction amount of the acrylate compound. A pressure-sensitive adhesive excellent in durability can be formed.

The tackifier of the fluorinated resin composition for a display adhesive according to an embodiment of the present invention may be a photocurable adhesive composition wherein the monomer is an aliphatic condensed ring having C6-C20 or an acrylate containing a fused ring.

(Meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, and combinations thereof, and acrylic acid-based adhesive compositions Based resins such as vinyl chloride, vinylidene chloride, vinylidene chloride, vinylidene chloride, and the like, such as polyolefins, polyesters, polyesters, polyesters, polyesters, polyesters, alkylester resins, styrene-butadiene copolymers, polyisoprene rubbers, polyoxybutylene rubbers, (Meth) acrylic resins including fluorine-containing alkyl acrylate polymer components, but are not limited thereto.

The epoxy ester (meth) acrylate of the fluororesin composition for a display adhesive according to an embodiment of the present invention is a copolymer of monofunctional epoxy ester (meth) acrylate obtained by reacting phenylglycidyl ether with (meth) acrylic acid, (methylphenyl) A monofunctional epoxy ester (meth) acrylate obtained by reacting (t-butylphenyl) phenylglycidyl ether with (meth) acrylic acid and a monofunctional epoxy ester (meth) (Meth) acrylate having an alkyl group having 1 to 30 carbon atoms such as a monofunctional epoxy ester (meth) acrylate obtained by reacting (ethylhexyl) glycidyl ether methyl (meth) acrylate with (meth) acrylic acid Preferably a monofunctional epoxy ester (meth) acrylate obtained by reacting phenylglycidyl ether with (meth) acrylic acid, (methylphenyl) phenyl (Meth) acrylate obtained by reacting monofunctional epoxy ester (meth) acrylate, (t-butylphenyl) phenylglycidyl ether and (meth) acrylic acid obtained by reacting glycidyl ether with Aromatic epoxy ester (meth) acrylate is preferred. The aromatic epoxy ester (meth) acrylate has the effect of improving the elongation at the time of tensile fracture and increasing the transparency.

The (meth) acrylate compound of the present invention comprising an epoxy group and an ester group can increase heat resistance of the surface, has an advantage of maximizing antifouling property and water repellency, and also improves transparency.

The photopolymerization initiator of the fluorinated resin composition for a display adhesive according to an embodiment of the present invention is a photopolymerization initiator such as a benzoin compound, an acetophenone compound, an acylphosphine oxide compound, a titanocene compound, a thioxene compound, or an oxime ester compound; Amine, and quinone. Specific examples of the sensitizer include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1 -hydroxy-cyclohexyl- Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-methyl-1- (4-methoxyphenyl) -2-methyl-propan- -Methylthiophenyl) -2-morpholinopropane-1-one, 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -Butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (5-2,4-cyclopentadiene- 1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, (O-benzoyloxime)], ethanone 1 [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- Reaction dogs (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 1 -hydroxy-cyclohexyl-phenyl-ketone in the presence of a strong base such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide desirable.

In addition, the solvent of the fluorinated resin composition of the present invention may generally include any organic solvent that can be used in the adhesive composition. Specific examples thereof include propylene glycol monoethyl ether acetate, toluene, methyl ethyl ketone, ethyl acetate, butyl acetate, , Methanol, butyl carbitol, butyl carbitol acetate, butyl cellosolve, butyl cellosolve acetate or terpineol.

In this case, the solvent is preferably contained in an amount of less than 30 parts by weight based on 100 parts by weight of the total composition. When the pressure-sensitive adhesive layer is applied to the display thick film (thickness of 100 占 퐉 or more) when the amount is 30 parts by weight or more, the solvent can be dried and foamed at the time of curing, and bubbles are thereby generated. In addition, when it is applied in an amount less than 30 parts by weight, the impact resistance of the touch panel can be improved and the printed steps of the surface can be absorbed.

The resin composition according to an embodiment of the present invention may further include a halogenated olefin monomer other than fluorine. By including a halogenated olefin monomer together with a fluorinated urethane acrylate oligomer, water repellency and oil repellency can be further enhanced.

The halogenated olefin monomer may include olefins of 2 to 20 carbon atoms substituted with 1 to 10 halogen atoms (chlorine, bromine, iodine), preferably chlorinated olefins of 2 to 20 carbon atoms, especially 1 to 5 chlorine Is preferably a chlorinated olefin having 2 to 4 carbon atoms containing an atom. Specific examples thereof include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, vinylidene bromide, and vinylidene iodide.

