KR20150106770A - Ultraviolet hardening typed adhesive composition with low dielectric constant and excellent adhesion and anti-environment property for bonding cover window on panel display, and manufacturing method thereof - Google Patents
Ultraviolet hardening typed adhesive composition with low dielectric constant and excellent adhesion and anti-environment property for bonding cover window on panel display, and manufacturing method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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Abstract
Description
The present invention relates to a UV-curable adhesive composition for bonding a flat display cover window having a low dielectric constant for adhering a cover window to a front portion of a flat panel display and having excellent adhesive strength and environmental resistance, and a method for producing the same.
In general, a flat panel display (FLAT PANEL DISPLAY) includes a liquid crystal display (LCD), a plasma display (PDP), an organic light emitting diode display (OLED), an electroluminescence display Has recently been widely used in electronic products having display devices such as a computer, a TV, a notebook, a smart phone, a tablet PC, and a digital camera.
Conventionally, a cover plate is provided on a front surface of a flat panel display. As such a cover plate, an anti-reflection glass, an anti-reflection plastic, a touch sensor, or the like is used.
Conventionally, the touch sensor window and the cover window are separated from each other and adhered to the cover window through the adhesive. In this method, the touch sensor window is bonded to the front surface of the flat panel display and the cover window is bonded to the touch sensor window. In recent years, technology has been developed in the direction of manufacturing a touch sensor on a cover window to integrate and integrate the touch sensor, thereby making it effective on the design side and thinning the product thickness.
Recently, the electrostatic touch method, which is a method of touching with a minute current flowing in the body instead of the pressure sensitive touch method in which the pressure applied to the conductive layer in the liquid crystal is recognized, has advantages of easier touch, elaborate and high image quality. The trend is expanding. However, in the case of such an electrostatic touch sensor, a sensor for measuring change in charge is sensitive, and malfunction of the touch sensor may occur. Particularly, when the dielectric constant is high, the risk of malfunction of the capacitive touch sensor increases, so it is preferable to use an adhesive having a low dielectric constant of 3 or less in the case of the capacitive touch sensor.
However, in the case of using an ultraviolet curable adhesive for bonding a cover window and a flat panel display in which a touch sensor is integrated, the shrinkage ratio of the adhesive should be low in order to reduce the damage caused by shrinkage during curing. In addition, the refractive index of the cured adhesive should be close to 1.52, which is the refractive index of the glass used in the cover window, and it is necessary to develop an ultraviolet curable adhesive which has excellent adhesion to glass and can maintain the adhesive force even in a high temperature or high humidity environment.
In order to prevent malfunction of a touch sensor when used in a liquid crystal display device to which an electrostatic touch sensor is applied, the present inventor has proposed an ultraviolet curing type adhesive having a low dielectric constant and a low shrinkage rate and excellent adhesion and environmental resistance, As a result of repeated researches for development, it has been found that an adhesive prepared by using a polyurethane acrylate oligomer, polybutene, hydroxyethyl methacrylate or the like has a low dielectric constant of 3 or less and exhibits a higher refractive index and a lower shrinkage rate than conventional Excellent adhesion and environmental resistance, and completed the present invention.
The object of the present invention is to provide a polyurethane resin composition which comprises 45 to 85% by weight of a polyurethane acrylate oligomer having a low dielectric constant, 10 to 50% by weight of polybutene having a low dielectric constant, 1 to 40% by weight of an acrylate monomer having a low dielectric constant, 0.1 to 5% by weight, an adhesion promoting agent of 0.05 to 10% by weight, and an additive of 0.05 to 5% by weight as an additive, which has a low dielectric constant and is excellent in adhesion and environmental resistance.
Another object of the present invention is to provide a method for producing the ultraviolet curable adhesive composition.
In order to solve the above problems, the present invention provides a polyurethane resin composition comprising 45 to 85% by weight of a polyurethane acrylate oligomer having a low dielectric constant, 10 to 50% by weight of polybutene having a low dielectric constant, 1 to 40 The present invention provides an ultraviolet curable adhesive composition having a low dielectric constant and excellent adhesion and environmental resistance, comprising 0.1 to 5% by weight of a photoinitiator, 0.05 to 10% by weight of an adhesion promoter, and 0.05 to 5% by weight of a polythiol resin as an additive .
