WO2013069870A1

WO2013069870A1 - Uv-cured adhesive composition, uv-cured adhesive film including same, display device including same, and module assembly method using same

Info

Publication number: WO2013069870A1
Application number: PCT/KR2012/005269
Authority: WO
Inventors: 김이준; 하경진; 권지혜; 남이리나; 오세일
Original assignee: 제일모직 주식회사
Priority date: 2011-11-07
Filing date: 2012-07-03
Publication date: 2013-05-16
Also published as: TW201323555A; TWI506112B

Abstract

The present invention relates to a UV-cured adhesive composition, a display device including the same, and a module assembly method using the same. More specifically, the present invention comprises a compound including a structure of chemical formula 1, a compound formed from the compound, or a mixture thereof.

Description

Photocurable pressure-sensitive adhesive composition, an optical pressure-sensitive adhesive film comprising the same, a display device comprising the same and a module assembly method using the same

The present invention relates to a photocurable pressure-sensitive adhesive composition, an optical pressure-sensitive adhesive film comprising the same, a display device including the same, and a module assembly method using the same.

In recent years, a major development goal in display panels is to improve outdoor visibility and to increase impact strength by compensating for weakness caused by panel enlargement. The optical adhesive film improves outdoor visibility and serves as an impact reinforcement.

The display panel has an outermost window layer made of glass, an air layer under the window layer, and an ITO glass under the air layer. The air layer is filled with an optical adhesive film, which is a transparent material having a similar refractive index with glass, to improve outdoor visibility.

The liquid pressure-sensitive adhesive composition is applied by thermally curing or photocuring and film-forming into an optical pressure-sensitive adhesive film in a state filled with a substrate. Liquid compositions are easy to remove bubbles, but have high shrinkage upon curing. In addition, the liquid composition may corrode the substrate due to high acidity of less than about 4 pH, and may cause problems in adhesion and impact resistance when attached to the substrate.

In addition, the liquid pressure-sensitive adhesive composition can solve the problem of poor bubbles compared to the film-like pressure-sensitive adhesive. However, defects may occur when the liquid phase is applied or when it is cured or cured. If a defect occurs, it needs rework, which is the process of removing and reusing parts. There is a problem in that the reworkability is poor, or it may take a long time to remove the cured resin and the material cannot be used again. However, if the initial adhesive strength is lowered for reworkability, future adhesion problems may occur.

In addition, the liquid pressure-sensitive adhesive composition may cause an overflow phenomenon when applied to the ITO film and pressed in the process of curing. Therefore, the process of manually washing the adhesive composition which overflowed using the wiper etc. was required. In order to overcome this problem, there is a method of controlling the fluidity by increasing the viscosity of the liquid pressure-sensitive adhesive composition. However, this method can solve the problem of overflow of the pressure-sensitive adhesive composition, but if the viscosity is too high, uniform spreadability on the ITO film may not be good. In particular, there is a problem that can not be used in an optical display having a large area.

In addition, as the touch screen market grows and the product range varies from small size such as mobile phones to large size displays such as TVs, it works between the upper window and the lower TSP sensor glass to improve outdoor visibility and impact resistance. Development of an adhesive is required.

In addition, the liquid pressure-sensitive adhesive composition may shrink during photocuring, such that leakage such as light leakage may occur at an edge portion. In addition, the temperature generated during display driving may cause a decrease in adhesive force of the pressure-sensitive adhesive, peeling of the edge portion, or lifting. This problem is particularly problematic for large size displays.

In addition, the liquid pressure-sensitive adhesive composition has no problem of foreign matter or bubble generation, it can be applied to a display of various sizes from small to large size. Basically, the optical adhesive is used in the lamination process of the window and the TSP, so it must have high adhesion. Another important physical property required for such optical adhesives is outdoor visibility and impact resistance. In particular, devices such as mobile phones are frequently dropped or hit while carrying, so the impact resistance that can mitigate the impact is important.