The halogenated olefin monomers may include 0 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total resin composition. When the amount of the halogenated olefin monomer is more than 50 parts by weight, it is preferable that the impact resistance is lowered, the elongation at the time of tensile fracture is lowered, and cracks are formed at the time of forming the adhesive layer.

The fluorinated resin composition according to an embodiment of the present invention may further include an inorganic material and a silane coupling agent.

The inorganic substance may be any silane compound, and may include, but is not limited to, tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS).

In addition, the silane coupling agent basically facilitates the mixing of the fluorinated urethane acrylate oligomer, the acrylate compound and the silane compound, which are organic compounds, through the hydrolysis and condensation reaction, and further improves the interface reforming, Any silane compound which can be used as a silane coupling agent may be used. Specific examples thereof include methacryloyloxypropyltrimethoxysilane (MPTMS), 3-aminopropyltriethoxysilane , 3-aminopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 30 acryloxypropyltri Methoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Vinyltriethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and the like. And may include any one or more of them, and may preferably include methacryloyloxypropyltrimethoxysilane.

The inorganic material may include 10 to 80 parts by weight, preferably 50 parts by weight, and the silane coupling agent may include 10 to 100 parts by weight based on 100 parts by weight of the total fluorinated resin composition.

By including an inorganic substance, it is possible to increase the pencil hardness and the adhesive force in the glass base material, and in particular, it is possible to form a composition for an adhesive excellent in ozone resistance and light transmittance.

When the amount of the inorganic substance is less than 10 parts by weight, the ozone resistance is lowered, and the pencil strength is weakened. When the amount of the inorganic substance is more than 80 parts by weight, adhesion strength to glass may be high, There is a problem that a peeling phenomenon occurs, so it is preferable to satisfy the above-described numerical range.

The fluororesin composition according to an embodiment of the present invention may further contain additives in an amount of 0.1 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the entire composition. The additives may be leveling agents, defoaming agents, Antioxidants, Surfactants, Ultraviolet absorbers. A wetting agent, and an antirust agent.

In this case, the stabilizer may be, for example, a diethylethanolamine, a tertiary amine such as trihexylamine, a hindered amine, an organic phosphate, a hindered phenol, gelatin, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose , Water-soluble polymers such as carboxymethylcellulose, polyethylene glycol, polyoxyethylene-polyoxypropylene block copolymer, polyacrylamide, polyacrylic acid, polyacrylate, sodium alginate and polyvinyl alcohol partial saponification, tricalcium phosphate, titanium oxide , Calcium carbonate, and silicon dioxide, but is not limited thereto.

In addition, the surfactant that can be added for stabilizing the dispersion may include at least one of sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, sodium lauryl sulfate or polyethylene glycol nonylphenyl ether as a specific example, It is not.

The fluorinated resin composition for a display adhesive according to an embodiment of the present invention may have a surface energy of 1 to 18 mN / m, and preferably 10 mN / m. In order to suppress penetration by reducing the wettability of water and oil by keeping the surface energy of ordinary oil (20 mN / m) and water surface energy (70 mN / m) or lower, The surface energy of the solution is low, but the wettability of the oil can not be reduced to equal or exceed the surface energy as compared with the oil. Therefore, a problem of deterioration of oil repellency occurs.

Also, the sebum reliability can withstand 120 hours or more at 60 DEG C, 90% RH (relative humidity), and has sebum reliability that can withstand 100 to 500 hours.

With respect to the cosmetic property, it is possible to form an adhesive composition suitable for a wearable display since it has endurance to withstand at least 85 ° C and 85% RH for 24 hours or more, preferably 12 to 48 hours .

In addition, since the dielectric constant is as low as 5 or less, it can have an electrical characteristic suitable for application as an adhesive on a display.

In addition, the viscosity is 40000 to 50000 cps, and the viscosity of the adhesive layer can be optimally formed by applying the adhesive once to the thick film of the display at room temperature and pressure. If the viscosity is less than 40,000 cps, not only the adhesion is reduced but also it is difficult to apply the adhesive layer to the desired point when applied to the display and it is inefficient to apply the adhesive agent several times. When the viscosity exceeds 50000 cps, There is a problem that the remnant workability is deteriorated because the residue of the adhesive remains at the time of the removal process.

The moisture permeability may be 10 to 200 g / m ² , 1day, and when the fluorinated urethane acrylate oligomer contains carbonate, it may be 10 to 100 g / m ² , 1 day. The water repellency is excellent.