The ultraviolet curable adhesive composition may further comprise 60 to 80% by weight of a polyurethane acrylate oligomer having a low dielectric constant, 10 to 30% by weight of polybutene having a low dielectric constant, 3 to 10% by weight of an acrylate monomer having a low dielectric constant , 0.1 to 5 wt% of a photoinitiator, 0.05 to 10 wt% of an adhesion promoter, and 0.05 to 5 wt% of a polythiol resin as an additive.
The number average molecular weight of the polyurethane acrylate oligomer may be 10,000 to 11,000 g / mol.
The polybutene having a low dielectric constant may include at least one of polybutene having an average molecular weight of 200 to 10,000 g / mol.
The acrylate monomer may be at least one selected from the group consisting of diethylaminoethyl acrylate, dimethylaminoethyl acrylate, t-octyl acrylate, N, N-dimethyl acrylamide, isobornyl acrylate, tricyclo- Acrylate, methacryloxypropyleneglycol acrylate, methoxypolyethylene glycol acrylate, stearyl acrylate, octadecyl acrylate, dodecyl acrylate, dodecyl acrylate, dodecyl acrylate, dicyclopentanyl acrylate, dicyclopentadiene acrylate, Hexyl acrylate, isoamyl acrylate, pentyl acrylate, t-butyl acrylate, isoamyl acrylate, isoamyl acrylate, isoamyl acrylate, isoamyl acrylate, isoamyl acrylate, undecyl acrylate, isodecyl acrylate, decyl acrylate, nonyl acrylate, isooctyl acrylate, Isobutyl acrylate, amyl acrylate , Butyl acrylate, isopropyl acrylate, propyl acrylate, ethyl acrylate, methyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, -3,7-dimethyloctyl acrylate. ≪ / RTI >
In addition, the photoinitiator may be selected from the group consisting of 2,2-dimethoxy-2-phenyl-acetophenone, xanthone, 1-hydroxycyclohexyl phenyl ketone, benzaldehyde, anthraquinone, 3- -Phenol) -2-hydroxy-2-methylpropan-1-one, thioxanthone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'- diaminobenzophenone, Ether and benzoin ethyl ether.
In addition, the adhesion promoter may be selected from the group consisting of vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxyclorohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, Aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- Aminopropyltrimethoxysilane hydrochloride, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, (Triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like. [0035] The term " catalyst "
In addition, the polythiol resin may be selected from the group consisting of trimethiolpraphan tris 3-mercaptopropionate (TMMP), tri-mercaptopropionyloxyethoxyisocyanurate (TEMPIC), pentaerythritol tetrakis 3 -Mercaptopropionate (PEMP), dipentaerythritol hexakis 3-mercaptopropionate (DPMP), and the like.
The ultraviolet curable adhesive composition of the present invention can be used for bonding a cover window to a front portion of a flat panel display, and exhibits a low dielectric constant with a dielectric constant of 3 or less.
The present invention also relates to a polyurethane resin composition comprising 45 to 85% by weight of a polyurethane acrylate oligomer having a low dielectric constant, 10 to 50% by weight of polybutene having a low dielectric constant, 1 to 40% by weight of an acrylate monomer having a low dielectric constant, 0.1 to 5% by weight of an adhesion promoting agent, 0.05 to 10% by weight of an adhesion promoter, and 0.05 to 5% by weight of a polythiol resin as an additive. In order to synthesize a polyurethane acrylate oligomer having a low dielectric constant, Acrylate monomers are reacted in a reactor to activate the polyol; Mixing the diisocyanate in the reactor to synthesize a urethane prepolymer; And introducing an acrylate monomer into the inside of the reactor to synthesize a polyurethane acrylate oligomer. The present invention also provides a method for producing an ultraviolet curable adhesive composition having a low dielectric constant and excellent adhesion and environmental resistance.
The ultraviolet curable adhesive composition according to the present invention has a low dielectric constant and can prevent a touch malfunction in the manufacture of a touch panel, exhibits a higher refractive index and a lower shrinkage ratio than conventional ones, has an excellent adhesive force and maintains an adhesive strength even in a high temperature or high humidity environment It is also excellent in environmental friendliness and excellent in adhesion reliability. Therefore, it is possible to overcome the disadvantages of the conventional ultraviolet curable adhesive and to use it to bond the cover window to the touch sensor window of the flat panel display.
1 is a flowchart showing a method of producing an ultraviolet curable adhesive composition according to the present invention.
2 is a cross-sectional view schematically showing a state in which a cover window integrated with a touch sensor is adhered to a front portion of a flat panel display using an ultraviolet curable adhesive composition according to the present invention.
Hereinafter, the configuration of the present invention will be described in detail with reference to the drawings with reference to the drawings.