The method of improving impact resistance is to control the storage elastic modulus of an optical adhesive. This is because the lower the storage elastic modulus of the optical pressure-sensitive adhesive can alleviate the deformation by absorbing the impact received by the optical pressure-sensitive adhesive from the outside. In addition, there is a method of adjusting the elastic modulus as a method of improving impact resistance. By lowering the elastic modulus, deformation can be alleviated by absorbing the impact that the optical adhesive receives from the outside.

An object of the present invention is to secure good outdoor visibility, the pH is about 4 or more can minimize the corrosion of the substrate, or to improve the impact resistance by compensating the weak point of impact due to the enlargement of the panel, including the photocurable pressure-sensitive adhesive composition and the same It is to provide a display device.

Another object of the present invention is to provide a photocurable pressure-sensitive adhesive composition and a display device including the same, which can minimize the phenomenon in which high shrinkage occurs during photocuring and implement a pressure-sensitive adhesive film having a high elongation, or have excellent light transmittance and adhesion.

Still another object of the present invention is to provide a photocurable pressure-sensitive adhesive composition having excellent adhesion, tensile strength, impact strength, refractive index, appearance after curing, and liquid spreading property, and a display device including the same.

Still another object of the present invention is to provide an optical adhesive film having a low initial adhesive strength and a high final adhesive strength or a good rework property when initial failure is possible, and having a low curing shrinkage ratio, and a display device including the same. It is.

Still another object of the present invention is to provide a photocurable pressure-sensitive adhesive composition and a display device using the same, which can be quickly cured or solve the problem of overflowing from the module assembly.

It is still another object of the present invention to provide a module assembly method that does not require the step of removing the overflowed pressure-sensitive adhesive composition in module assembly.

Another object of the present invention is to provide a photocurable pressure-sensitive adhesive composition and a display device including the same to minimize the curing shrinkage during curing.

Still another object of the present invention is to provide a photocurable pressure-sensitive adhesive composition which minimizes light leakage and leakage during curing, and a display device including the same.

Still another object of the present invention is to provide a liquid-type photocurable pressure-sensitive adhesive composition that can be used in a large size display, and a display device including the same.

Another object of the present invention relates to an optical pressure-sensitive adhesive film comprising the photocurable pressure-sensitive adhesive composition.

Still another object of the present invention is to provide a photocurable pressure-sensitive adhesive composition capable of realizing an adhesive layer having a low storage modulus and a display device including the same.

Another object of the present invention is to provide a photocurable pressure-sensitive adhesive composition and a display device including the same, which can realize an adhesive layer having a low elastic modulus.

Still another object of the present invention is to provide a photocurable pressure-sensitive adhesive composition capable of realizing a pressure-sensitive adhesive layer capable of ensuring high adhesion and a display device including the same.

One aspect of the present invention relates to a photocurable pressure-sensitive adhesive composition.

In one embodiment, the composition may include a compound comprising a structure of Formula 1:

In one embodiment, the composition may further comprise a binder, a photocurable monomer and an initiator.

In another embodiment, the composition may further comprise one or more selected from the group consisting of UV absorbers and antioxidants.

In another embodiment, the composition may include a binder, a compound including the structure of Chemical Formula 1, a photocurable monomer, and an initiator.

In another embodiment, the composition comprises a binder, a compound comprising the structure of Formula 1, the pH is about 4 or more, the adhesion may be about 20kgf or more.

In another embodiment, the composition comprises a binder, a compound comprising the structure of Formula 1, the cure shrinkage is about 3% or less, the elongation after curing by ASTM D638 may be about 400 to 800%. .

In another embodiment, the composition comprises a urethane bond and —SiX ₁ X ₂ X ₃ (wherein X ₁ , X ₂ and X ₃ are the same or different, hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a carbon atom 1- Aromatic compound containing an alkoxy group of 10 or an aryl group having 6 to 20 carbon atoms), and the aromatic compound may be formed from a compound including the structure of Chemical Formula 1.