The adhesive force may be 1000 to 3000 gf / cm, and preferably 1500 to 2300 gf / cm. In addition, as described above, it can be confirmed that when an inorganic material and a silane coupling agent are included, the adhesive force in glass has a relatively higher value.

In addition, the ionic impurities (Cl ^- , Na ⁺ ) of the fluorinated resin composition of the present invention may be 5 ppm or less.

When the fluororesin composition for a display adhesive according to the embodiment of the present invention is applied to the back surface of a display with an adhesive, the adhesive layer may be formed to have a thickness of 10 to 1000 mu m, preferably 25 to 500 mu m. If the thickness is out of the above range, it may be too thin to reduce the adhesive strength, and it may be too thick to remove the residue as needed, resulting in poor reworkability.

The number average molecular weight of the fluorinated resin composition may be 10,000 to 300,000 g / mol. If the number average molecular weight is less than 10,000 g / mol, the degree of alignment of the molecules decreases and the surface energy increases. When the number average molecular weight exceeds 300,000 g / The solubility in the solvent decreases sharply.

A method for preparing a fluorinated urethane acrylate oligomer in a resin composition for a display adhesive according to an embodiment of the present invention comprises: preparing a fluorine compound solution by mixing a fluorine compound with an aqueous solvent; Adding a polyol compound to proceed a polymerization reaction; Polymerizing the fluorinated polyol copolymer and the polymerization inhibitor into a reactor, and removing the water by reducing the pressure to 1 atm or less for 10 minutes to 1 hour; Adding a diisocyanate compound to the water-removed fluorinated polyol copolymer and stirring at 200 to 300 rpm; Adding a condensation polymerization catalyst to the mixture to maintain the mixture at 50 to 85 and reacting for 2 to 3 hours; Acrylate compound is added and the temperature is raised to 60 to 90 to prepare a fluorinated urethane acrylate oligomer.

A method for producing a fluorinated resin composition for a display adhesive according to an embodiment of the present invention is a method for producing a fluorinated resin composition for a display adhesive, which comprises: 10 to 60 parts by weight of a fluorinated urethane acrylate oligomer prepared by the above- 30 to 70 parts by weight of an epoxy ester (meth) acrylate, and 0.1 to 10 parts by weight of a photopolymerization initiator are added to a stirrer, and the mixture is stirred at 300 to 500 rpm under an ultraviolet blocking lamp and at a room temperature for 50 to 120 minutes. After stirring, the mixture is filtered through a 200-mesh filter, and then allowed to stand at room temperature for 36 to 48 hours to completely remove bubbles, thereby preparing a fluororesin composition for a display adhesive.

Further, it can be applied to a base film and cured at an energy of 2000 to 3000 mJ / cm ² to form a display adhesive.

The coating composition for electrode protection according to an embodiment of the present invention comprises 50 to 70 parts by weight of a fluorinated urethane acrylate oligomer prepared by at least one kind of the above-mentioned production method, hydroxyethyl methacrylate, caproic acid acrylate, trimethylolpropane 30 to 40 parts by weight of at least one acrylic monomer selected from the group consisting of triacrylate, tetrahydroperfuryl acrylate, hydroxypropyl acrylate and phenoxyethyl acrylate, and 0.1 to 10 parts by weight of at least one photopolymerization initiator .

In addition, less than 5 parts by weight of an antioxidant or a silane coupling agent may be included as an additive.

In this case, the photopolymerization initiator includes the above-mentioned photopolymerization initiator, and in addition, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 6-trimethylbenzoyl) -phosphine oxide or phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide, preferably 2-hydroxy-2-methyl- -Propanone, and phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide are preferable.

The above-mentioned acrylic monomer is used as a reactive diluent of an oligomer to impart workability of a resin formulation, and it is also polymerized by irradiation with ultraviolet rays to serve as a cross-linking agent between polymers, and hydroxyethyl methacrylate, caproic acid acrylate When the monomer is used as a monomer, the reactivity is high and the curing rate is high, and in particular, the odor is remarkably reduced when the monomer is used as the monomer, trimethylolpropane triacrylate, tetrahydroperfuryl acrylate, hydroxypropyl acrylate and phenoxyethyl acrylate. And it is preferable that 1 to 10 parts by weight of trimethylolpropane triacrylate is included in the total amount by weight in order to significantly reduce the smell.