The ultraviolet curable adhesive composition according to the present invention comprises 45 to 85% by weight of a polyurethane acrylate oligomer having a low dielectric constant, 10 to 50% by weight of polybutene having a low dielectric constant, 1 to 40 0.1 to 5 wt% of a photoinitiator, 0.05 to 10 wt% of an adhesion promoter, and 0.05 to 5 wt% of a polythiol resin as an additive.
More preferably, the ultraviolet curable adhesive composition comprises 60 to 80% by weight of a polyurethane acrylate oligomer having a low dielectric constant, 10 to 30% by weight of polybutene having a low dielectric constant, acrylate monomers 3 to 4 having a low dielectric constant, 10 to 10% by weight of a photoinitiator, 0.1 to 5% by weight of a photoinitiator, 0.05 to 10% by weight of an adhesion promoter and 0.05 to 5% by weight of a polythiol resin as an additive.
As used herein, the term "dielectric constant" refers to the real part of the dielectric constant. The dielectric constant refers to the permittivity of each dielectric relative to the dielectric constant of air.
The high dielectric constant is basically understood as meaning that electric energy is transmitted well. However, it can be understood differently according to AC or DC. In the concept of DC, it means that the energy flows more finely as a fine particle current. In AC concept, it means that the wavelength of electromagnetic wave becomes shorter, Can be understood. Accordingly, in the case of a liquid crystal display device to which the electrostatic touch sensor is applied, it is preferable that the dielectric constant of the adhesive used is 3 or less in order to prevent malfunction of the touch sensor.
It is preferable that the polyurethane acrylate oligomer having a low dielectric constant has a low number average molecular weight of 10,000 to 11,000 g / mol. When the number average molecular weight is less than 10,000 g / mol, The high shrinkage may cause shrinkage of the polarizing film located at the outermost edge of the flat panel display, resulting in a decrease in adhesion. When the number average molecular weight exceeds 11,000 g / mol, bubble removal is difficult , There is a problem that the wettability with the adherend may be lowered by the low-viscosity polymer having a high viscosity.
The polybutene contained in the ultraviolet curable adhesive composition according to the present invention may include one of polybutene having a number average molecular weight of 200 to 10,000 g / mol. The polybutene is a plasticizer olefinic oligomer and can improve the adhesion of the composition. In a preferred embodiment, the content of polybutene having a low dielectric constant of the present invention is 10 to 50% by weight, more preferably 10 to 30% by weight.
Among the acrylate monomers contained in the ultraviolet curable adhesive composition, monofunctional monomers include diethylaminoethyl acrylate, dimethylaminoethyl acrylate, t-octyl acrylate, N, N-dimethyl acrylamide, N-vinyl caprolactam, N Acrylic acid esters such as vinylpyrrolidone, acryloylmorpholine, isobutoxymethyl acrylamide, diacetone acrylamide, vinyl acrylate, isobornyl acrylate, tricycloctecanyl acrylate, dicyclopentanyl acrylate, dicyclopentadiene acrylate , Methoxypolypropylene glycol acrylate, methoxypolyethylene glycol acrylate, ethoxyethoxyethyl acrylate, methoxyethylene glycol acrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, phenoxyethyl acrylate, Cyclohexyl acrylate, benzyl But are not limited to, acrylate, acrylate, epoxy diethylene glycol acrylate, butoxy ethyl acrylate, tetrahydroperfuryl acrylate, stearyl acrylate, octadecyl acrylate, lauryl acrylate, dodecyl acrylate, undecyl acrylate, isodecyl Acrylate, isobutyl acrylate, hexyl acrylate, isoamyl acrylate, pentyl acrylate, t-butyl acrylate, isobutyl acrylate, decyl acrylate, decyl acrylate, nonyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, octyl acrylate, Propyl acrylate, isopropyl acrylate, ethyl acrylate, methyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, Ethyl methacrylate, 7-amino-3,7-dimethyloctyl acrylate, N, N -Diethyl acrylamide, and N, N'-dimethyl-aminopropyl acrylate may be used.
Examples of the polyfunctional monomer in the acrylate monomer contained in the ultraviolet curable adhesive composition include trimethylolpropane triacrylate, pentaerythritol triacrylate, ethylene glycol diacrylate, 1,6-hexadiol diacrylate, tripropylene At least one of glycol diacrylate, trimethylolpropane trioxyethyl acrylate, tricyclodecane dimethanol diacrylate and tris (2-hydroxyethyl) isocyanurate diacrylate can be used.