In another embodiment, the composition comprises a urethane bond and -SiX ₁ X ₂ X ₃ (wherein X ₁ , X ₂ and X ₃ are the same or different, hydrogen, hydroxyl groups, alkyl groups of 1-10 carbon atoms, 1-10 carbon atoms) An alkoxy group or an aryl group having 6 to 20 carbon atoms), wherein the aromatic compound is formed from a compound comprising the structure of Formula 1 of claim 1, and B and A may be about 2 or more when the initial adhesive strength of the adhesive is left at A, 70 ° C. for 1 hour and then the adhesive strength is referred to as “B”.

In another embodiment, the composition comprises (A) a binder, (B) a photocurable monomer, (C) a compound comprising the structure of Formula 1 and (D) a photoinitiator, wherein the photoinitiator has an absorption wavelength A photoinitiator (D1) of greater than about 350 nm to 400 nm or less and a photoinitiator (D2) having an absorption wavelength of greater than or equal to about 200 nm and less than or equal to 350 nm may be included in a weight ratio of about 1: 0.5 to 1: 5.

In another embodiment, the composition may include a binder, have a viscosity of about 2,000-4,000 cps at 25 ° C., and a cure shrinkage of about 1.5% or less.

In one embodiment, the binder has a urethane (meth) acrylate copolymer having a weight average molecular weight of (A1) of about 30,000 g / mol or more and 60,000 g / mol or less, and (A2) weight average molecular weight of about 5,000 g / mol or more It may be a mixture of urethane (meth) acrylate copolymers of less than 30,000 g / mol.

In one embodiment, the composition may further comprise a compound, a UV absorber, an antioxidant or a mixture thereof comprising the structure of Formula 1.

According to another aspect of the present invention, a display device may include an optical adhesive film made of the photocurable pressure sensitive adhesive composition or the photocurable pressure sensitive adhesive composition composition.

Another aspect of the present invention is a module assembly method comprising the steps of temporarily curing the photocurable pressure-sensitive adhesive composition in the laminate filled with the photocurable pressure-sensitive adhesive composition between the transparent electrode film layer and the window glass layer; Irradiating a light source from the side of the laminate; And it may include the step of curing the cured pressure-sensitive adhesive composition.

The present invention provides a photocurable pressure-sensitive adhesive composition which minimizes the curing shrinkage rate during curing. The present invention provides a photocurable pressure-sensitive adhesive composition which minimizes light leakage and leakage during curing. The present invention has the effect of providing a liquid-type photocurable pressure-sensitive adhesive composition that can be used in a large size display.

In addition, the present invention ensures good outdoor visibility, the pH is about 4 or more can minimize the corrosion of the substrate, to improve the impact resistance by compensating for the weak point due to the large size of the panel to improve the impact resistance, high shrinkage rate during light curing The invention provides a photocurable pressure-sensitive adhesive composition which minimizes the phenomenon occurring, has excellent elongation, excellent adhesion, light transmittance and adhesion, excellent tensile strength, refractive index, appearance after curing, and liquid spreading property, and a display device including the same. Has an effect.

In addition, the present invention can implement a pressure-sensitive adhesive film having a low initial adhesive force and a high final adhesive force, and can implement a pressure-sensitive adhesive film having good rework property at an initial failure, and has a low curing shrinkage ratio. Provided has the effect of the invention.

In addition, the present invention has the effect of providing a photocurable pressure-sensitive adhesive composition, a display device including the same, and a module assembly method using the same, which can be quickly cured and solve the problem of overflowing from the module assembly.

In addition, the present invention has the effect of providing a photocurable pressure-sensitive adhesive composition capable of realizing a pressure-sensitive adhesive layer having a low storage modulus, and the implementation of a pressure-sensitive adhesive layer having a low elastic modulus. In addition, the present invention has the effect of providing a photocurable pressure-sensitive adhesive composition capable of realizing a pressure-sensitive adhesive layer capable of ensuring a high adhesive force.

1 is a cross-sectional view of a display device according to an embodiment of the present invention.

Figure 2 shows the step of curing the photocurable pressure-sensitive adhesive composition in the module assembly method.

3 and 4 show the step of irradiating the light source from the side of the laminate in the module assembly method.

Figure 5 shows the step of curing the photocurable pressure-sensitive adhesive composition in the module assembly method.