In addition, when the monomer and the fluorinated urethane acrylate oligomer are contained, unlike the conventional coating composition which is cured at an exposure amount of 2400 mJ / cm ² , since the reactivity is high and the curing speed is fast, the curing is possible at 1500 mJ / cm ² , The productivity can be improved.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Manufacturing example  1. Fluorinated urethane Acrylate  Preparation of oligomers

2,3,4,5,6-pentafluorobenzyl alcohol and hexafluoro-2,3-bis (trifluoromethyl) butane-2,3-diol are mixed in a water solvent by stirring, and then hydrogenated polybutadiene The polyol is added to proceed the polymerization reaction with the fluorine compound. The polymerized fluorinated polyol copolymer and the polymerization inhibitor butylhydroxytoluene are put into a reactor and the pressure is reduced to 1 atm or less for 10 minutes to 1 hour to remove moisture. (IPDI) is added to the water-removed mixture and the mixture is stirred at 200 to 300 rpm. Bis (2-dimethylaminoethyl) ether is added as a condensation polymerization catalyst to maintain the temperature at 50 to 85 ° C for 2 to 3 hours Lt; / RTI > After completion of the reaction, 2-hydroxyethyl acrylate having a hydroxy group is added, the temperature is raised to 60 to 90, methyltetramethylene diamide is added, and the reaction is continued until the -NCO peak disappears on the IR to obtain fluorinated urethane acrylate oligomer .

Manufacturing example  2. Fluorinated urethane Acrylate  Preparation of oligomers

The fluorine compound is reacted with 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro The procedure of Preparation Example 1 was repeated except that the oligomer was changed to 1,8-octanediol.

Manufacturing example  3. Fluorinated urethane Acrylate  Preparation of oligomers

An oligomer was prepared in the same manner as in Production Example 1 except that diisocyanate was changed to 1,4-xylene diisocyanate.

Manufacturing example  4. Fluorinated urethane Acrylate  Preparation of oligomers

30% by weight of isophorone diisocyanate was added to a mixture of 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane in a weight ratio of 1: The oligomer was prepared in the same manner as in Production Example 1. [

Manufacturing example  5. Fluorinated urethane Acrylate  Preparation of oligomers

The stainless steel high-pressure reactor is purged with nitrogen, purged again with carbon dioxide, and then mixed with 1 mol of 4-fluoroethylene glycol and 1.5 mol of dimethyl carbonate. 0.5 mmol of di-t-butylaluminum hydrate as a catalyst is added thereto, and carbon dioxide is pressurized to 5 atm. The reaction is continued for 4 hours while maintaining the reaction temperature at about 80 ° C. After completion of the reaction, the reaction product was washed with water, and the water remaining in the diol oligomer was removed by using anhydrous magnesium to prepare a fluorinated polyethylene carbonate diol. Then, the fluorinated polyethylene carbonate diol prepared in place of the fluorine compound of Preparation Example 1 was added, An oligomer is prepared in the same manner as in Production 1.

Example  One

40 parts by weight of the fluorinated urethane acrylate oligomer of Production Example 1, 12 parts by weight of dicyclopentadienyl (meth) acrylate, 100 parts by weight of a monofunctional epoxy resin obtained by reacting phenylglycidyl ether with (meth) acrylic acid, 60 parts by weight of ester (meth) acrylate and 5 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one were put and stirred at 400 rpm and 25 DEG C for 70 minutes under an ultraviolet blocking lamp. After stirring, the mixture was filtered through a 200-mesh filter and left at 25 DEG C for 48 hours. Thereafter, the bubbles were completely removed, and the resultant was coated on a PET (polyethylene terephthalate) film to have a thickness of 300 μm and then cured at an energy of 2500 mJ / cm ² to form an adhesive layer with a fluororesin composition for a display adhesive.

Example  2

Except that 20 parts by weight of the fluorinated urethane acrylate oligomer of Production Example 1 was added.

Example  3

Was prepared in the same manner as in Example 1, except that 60 parts by weight of the fluorinated urethane acrylate oligomer of Production Example 1 was added.

Example  4

The fluorinated urethane acrylate oligomer of Production Example 2 was changed to the fluorinated urethane acrylate oligomer.

Example  5

The fluorinated urethane acrylate oligomer of Production Example 3 was changed to the fluorinated urethane acrylate oligomer.

Example  6

The fluorinated urethane acrylate oligomer of Production Example 4 was changed to the fluorinated urethane acrylate oligomer.

Example  7

Was prepared in the same manner as in Example 1, except that the fluorinated urethane acrylate oligomer containing carbonate of Production Example 5 was used.