Examples of the photoinitiator contained in the ultraviolet curable adhesive composition include 2,2-dimethoxy-2-phenyl-acetophenone, xanthone, 1-hydroxycyclohexyl phenyl ketone, benzaldehyde, anthraquinone, 2-methylpropan-1-one, thioxanthone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dia At least one of minobenzophenone, benzoin propyl ether and benzoin ethyl ether may be used.
Examples of such photoinitiators include Micure TPO, PBZ, BP, EPD, DETX, BMS, MS-7, HP-8, CP-4 and BK-6 of Irgacure 184, 500 and 1173 of Ciba Geigy, , 2959, MBF, 754, 651, 369, 907, 1300, 4265, 819, 819DW, 2022, 2100, 784, 250, Darocure TPO.
As the adhesion promoter contained in the ultraviolet curable adhesive composition, silane is used, and specifically vinyl chloride, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-tri Aminopropyltrimethoxysilane, N- (vinylbenzene) -2-aminoethyl-3-aminopropyltrimethoxysilane, N- Mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, One or more of isopropyltriethoxysilane may be used.
The additives included in the ultraviolet curable adhesive composition are added in order to increase the adhesive strength and maintain the adhesive strength even in a high temperature or high humidity environment so as to improve the adhesion reliability. The additive is a liquid and has a polychiol Resin.
Here, the polythiol resin may be at least one selected from the group consisting of trimethiolpafantris tris 3-mercaptopropionate (TMMP), tri-mercaptopropionyloxyethoxyisocyanurate (TEMPIC), pentaerythritol tetrakis 3- Capped propionate (PEMP), and dipentaerythritol hexakis 3-mercaptopropionate (DPMP) may be used.
The ultraviolet curable adhesive composition of the present invention may further comprise a wetting agent, a defoaming agent, and the like. The wetting agent is added to improve the spreadability by lowering the surface tension of the adhesive when the surface tension is low on the surface to be adhered, and the defoaming agent is added for removing the bubbles generated by the vortex that may occur during the application of the adhesive .
In another aspect, the present invention provides a polyurethane resin composition comprising 45 to 85% by weight of a polyurethane acrylate oligomer having a low dielectric constant, 10 to 50% by weight of polybutene having a low dielectric constant, 1 to 40 By weight of a photoinitiator, 0.1 to 5% by weight of a photoinitiator, 0.05 to 10% by weight of an adhesion promoter and 0.05 to 5% by weight of a polythiol resin as an additive, wherein the polyurethane acrylate oligomer having a low dielectric constant Reacting the polyol and the acrylate monomer in a reactor to activate the polyol; Mixing the diisocyanate in the reactor to synthesize a urethane prepolymer; And introducing an acrylate monomer into the inside of the reactor to synthesize a polyurethane acrylate oligomer. The present invention also provides a method for producing an ultraviolet curable adhesive composition having a low dielectric constant and excellent adhesion and environmental resistance.
1 is a flowchart showing a method of producing an ultraviolet curable adhesive composition according to the present invention.
Referring to FIG. 1, in order to prepare the polyurethane acrylate oligomer, a polyol and an acrylate monomer are mixed and reacted in a reactor to activate a polyol (Step S1). At this time, the polyol has the greatest influence on optical properties such as physical properties and refractive index of the polyurethane acrylate oligomer, and it is most preferable that the structure of the synthesized polyurethane acrylate oligomer is linear. Therefore, diol), and examples thereof include monomolecular diols such as 1,3-butanediol, 1,4-butanediol, hydroxylated liquid butadiene, neopentyl glycol, 1,4-cyclohexanedimethanol, bisphenol A, Bisphenol F, reduced bisphenol A, reduced bisphenol F, dicyclopentadiol, and tricyclodecanediol.
In addition, high transparency and low shrinkage are required, so polyol requires light transmittance of 95% or more.
Next, a step (S2) of synthesizing a urethane prepolymer by mixing and reacting the diisocyanate in a reactor is carried out, wherein the diisocyanate is at least one selected from the group consisting of isophorone diisocyanate, 2,4-toluene diisocyanate and its isomers, hexamethylene diisocyanate, Propane diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate, 1,6-hexane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl Phenylenediisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, p-phenylenediisocyanate, m-phenylenediisocyanate, 1,5-naphthalene diisocyanate, One selected from among 1,3-xylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 1,4-xylene diisocyanate and 1,3-xylene diisocyanate have.