100: adhesive layer, 200: cover glass, 300: transparent conductive film, 400: window glass, 500: touch screen panel, 1: transparent electrode film (ITO film), 2: window glass layer, 3: photo-curable pressure-sensitive adhesive composition, 3 ': temporary cured product of photocurable pressure-sensitive adhesive composition, 3' ': photocurable pressure-sensitive adhesive composition cured outside of transparent electrode film (ITO film), 4: UV lamp, 5: LED light source

Photocurable pressure-sensitive adhesive composition of one aspect of the present invention is a non-curable compound, It may include a compound formed from the non-curable compound, or a mixture thereof.

In the present specification, 'substituted' in 'substituted or unsubstituted' is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 carbon atoms. Substituted with an aralkyl group of -20 or the like.

In a first embodiment of the photocurable pressure sensitive adhesive composition, the composition may comprise a noncurable compound, a binder, a photocurable monomer and an initiator.

비경화성 화합물Non-curable compound

The non-curable compound may comprise a structure of formula (I):

(In the above, n and m are independently an integer of about 0 to 10, except that both n and m are 0,

Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q ₆ , Q ₇ and Q ₈ are independently hydrogen, linear or branched carbon atoms of 1 to 10 carbon atoms substituted with alkyl, hydroxyl and hydroxyl groups. An alkyl group of 10,-(-CH _2- ) sO-[-CH ₂ -CH ₂ O-] t-CH ₂ CH ₂ OH (s is an integer of about 0-5, t is an integer of about 0-5) Is selected from the group consisting of

At least one or more of Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q ₆ , Q ₇ and Q ₈ is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group,-(-CH _2- ) sO -[-CH ₂ -CH ₂ O-] t-CH ₂ CH ₂ OH (s is an integer of about 0-5, t is an integer of about 0-5).

Preferably n and m may be independently an integer of about 0-5, more preferably about 0-1.

In embodiments, the non-curable compound may have a structure of Formula 1-1 or 1-2:

A1-(-CH ₂ O-) n1-(-CH _2- ) m1-A2-(-CH ₂ O-) n2-(-CH _2- ) m2-A3-(-CH ₂ O-) n3- ( -CH _2- ) m4-A4

A1-(-CH ₂ O-) n1-(-CH _2- ) m1-A2-(-CH ₂ O-) n2-(-CH _2- ) m2-A3-(-CH ₂ O-) n3- ( -CH _2- ) m3-A4-(-CH ₂ O-) n4-(-CH _2- ) m4-A5

(In the above, n1, n2, n3, n4, m1, m2, m3 and m4 are independently integers of 0-10, provided that when n1 and m1 are both 0, when n2 and m2 are both 0, n3 and Unless m3 is all zeros, or if both n4 and m4 are zero,

A1 to A5 are any one of the following general formulas (a), (b), (c) or (d).

(a)

(b)

(c)

(d)

In the above, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are the same or different, independently hydrogen, linear or branched C 1-10 alkyl group, hydroxyl group, C 1-10 alkyl group substituted with hydroxyl group, -(-CH _2- ) sO-[-CH ₂ -CH ₂ O-] t-CH ₂ CH ₂ OH (s is an integer of about 0-5, t is an integer of about 0-5) At least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group, or-(-CH _2- ) sO-[-CH ₂ -CH ₂ O-] t-CH ₂ CH ₂ OH (s is an integer of about 0-5, t is an integer of about 0-5).

Preferably n and m may be independently an integer of about 0 ~ 1.

The non-curable compound may include about 2-10, preferably about 4-5 aromatic rings.

The hydroxyl group is an alkyl group having 1 to 10 carbon atoms directly attached to or substituted with an aromatic ring,-(-CH _2- ) sO-[-CH ₂ -CH ₂ O-] t-CH ₂ CH ₂ OH (s is An integer of about 0-5, t is an integer of about 0-5), and the like. The hydroxyl group serves to increase the adhesion of the pressure-sensitive adhesive composition.