Example  8

The procedure of Example 1 was repeated except that 20 parts by weight of vinyl chloride was added to 100 parts by weight of the entire composition.

Example  9

50 parts by weight of tetraethoxysilane (TEOS, 99%, Aldrich) and 70 parts by weight of methacryloyloxypropyltrimethoxysilane (MPTMS, 97%, Alfa Aesar) were added to 100 parts by weight of the total composition Was prepared in the same manner as in Example 1. The results are shown in Table 1. < tb > < TABLE >

Comparative Example  One

Was prepared in the same manner as in Example 1, except that the fluorinated urethane acrylate oligomer was changed to an acrylic acid isobutyl ester-based copolymer.

Comparative Example  2

Was prepared in the same manner as in Example 1, except that the fluorinated urethane acrylate oligomer was changed to fluorine-free urethane acrylate.

Comparative Example  3

Was prepared in the same manner as in Example 1, except that the monofunctional epoxy ester (meth) acrylate reacted with phenylglycidyl ether and (meth) acrylic acid was changed to 2-ethylbutyl acrylate.

Comparative Example  4

A fluorinated urethane acrylate oligomer was prepared in the same manner as in Example 1 except that the fluorinated urethane acrylate oligomer was changed to a silicone oligomer.

One. Water permeability  Measure

Examples 1 to 9 and Comparative Examples 1 to 3 were measured for moisture permeability according to KS M ISO15106-1 under the environment of a humidity of 90% at 40 DEG C, and the results are shown in Table 1 below.

2. Surface energy measurement

Examples 1 to 9 and Comparative Examples 1 to 3 were placed on a stage, and 1 쨉 l of water injected into the syringe was dropped. At this time, an average value was determined by repeatedly measuring the tackiness angle of the water droplet surface and the surface of the ultraviolet curable film layer 5 times through a photograph taken with a contact angle meter (Cahn Company DCA300). In the same manner, the contact angle between the diiodomethane surface and the surface of the ultraviolet curable film layer was measured five times and the average value was determined. Surface energy was calculated from the contact angle of the water droplet surface and the diiodomethane surface obtained from the above using the OWEK method (Owen, Wendt, Rabel, Kaeble method) and is shown in Table 1 below.

3. Adhesion measurement

Each of Examples 1 to 9 and Comparative Examples 1 to 3 was adhered to a glass substrate. After 30 minutes, the specimen was cut to 7.5 inches in length and 1 inch in width and the adhesive strength (peel strength) was measured according to ASTM D1002. Respectively.

4. Viscosity measurement

Examples 1 to 9 and Comparative Examples 1 to 3 were measured using a composition solution prior to curing and the viscosity was measured according to KS M ISO 3219 by measuring the viscosity at a specific shear rate using a rotational viscometer The results are shown in Table 1 below.

5, dielectric constant measurement

The dielectric constant means (capacitance of resin as dielectric) / (capacitance of air as dielectric), and dielectric constant is measured according to the test standard of ASTM D150 and is shown in Table 1 below.

6. Measurement of sebum reliability

Artificial sebum prepared by mixing 59 wt% of Triglyceride (Lexol GT865), Isostearic acid (23.7 wt%) and Squalane 17.3 wt% was applied to four outer surfaces of Examples 1 to 9 and Comparative Examples 1 to 3 After leaving for 120 hours, 240 hours, and 480 hours in an environment of 60 ° C and 90% humidity, samples were taken out after being left standing for 2 hours at room temperature, and appearance changes were observed. The results are shown in Table 1 .

<Degree of appearance change>

0: no sebum / cosmetic compound on the surface and no adhesion of wetting or dropping

1: Not wet on the surface, but showing adhesion in the form of droplets.

2: Small individual droplet wetting on the surface.

3: showing a wetting rate of about half the surface and showing a small individual wetting penetration of the film

4: wetting the entire surface

5: The surface and the back are entirely wetted

7. My Cosmetics  Measure

After applying the UV blocking cream (SPF 30, Nivea line spray) to the specimen and leaving it for 24 hours and 48 hours in an environment of 85 ° C and 85% humidity, remove the sample again and leave it at room temperature for 2 hours. The outer appearance was cleaned with a cloth moistened with alcohol, and appearance changes were observed. The results are shown in Table 1 below.

8. Measurement of yield (TON)

The amount of the reactant converted per gram of catalyst was measured, and the yields of Examples 1 to 9 and Comparative Examples 1 to 3 were obtained.