Next, in the above-mentioned production method, a urethane prepolymer and an acrylate monomer, which are synthesized so as to induce a reaction with a radical generated from a photoinitiator decomposed by ultraviolet rays, are injected into a reactor to form a linear polyurethane acrylate (3), wherein the acrylate monomer capable of reacting with the urethane prepolymer is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2 -Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-hydroxybutyl methacrylate is preferably used.
Here, in the step of synthesizing the polyurethane acrylate oligomer, it is preferable to add 1 to 2 moles of an acrylate monomer to 1 mole of the urethane prepolymer.
Next, using the prepared polyurethane acrylate oligomer as a base material, the remaining raw materials are added to the blender and stirred for one hour (S4), and then filtered to complete the adhesive composition (S5).
More specifically, the polyol used in the present invention may be a polyol having a structure represented by the following formula (1).
The structural formula of the urethane prepolymer synthesized using the polyol having the structure of the formula (1) is shown in the following formula (2). In the general formula (2), n is an integer of 2 to 7, and R 1 is dependent on the diisocyanate used.
When n is an integer of 2 to 7, the urethane group bonding number of the urethane prepolymer is 6 to 16. When the urethane group bonding number is less than 6, the curing density of the final composition is increased to increase the hardness and shrinkage ratio after curing, which may cause deformation of the adhesive base and decrease the adhesive strength, and it is difficult to realize various viscosity of the final composition due to low viscosity. On the other hand, when the urethane group bonding number exceeds 16, a urethane prepolymer having a relatively high viscosity is synthesized, and it is difficult to react the urethane prepolymer synthesized due to the high viscosity with the acrylate monomer. Even if the urethane prepolymer is produced, But also the wettability with the substrate is lowered to decrease the adhesive strength, and the time for feeding the raw material and the reaction time are increased during the production of the final composition, and the workability is lowered.
The structural formula of the polyurethane acrylate oligomer synthesized using the urethane prepolymer having the structure of Formula 2 is shown in Formula 3 below. In formula (3), m is an integer from 2 to 7, R 1 is based on the diisocyanate used, and R 2 and R 3 depend on the acrylate monomer used.
The ultraviolet curable adhesive composition of the present invention produced by the above method exhibits a dielectric constant of 3 or less, preferably 2.2 or less, and can prevent a malfunction of the touch sensor when it is used for bonding to a flat panel display cover window.
2 is a cross-sectional view schematically showing a state in which a cover window integrated with a touch sensor is adhered to a front portion of a flat panel display using an ultraviolet curable adhesive composition according to the present invention. Referring to FIG. 2, a
Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.
Example
(CAS No. 5888-33-5) and isophorone diisocyanate (CAS No. 4098-71-9) were added to a 3-liter round bottom flask in order to synthesize a polyurethane low polymer exhibiting low dielectric constant 1680 g (0.6 mole) of a polyol having a number average molecular weight of 2,800 g / mol (CAS No. 69102-90-5) and 177.6 g (0.8 mole) of a polyol having a number average molecular weight of 134 g / mol (CAS No. 25265-71 -8) (13.4 g, 0.1 mol).
While stirring them, 0.12 g of dibutyltin laurate as a reaction catalyst and 0.7 g of methylhydroquinone as a polymerization inhibitor for controlling the addition initiation reaction caused by heat during the synthesis were added. After the addition was completed, the temperature of the reactor was maintained at 70 캜 and stirred for 3 hours.
Next, 23.2 g (0.2 mol) of 2-hydroxyethyl acrylate (CAS No. 818-61-1) was slowly added thereto to conduct the reaction. After the completion of the addition, stirring was continued for 2 hours while maintaining the reaction temperature at 70 ° C.
It was confirmed by Fourier transform infrared spectroscopy (FTIR) that the isocyanate group peak at 2270 cm -1 disappeared, indicating that the reaction was completed and that the hydroxyl group completely reacted with the isocyanate group.
As a result of measurement using a gel permeation chromatograph (GPC), it was confirmed that the number average molecular weight of the ultraviolet curable polyurethane oligomer was 10,000 to 11,000 g / mol.
As a result of measuring the refractive index using the refractometer, the refractive index of the composite was 1.486.
By using the ultraviolet curing type polyurethane low polymer showing such a low dielectric constant, a high visibility ultraviolet curing type adhesive having a low shrinkage type and having a low dielectric constant was produced.