The non-curable compound does not include an unsaturated bond including a functional group capable of participating in photocuring of the pressure-sensitive adhesive composition, for example, a double bond such as a vinyl group. Therefore, even if the adhesive composition is cured, the non-curable compound does not participate in the curing reaction. Instead, the non-curable compound is a lipophilic molecule with a large portion of the aromatic ring in the molecule, the molecule is stabilized in the form of a planar structure by the aromatic ring, the strong attraction between the delocalized electrons of the aromatic ring Stacking is possible. As a result, the non-curable compound does not cure, but does not escape into the liquid phase, so that the non-curable compound exists in the cured product of the pressure-sensitive adhesive composition.

In embodiments, the non-curable compound may be a xylene-formaldehyde resin. The xylene-formaldehyde resin has the advantage of no migration. In addition, xylene-formaldehyde resin has elasticity, heat resistance, optical properties and low shrinkage properties.

The xylene-formaldehyde resin may comprise about 2 to 10 aromatic rings, preferably about 4 to 5 aromatic rings.

Specific examples of the non-curable compound may have a structure of Formulas 1a to 1e, but is not limited thereto. These may be applied alone or in combination of two or more, preferably two or more of them are mixed:

(Wherein R is hydrogen, hydroxyl or methyl and n is an integer from about 0-5)

The compound may have a refractive index of about 1.47 to 1.6. This increases the refractive index of the photocurable pressure-sensitive adhesive composition to reduce the difference in refractive index between the window and the TSP glass, thereby preventing the sharpness of the display screen from deteriorating due to the refraction or reflection of light.

The Mw of the compound may be about 50-3,000 g / mol. Within this range, it is possible to prevent the non-cured material from falling out of the film during curing to cause a curing failure.

The compound may be included in about 1-30% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, it is possible to prevent the hardening defects from occurring in the liquid phase without remaining in the film that is the hardened product upon curing. Preferably about 5-30% by weight, more preferably about 10-30% by weight.

The compound is lipophilic due to the aromatic ring, whereas the binder including the urethane (meth) acrylate copolymer and the like which occupies the largest portion in the pressure-sensitive adhesive composition described below is hydrophilic. Therefore, it is important to establish an appropriate mixing ratio between the compound and the urethane (meth) acrylate copolymer described below.

In the photocurable pressure-sensitive adhesive composition, the compound: binder may be included in a weight ratio of about 1: 0.5 to about 1:10. Within this range, the miscibility between the hydrophilic molecules and the lipophilic molecules is good, and the shrinkage rate during curing can be minimized. Preferably in a weight ratio of about 1: 1.5 to about 1: 6.

바인더bookbinder

The binder may be a urethane (meth) acrylate copolymer, butadiene rubber, isoprene rubber or mixtures thereof. Preferably it may be a urethane (meth) acrylate copolymer or a mixture comprising the same.

The viscosity of the urethane (meth) acrylate copolymer can be about 25,000-140,000 cps at 25 ° C. Within this range, the curing shrinkage rate can be reduced.

The Mw of the urethane (meth) acrylate copolymer may be about 10,000-30,000 g / mol, preferably about 10,000-26,000 g / mol. Within this range, the durability, adhesion, elongation, heat resistance, and moisture resistance of the optical adhesive may be good.

The PDI of the urethane (meth) acrylate copolymer can be about 1.0-1.9. Within the above range, the molecular weight distribution of the urethane (meth) acrylate copolymer is small, there may be an effect that the physical properties of the copolymer is equivalent.

The urethane (meth) acrylate copolymer may be prepared by first polymerizing a polyol and a diisocyanate compound to prepare a urethane oligomer, and further polymerizing a (meth) acrylate monomer.

Polyols include polypropylene glycol, polypropylenediol, ethylene glycol, polyethylene glycol, propylene glycol, polytetramethylene glycol, tetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol It may include, but is not limited to, one or more selected from the group consisting of polycarbonate polyols, polyester polyols, and 1,4-cyclohexanedimethanol.