9. Pencil Hardness

The pencil hardness according to ASTM D3363 was measured using the pencil hardness meter for the specimens of Examples 1 to 9 and Comparative Examples 1 to 3, and the measured values are shown in Table 1 below. (6b to 9H)

10. Measurement of impact resistance

Examples 1 to 9 and Comparative Examples 1 to 3 were measured according to ASTM D2796 using a Gardner impact tester and the results are shown in Table 1 below.

11. Heat resistance measurement

Each of the coated surfaces of Examples 1 to 9 and Comparative Examples 1 to 3 was subjected to a heat treatment at 300 ° C for 1 hour, followed by discoloration and cracking of the appearance before and after the heat treatment, and the results are shown in Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Water permeability (g / m ² , 1day) 120 187 98 115 157 118 82 75 127 867 721 937 131 Surface energy (mN / m) 11 15 7 10 17 9 5 4 10 77 75 81 23 Adhesion
(gf / cm) 1420 1372 1097 1511 1218 1987 2130 1146 2510 2109 2657 981 1728 Viscosity (cps) 43009 42480 44813 42870 47321 49138 42192 44529 47413 46850 44812 43281 47528 permittivity
(1 MHz) 4 5 4 4 5 4 5 5 4 8 9 9 8 My sebum credibility
(120 hr) 0 0 0 0 0 0 0 0 0 5 4 5 3 My sebum credibility
(240 hr) 0 0 0 0 One 0 0 0 0 5 5 5 4 My sebum credibility
(480 hr) One One 0 One One One 0 0 0 5 5 5 5 My cosmetics (24hr) 0 0 0 0 0 0 0 0 0 4 4 5 3 My cosmetic property (48hr) 0 0 0 0 0 0 0 0 0 5 4 5 5 yield
(mol / gCat) 2360 2160 2270 2050 2190 2370 2950 2550 2090 2330 2150 2110 2390 Pencil Hardness (6b-9H) 2H 2H 1H 2H 4H 6H 2H 3H 6H 2H 1H 2H 1H Impact resistance
(g * mm
1000 * 500) scratch No crack scratch scratch crack
none crack
none No crack scratch No crack fracture fracture fracture A large amount of cracks Heat resistance Minor discoloration Minor discoloration Minor discoloration Minor discoloration Minor discoloration No discoloration No discoloration Minor discoloration No discoloration Yellow Yellow Yellow Minor discoloration

First, with respect to the moisture permeability, Examples 1 to 9 have lower moisture permeability than Comparative Examples 1 to 4, indicating that water repellency is excellent.

More specifically, as the fluorine content in the resin composition increases, the moisture permeability decreases and the water repellency is superior to those of Examples 1 to 3, and when Examples 1 and 5 are compared, it is understood that the aromatic diisocyanate is more preferable than the aromatic diisocyanate It can be seen that the water permeability is lower when the fluorinated urethane acrylate oligomer contains carbonate or when the halogen monomer is contained in the resin composition, the moisture permeability is relatively lower and the water repellency is more excellent. In addition, in the case of Comparative Example 4, the water permeability was similar to those in Examples 1 to 9, and it was confirmed that the water repellency was suitable for the composition for a display adhesive.

The surface energy is a factor that directly affects the moisture permeability, the sebum reliability, and the cosmetic resistance. Examples 1 to 9 all contain fluorine, which may be lower than the surface energy of oil and water, and the wettability to water and oil is reduced It can be predicted that water repellency and oil repellency will be excellent. In Comparative Examples 1 and 3, water and oil seem to permeate because of a very high surface energy. In Comparative Example 4, the wettability to water is low compared to the surface energy of water in Comparative Example 4, The wettability to the oil is high and it is predicted that the oil repellency will be lower than that of the examples.

Even if the adhesive strength is too low, there is no adhesive force and peeling occurs. When the adhesive strength is too high, the residue remains and the reworkability is poor. Thus, in Examples 1 and 2 and Comparative Examples 1, 2 and 4 all have appropriate values for the adhesive for display, It can be confirmed that the adhesive strength is relatively excellent when the aliphatic diisocyanate is applied to the fluorinated urethane acrylate oligomer, and it is confirmed that when the fluorinated urethane acrylate oligomer contains carbonate or the inorganic compound is contained in the resin composition, the adhesive strength is superior.

In the case of the dielectric constant, in all of Examples 1 to 9, the dielectric constant is 5 or less, which means that the dielectric loss is small, and thus it has excellent electrical characteristics to be applied as a display adhesive. On the other hand, all of the comparative examples 1 to 4 have higher permittivity than those of the examples, and the dielectric loss is relatively high.