(CAS No. 9003-28-5), 2-hydroxyethyl methacrylate (CAS No. 868-77, manufactured by Nippon Polyurethane Industry Co., Ltd.), and the polyurethane acrylate oligomer -9), 0.25 g of an adhesion promoter, 1.0 g of an additive, 0.75 g of Irgacure 754 and 0.50 g of Irgacure 2959 were weighed to give a total weight of 100.00 g. The mixture was stirred at 350 rpm for 60 minutes at room temperature using a propeller- .
After stirring for 60 minutes, the mixture was filtered using a 5 占 퐉 filter to obtain an ultraviolet curable adhesive composition having a viscosity of 2,7000 cPs at 25 占 폚.
Comparative Example One
(CAS No. 7534-94-3) and 15 g of lauryl acrylate (CAS No. 2156-97-0) were used in the same manner as in the above-mentioned Example, except that 45 g of polyurethane acrylate oligomer, 20 g of isobornyl methacrylate To obtain an ultraviolet curable adhesive composition having a viscosity of 1,200 cPs at 25 ° C.
Comparative Example 2
In the same manner as in the above-described example, an ultraviolet curable adhesive composition having a viscosity of 2500 캜 at 25 캜 was obtained by adjusting 50 g of a polyurethane acrylate oligomer, 15 g of isobornyl methacrylate and 15 g of lauryl acrylate.
Comparative Example 3
An ultraviolet curable adhesive composition having a viscosity of 3,300 cPs at 25 占 폚 was obtained by adjusting 55 g of a polyurethane acrylate oligomer, 15 g of isobornyl methacrylate and 10 g of lauryl acrylate.
Dielectric constant measurement
LCR METER (Model No. 4824A) from HP and DIELECTRIC TEST FIXTURE (MODEL NO. 16451B) from AGILENT TECHNOLOGIES were used for dielectric constant measurement. The measurement specimen was cured in the form of a film having a thickness of 500 micrometers. When measured, the Cp value is measured in the LCR meter, and the dielectric constant is calculated using this value. The formula is as follows.
t a x C p
Dielectric constant (? R ) = ------------------
(d / 2) 2 x? x? 0
In the above equation, C p = Equivalent parallel capacitance [F]
t a = Average thickness of test material [m]
d = diameter of Guarded electrode [m 2 ]
epsilon 0 = 8.854 x 10 < -12 > [F / m].
12 times per sample, and the average value of 10 times excluding the maximum value and the minimum value was shown as a numerical value.
Adhesive strength measurement
The specimens were manufactured and evaluated according to ASTM (American Society for Testing Materials) D1002. An ultraviolet curable adhesive was applied to one end of the glass specimen with a length of 0.5 inches and a width of 1 inch, and one end of the other glass specimen was pressed and ultraviolet radiation was applied to adhere the specimen. The glass specimen was 4 inches long and 1 inch wide. Twelve times, the average value of ten times excluding the maximum value and the minimum value was taken as a numerical value. See ASTM D1002 for detailed adhesive strength assessment methods.
Hardness measurement
The ultraviolet curable adhesive composition was formed into a coating film having a thickness of 50 탆 by using a bar coater and cured at a light quantity of 2,000 mJ / cm 2 . The degree of curing was measured by comparing the spectral peaks at 1435 cm -1 , which is the characteristic wavelength of the acrylate group, using an infrared spectroscope.
Environmental friendliness Rating 1
Using an ultraviolet curable polyurethane adhesive composition, an adhesive was applied to a thickness of 100 mu m to adhere the two sheets of glass, and then left to stand at a temperature of 60 DEG C and a humidity of 95% for 96 hours. After drying at room temperature for 2 hours, the penetration of water and the deformation of the adhesive were observed using a microscope.
Environmental friendliness Rating 2
Using an ultraviolet curable polyurethane adhesive composition, an adhesive was applied to a thickness of 100 mu m to adhere the two sheets of glass, and then left at a temperature of 80 DEG C for 96 hours. After drying at room temperature for 2 hours, the adhesive was observed with a microscope.
Environmental friendliness Rating 3
Using an ultraviolet curable polyurethane adhesive composition, an adhesive was applied to a thickness of 100 mu m to adhere the two sheets of glass, and then left to stand at a temperature of -20 DEG C for 96 hours. After drying at room temperature for 2 hours, the adhesive was observed with a microscope.
Refractive index measurement
Refractive index was measured using a refractometer.
Shrinkage measurement
The liquid specific gravity and the solid specific gravity of the ultraviolet curable adhesive composition were measured according to Korean Industrial Standard KSM 0004 and KSM 0602 and the volume shrinkage was measured using the difference between the two values. The measurement equation is shown in Equation (1) below.