The diisocyanate compound may include one or more selected from the group consisting of isoprene, hexamethylene and toluene compounds, but is not limited thereto. For example, the diisocyanate compound is isophorone diisocyanate, hexamethylene diisocyanate, 2,4 or 2,6 toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate It may comprise one or more selected from the group consisting of isocyanates and mixtures thereof.

The (meth) acrylate monomer is a (meth) acrylic acid ester having a hydroxyl group, and may include a (meth) acrylic acid ester having a hydroxyl group in the terminal or structure and having an alkyl group having 2 to 10 carbon atoms. Preferably 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate or mixtures thereof.

The polymerization reaction of the polyol, the diisocyanate compound and the (meth) acrylate monomer can be carried out by conventional polymerization methods such as bulk polymerization, emulsion polymerization, suspension polymerization, and the like, and there is no particular limitation. The polymerization reaction can be carried out, for example, for about 40 ° C.-90 ° C. for about 2-24 hours.

The polymerization reaction can be carried out in the absence of a catalyst or in the presence of a catalyst, preferably a copolymer can be prepared using a catalyst.

The catalyst may be used, for example, one or more selected from the group consisting of dibutyltin dilaurate (DBTDL), triethylenediamine (TEDA), 1,4-diazabicyclo [2.2.2] octane, and the like. However, the present invention is not limited thereto. The catalyst may be used at about 0.05 to 2 parts by weight based on 100 parts by weight of the polyol.

The butadiene-based rubber may include polybutadiene rubber made from butadiene monomers. The Mw of butadiene rubber may be about 8,000 to 44,000 g / mol.

The butadiene rubber may be manufactured by a conventional polymerization method using butadiene, or may use a commercially available product (eg, UC-103, Kurary japan).

Isoprene-based rubber contains vinyl groups at its ends. The vinyl group participates in the curing of the pressure-sensitive adhesive composition to have an excellent modulus. In an embodiment, the isoprene-based rubber may be a (meth) acrylate modified isoprene rubber.

The isoprene-based rubber may have a structure of Formula 2:

(Wherein R is hydrogen or an alkyl group having 1 to 3 carbon atoms, m is an integer of about 1 to 300, n is an integer of about 0 to 60, p is an integer of about 1 to 10)

Preferably, n is an integer from about 1 to 60.

The isoprene-based rubber may have a weight average molecular weight (Mw) of about 10,000-50,000 g / mol, preferably about 17,000-35,000 g / mol. Within this range, it can have suitable flow properties and is also advantageous for shrinkage after curing.

The isoprene-based rubber may have a glass transition temperature (Tg) of about -70 to -50 ° C, preferably about -65 to -55 ° C. Within this range, it is possible to provide high adhesion and excellent film formation ability after photocuring and to provide excellent heat resistance.

The isoprene-based rubber may have a visible light transmittance of about 90% or more, preferably about 92 to 99% at a wavelength of about 400 nm to 800 nm. Within this range, outdoor visibility can be improved and impact resistance can be enhanced.

The isoprene-based rubber may have a melt viscosity of about 20 to 200 Pa · s, preferably about 30 to 190 Pa · s at 38 ° C. Within this range, the flow characteristics are excellent, so that the entire surface can be easily applied for a short time, and the bubbles that can be generated in the dispensing process can be minimized. The melt viscosity was 100 rpm at 38 ° C. with a Brookfield viscometer DV-II +, Spindle No. Measured with # 7.

In this embodiment, the binder may be included in about 25-83.7% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, it is possible to adjust the viscosity of the material to improve the workability and to exhibit a low curing shrinkage value. Preferably, about 40-60% by weight may be included.

광경화형 모노머Photocurable Monomer

The photocurable monomer is a vinyl monomer having a hydroxy group, a vinyl monomer having an alkyl group, a vinyl monomer having an alicyclic group, a (meth) acrylic monomer having an alicyclic hetero ring, a vinyl monomer having a carboxylic acid group, a vinyl group having a silane group Monomers, vinyl monomers having aromatic groups, and the like can be used.

Preferably, the photocurable monomer may include a vinyl monomer having a hydroxy group, a vinyl monomer having an alkyl group, a vinyl monomer having an alicyclic group, and a (meth) acrylic monomer having an alicyclic hetero ring.