With respect to the sebum reliability and cosmetic resistance, Examples 1 to 9 can confirm that oil repellency is maintained for at least 120 hours and oil repellency is maintained for up to 480 hours in terms of oil repellency reliability, and cosmetic resistance is 48 hours It can be confirmed that it is stable even in the case of Particularly, when the fluorine content is higher, the sebum reliability and cosmetic property are stable, and when the fluorinated urethane acrylate oligomer contains a carbonate group or further contains a halogenated monomer or an inorganic compound, the oil repellency is relatively more excellent You can see through these measurements. On the other hand, in Comparative Examples 1 to 3, Comparative Example 4, in which all of the oil was absorbed and the oil repellency was very low, and the moisture permeability was relatively low, showed poor physical properties such as sebum reliability and cosmetic resistance. It can be confirmed that the physical properties are lowered as compared with the examples. Also, through these experiments, it can be expected that the durability of the fluorinated resin composition according to the embodiment of the present invention also shows an excellent value.

Examples 1 to 9 are excellent in pencil hardness, impact resistance and heat resistance as compared with Comparative Examples 1 to 4, and are suitable for display adhesives , Particularly when an aromatic diisocyanate is used, when diisocyanurate is contained, or when an inorganic compound is further contained, these properties can be confirmed to exhibit relatively superior values.

Example  10

A urethane acrylate type reactive resin and a fluorine compound having an average particle diameter of 1 탆 were charged into a paste mixer and mixed at 1500 rpm for 30 minutes and defoaming the bubbles of the mixed solution was carried out to obtain a reactive resin in which a fluorine compound was dispersed .

Example  11

The procedure of Example 10 was repeated except that the average particle diameter of the fluorine compound was changed to 5 탆.

Example  12

Was prepared in the same manner as in Example 10, except that the average particle diameter of the fluorine compound was changed to 10 탆.

Example  13

A reactive resin obtained by mixing Example 1 and Example 11 is prepared.

Comparative Example  5

Was prepared in the same manner as in Example 10, except that the average particle diameter of the fluorine compound was changed to 50 nm.

Comparative Example  6

Was prepared in the same manner as in Example 10, except that the average particle diameter of the fluorine compound was changed to 25 占 퐉.

In the resin of Comparative Example 6, it was confirmed that the fluorine compound was not easily mixed and precipitation occurred.

The moisture permeability, surface energy, adhesive force and sebum reliability were measured for Examples 10 to 12 and Comparative Examples 5 and 6, and the results are shown in Table 2 below.

division Example 10 Example 11 Example 12 Example 13 Comparative Example 5 Comparative Example 6 Water permeability (g / m ² , 1day) 250 195 201 61 941 335 Surface energy (mN / m) 21 17 19 6 79 28 Adhesion
(gf / cm) 1328 1519 1254 1480 2788 570 My sebum credibility
(120 hr) One 0 0 0 5 2 My sebum credibility
(240 hr) One One One 0 5 3 My sebum credibility
(480 hr) 2 2 One 0 5 5 My cosmetics (24hr) 0 0 0 0 4 3 My cosmetic property (48hr) 0 0 0 0 5 4

As shown in Table 2, in Comparative Example 5 in which the diameter of the fluorine compound was very small, the interaction between the fluorine compound and the reactive resin was insufficient and the effect of containing the fluorine compound was insignificant. Thus, the moisture permeability, surface energy, In Comparative Example 6 in which the diameter is relatively large, the interaction can be formed well, but the diameter is too large to disperse easily, and it can be confirmed that the precipitation occurs, There is a problem that the water repellency and oil repellency are somewhat lower than those of the examples, and in particular, there is a problem that it is difficult to apply for a display adhesive because the adhesion is very weak.

In addition, in Example 13 including both the method of physically dispersing a fluorine compound and the method of chemically introducing a fluorine compound, the overall physical properties such as moisture permeability, surface energy, adhesive force, oil repellency and the like are excellent, It can be confirmed that it is a preferable method to use a fluorine compound in combination.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Therefore, the spirit of the present invention should not be construed as being limited to the above-described embodiments, and all of the equivalents or equivalents of the claims, as well as the following claims, I will say.