The measurement results of the adhesive strength, curing degree, environmental resistance, refractive index and shrinkage ratio of the above Examples and Comparative Examples are shown in Table 1 below.
As can be seen from Table 1, the ultraviolet curable adhesive composition according to the present invention had the lowest dielectric constant of 2.2 and had an adhesive force of 3 with glass-PMMA and an adhesive force of 4 with glass-glass, , The shrinkage rate is extremely low, the refractive index is 1.50, which is higher than that of the comparative example, and the environmental resistance is also excellent.
On the other hand, in the case of Comparative Examples 1, 2 and 3 in which the content of the polyurethane acrylate oligomer was decreased as compared with the examples, the compositions of the polyurethane acrylate oligomer and lauryl acrylate were changed to viscosity of 1,000 cps, And 3,000 cps of adhesives were prepared. These adhesives had a high curing rate, but showed a higher dielectric constant than the examples. Also, the adhesive strength was lower than those of the examples, and water penetration or deformation of the adhesive occurred in a high temperature or high humidity environment The environmental resistance also does not meet the embodiment of the present invention.
As a result, the ultraviolet curable adhesive composition produced by the production method of the present invention exhibits a low dielectric constant, has excellent adhesive strength, maintains adhesive strength even in a high temperature or high humidity environment, and is excellent in environmental resistance, And the hardening rate was fast. Therefore, it is possible to overcome the disadvantages of the conventional ultraviolet curable adhesive and to use the touch sensor for bonding the integrated cover window and the flat panel display.
Although the present invention has been described in connection with the above-mentioned embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made therein without departing from the spirit and scope of the invention, It is obvious that the claims fall within the scope of the claims.
Claims (13)
60 to 80% by weight of a polyurethane acrylate oligomer having a low dielectric constant, 10 to 30% by weight of polybutene having a low dielectric constant, 3 to 10% by weight of an acrylate monomer having a low dielectric constant, 0.1 to 5% 0.05 to 10% by weight of an adhesion promoting agent and 0.05 to 5% by weight of a polythiol resin as an additive, and having an excellent adhesive strength and environmental resistance.
Wherein the polyurethane acrylate oligomer has a number average molecular weight of 10,000 to 11,000 g / mol.
Wherein the polybutene has a number average molecular weight of 200 to 10,000 g / mol.
The acrylate monomer may be selected from the group consisting of diethylaminoethyl acrylate, dimethylaminoethyl acrylate, t-octyl acrylate, N, N-dimethyl acrylamide, N-vinyl caprolactam, N- vinyl pyrrolidone, , Isobutoxymethyl acrylamide, diacetone acrylamide, benzyl acrylate, isobornyl acrylate, tricycloctecanyl acrylate, dicyclopentanyl acrylate, dicyclopentadiene acrylate, methoxypolypropylene glycol acrylate, methoxypolypropylene glycol acrylate, Ethoxyethoxyethyl acrylate, methoxyethylene glycol acrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, phenoxyethyl acrylate, cyclohexyl acrylate, benzyl acrylate, epoxy Diethylene glycol acrylate, butoxy Ethyl acrylate, tetrahydrofurfuryl acrylate, stearyl acrylate, octadecyl acrylate, lauryl acrylate, dodecyl acrylate, undecyl acrylate, isodecyl acrylate, decyl acrylate, nonyl acrylate, 2 Acrylate, isobutyl acrylate, isobutyl acrylate, iso-octyl acrylate, octyl acrylate, heptyl acrylate, hexyl acrylate, isoamyl acrylate, pentyl acrylate, , Isopropyl acrylate, propyl acrylate, ethyl acrylate, methyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, -Dimethyloctyl acrylate, N, N-diethylacrylamide, N, N'-dimethyl-aminopropyl acrylate Trimethylolpropane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethylene glycol diacrylate, 1,6-hexadiol diacrylate, tripropylene glycol diacrylate, trimethylolpropane trioxyethyl acrylate, tricyclo Decane dimethanol diacrylate, and tris (2-hydroxyethyl) isocyanurate diacrylate.
The photoinitiator may be selected from the group consisting of 2,2-dimethoxy-2-phenyl-acetophenone, xanthone, 1-hydroxycyclohexyl phenyl ketone, benzaldehyde, anthraquinone, 3-methylacetophenone, 1- (4- 2-methylpropan-1-one, thioxanthone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether and benzo Ethyl ether. ≪ RTI ID = 0.0 > 5. < / RTI >
The adhesion promoter may be selected from the group consisting of vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxyclorohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- 3-aminopropyltrimethoxysilane hydrochloride, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylsilane, N- Wherein the adhesive composition comprises at least one selected from the group consisting of trimethoxy silane, bis (triethoxy silylpropyl) tetrasulfide, and 3-isocyanatopropyl triethoxy silane.
Wherein the polythiol resin is selected from the group consisting of trimethiolpraphan tris 3-mercaptopropionate (TMMP), tri-mercaptopropionyloxyethyisocyanate (TEMPIC), pentaerythritol tetrakis 3-mercapto (PEMP), and dipentaerythritol hexakis 3-mercaptopropionate (DPMP). The ultraviolet curable adhesive composition according to claim 1,
The adhesive composition for use in an ultraviolet curable adhesive for flat panel display cover window adhesion, wherein the adhesive has a dielectric constant of 3 or less.
To synthesize a polyurethane acrylate oligomer having a low dielectric constant,
Reacting the polyol and the acrylate monomer in a reactor to activate the polyol; Mixing the diisocyanate in the reactor to synthesize a urethane prepolymer; And introducing an acrylate monomer into the inside of the reactor to synthesize a polyurethane acrylate oligomer. The method of manufacturing an ultraviolet-curable adhesive composition having a low dielectric constant and excellent in adhesion and environmental resistance.
Wherein the step of synthesizing the polyurethane acrylate oligomer comprises adding 1 to 2 moles of an acrylate monomer to 1 mole of the urethane prepolymer.
The diisocyanate may be at least one selected from the group consisting of isophorone diisocyanate, 2,4-toluene diisocyanate and isomers thereof, hexamethylene diisocyanate, 2,2-bis-4'-propane diisocyanate, Isocyanate, 1,6-hexane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethylphenylene diisocyanate, 3,3'-dimethyl- Naphthalene diisocyanate, 1,4-xylene diisocyanate, 1,3-xylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 1,4-xylene diisocyanate, Xylene diisocyanate, 1,3-xylene diisocyanate, 1,3-xylene diisocyanate, and 1,3-xylene diisocyanate.
The acrylate monomers capable of reacting with the urethane prepolymer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2- Acrylate, and 2-hydroxybutyl methacrylate.
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| KR1020140029245A KR20150106770A (en) | 2014-03-12 | 2014-03-12 | Ultraviolet hardening typed adhesive composition with low dielectric constant and excellent adhesion and anti-environment property for bonding cover window on panel display, and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140029245A KR20150106770A (en) | 2014-03-12 | 2014-03-12 | Ultraviolet hardening typed adhesive composition with low dielectric constant and excellent adhesion and anti-environment property for bonding cover window on panel display, and manufacturing method thereof |
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| KR20150106770A true KR20150106770A (en) | 2015-09-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20180032040A (en) * | 2016-09-21 | 2018-03-29 | 동우 화인켐 주식회사 | Adhesive Composition and Adhesive Sheet Using the Same |
| KR102229884B1 (en) * | 2020-07-01 | 2021-03-18 | 동우 화인켐 주식회사 | Adhesive Composition and Adhesive Sheet Using the Same |
| WO2021075587A1 (en) * | 2019-10-18 | 2021-04-22 | Mitsubishi Electric Corporation | On-orbit additive manufacturing of parabolic reflectors via solar photopolymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20180032040A (en) * | 2016-09-21 | 2018-03-29 | 동우 화인켐 주식회사 | Adhesive Composition and Adhesive Sheet Using the Same |
| WO2021075587A1 (en) * | 2019-10-18 | 2021-04-22 | Mitsubishi Electric Corporation | On-orbit additive manufacturing of parabolic reflectors via solar photopolymerization |
| KR102229884B1 (en) * | 2020-07-01 | 2021-03-18 | 동우 화인켐 주식회사 | Adhesive Composition and Adhesive Sheet Using the Same |
| WO2022005139A1 (en) * | 2020-07-01 | 2022-01-06 | 동우 화인켐 주식회사 | Adhesive composition and adhesive sheet using same |
| CN116554826A (en) * | 2023-05-06 | 2023-08-08 | 浙江东腾新材料有限公司 | Special high-low temperature resistant adhesive for silent tire and preparation method thereof |
| CN116554826B (en) * | 2023-05-06 | 2024-01-05 | 浙江东腾新材料有限公司 | Special high-low temperature resistant adhesive for silent tire and preparation method thereof |
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