Claims (10)

Dispersing a fluorine compound containing one or two hydroxyl groups in a urethane acrylate-based reactive resin to prepare a urethane acrylate-based reactive resin composition having fluorine particles dispersed therein;
Introducing fluorine into the urethane acrylate oligomer of the urethane acrylate-based reactive resin to prepare a fluorinated urethane acrylate-based reactive resin composition; And
And a step of mixing the urethane acrylate-based reactive resin composition in which the fluorine compound containing one or two hydroxyl groups is dispersed and the fluorinated urethane acrylate-based reactive resin composition to prepare a fluororesin composition for a display adhesive Way. The method according to claim 1,
The step of preparing the urethane acrylate-based reactive resin composition, in which the fluorine compound containing one or two hydroxyl groups is dispersed,
Adding a fluorine compound containing the urethane acrylate-based reactive resin and one or two hydroxyl groups to a paste mixer;
Mixing the paste mixer at 800 to 3000 rpm for 5 to 60 minutes; And
And a step of defoaming the bubbles of the mixed solution prepared in the step (b). The method according to claim 1,
The step of preparing the fluorinated urethane acrylate-based reactive resin composition comprises:
Preparing a fluorinated urethane acrylate oligomer; And
And a step of preparing a fluorinated urethane acrylate-based reactive resin composition by using the fluorinated urethane acrylate oligomer, an adhesion-imparting agent, an epoxy ester acrylate-based compound and a photopolymerization initiator. Way. The method of claim 3,
Wherein the step of preparing the fluorinated urethane acrylate oligomer comprises:
Mixing a fluorine compound with an aqueous solvent to prepare a fluorine compound solution;
Adding a polyol compound to proceed a polymerization reaction;
Introducing the polymerized fluoropolyol copolymer and polymerization inhibitor into a reactor, and then removing the water by reducing the pressure to 1 atm or less for 10 minutes to 1 hour;
Adding a diisocyanate compound to the water-removed fluorinated polyol copolymer and stirring at 200 to 300 rpm;
Adding a polycondensation catalyst to the mixture to which the diisocyanate has been added, and maintaining the temperature at 50 to 85 ° C for 2 to 3 hours; And
Acrylate compound is added and the temperature is raised to 60 to 90 占 폚 to prepare a fluorinated urethane acrylate oligomer. The method of claim 3,
The step of preparing the fluorinated urethane acrylate resin composition comprises:
10 to 60 parts by weight of the fluorinated urethane acrylate oligomer, 0.5 to 15 parts by weight of a tackifier, 30 to 70 parts by weight of an epoxy ester acrylate, 0.1 to 10 parts by weight of a photopolymerization initiator To the agitator;
Stirring at 300 to 500 rpm under an ultraviolet blocking lamp, and at a room temperature for 50 to 120 minutes;
Stirring, filtering with a 200-mesh filter, and then standing at room temperature for 36 to 48 hours; And
And completely removing the bubbles of the mixed solution prepared in the above step to prepare a fluorinated resin composition. 6. The method of claim 5,
Further comprising the step of applying the fluorinated urethane acrylate resin composition to a substrate film and then curing the fluorinated urethane acrylate resin composition at an energy of 2000 to 3000 mJ / cm ² to form an adhesive for a display. Way. A fluororesin composition for a display adhesive, which is produced using the method for producing a fluororesin composition for a display adhesive according to any one of claims 1 to 6. 8. The method of claim 7,
Wherein the fluoride resin composition has an oil repellency reliability of 60 to 90% RH (relative humidity) for 100 to 500 hours. 8. The method of claim 7,
Wherein the fluorinated resin composition has a surface energy of 1 to 18 mN / m. 50 to 70 parts by weight of a fluorinated urethane acrylate oligomer prepared by the manufacturing method according to claim 4;
At least one acrylic monomer 30 selected from the group consisting of hydroxyethyl methacrylate, caproic acid acrylate, trimethylolpropane triacrylate, tetrahydroperfuryl acrylate, hydroxypropyl acrylate and phenoxyethyl acrylate To 40 parts by weight; And
2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1 -hydroxy- cyclohexyl- Hydroxy-1- [4- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, Methylphenyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl Bis (2,6-difluoro-3) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (5-2,4-cyclopentadien- - (1H-pyrrol-1-yl) -phenyl) titanium, 1,2-octanedione 1- [4- (phenylthio) -2- (O- benzoyloxime)], At least one compound selected from the group consisting of 6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyl oxime) and diphenyl (2,4,6- trimethylbenzoyl) One species Of the electrode protective fluorinated coating composition comprising a photopolymerization initiator 0.1 to 10 parts by weight.