The photocurable monomer may be included in about 15-40% by weight, preferably about 15-30% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, the viscosity of the material can be adjusted to improve workability and exhibit low shrinkage values.

The vinyl monomer having a hydroxy group is not particularly limited as long as it is a monomer having a hydroxy group and a carbon-carbon double bond. The monomer may have one or more hydroxy groups. The hydroxyl group may be at the monomer end or inside the structure. The vinyl monomer having a hydroxy group may be a (meth) acrylic acid ester having a hydroxy group and an alkyl group having 1 to 20 carbon atoms. For example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 1 , 6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) Acrylate, trimethylolethane di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 2-hydroxy-3-phenyloxy (Meth) acrylate, 4-hydroxycyclo As hexyl (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and the like can be used are, but are not necessarily limited thereto. The vinyl monomers having these hydroxyl groups may be used alone or in combination of two or more thereof. Vinyl-based monomer having a hydroxyl group may be included in about 1-10% by weight, preferably about 2-8% by weight in the pressure-sensitive adhesive composition.

The vinyl monomer having an alkyl group may include a (meth) acrylic acid ester having a linear or branched alkyl group having 1 to 20 carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, iso-butyl (meth) acrylic Latex, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl ( It may mean one or more selected from the group consisting of metha) acrylate, decyl (meth) acrylate and lauryl (meth) acrylate, but is not limited thereto. Vinyl-based monomer having an alkyl group may be included in about 1-10% by weight, preferably about 1-5% by weight in the pressure-sensitive adhesive composition. It is possible to obtain a result that can solve the stress stress within the above range.

The vinyl monomer having an alicyclic group may include a (meth) acrylic acid ester having a monocyclic or heterocyclic alicyclic ring having 4 to 20 carbon atoms. Preferably, the (meth) acrylic acid ester which has a C6-C20 monocyclic or heterocyclic alicyclic ring can be included. For example, the monomer may include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, and the like. Vinyl-based monomer having an alicyclic group may be included in about 5-20% by weight, preferably about 6-18% by weight of the pressure-sensitive adhesive composition on a solids basis. By adjusting the viscosity of the optical pressure-sensitive adhesive within the above range can be obtained a result of ease of workability during coating.

The (meth) acrylic monomer having an alicyclic hetero ring may include a (meth) acrylic monomer having a monocyclic alicyclic hetero ring having 4 to 6 carbon atoms having nitrogen, oxygen, or sulfur. For example, the monomer may include acryloyl morpholine and the like. The (meth) acrylic monomer having an alicyclic hetero ring may be included in an amount of about 1-10% by weight, preferably about 1-5% by weight, in the pressure-sensitive adhesive composition. Within this range, a result of increasing adhesion between the optical adhesive and the transparent electrode film such as glass or ITO film can be obtained.

The vinyl monomer having a carboxylic acid group is, for example, β-carboxyethyl (meth) acrylate, (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid, acrylic acid, methacrylic acid, fumaric acid, maleic acid, or the like. It may mean one or more selected from the group consisting of, but is not limited to these. The vinyl monomer having a carboxylic acid group may be included in an amount of about 0-10% by weight, preferably about 1-10% by weight in the pressure-sensitive adhesive composition. The result which raises the adhesive force of an optical adhesive within the said range can be obtained.

The monomer which has a vinyl group and a silane group can raise the adhesive force to glass. Such monomers include "(R ₁ ) (R ₂ ) (R ₃ ) Si- (CH ₂ ) n-COO-CR ₄ = CH ₂ (wherein R ₁ , R ₂ and R ₃ are independently hydrogen, halogen, An alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R ₄ is hydrogen or an alkyl group having 1 to 3 carbon atoms, n is about 0-10) or a monomer represented by "(R ₁₁ ) (R ₂₁ ) (R ₃₁ ) Si-CR ₄₁ = CH ₂ (wherein R ₁₁ , R ₂₁ and R ₃₁ are independently hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R ₄₁ is Hydrogen or an alkyl group having 1 to 3 carbon atoms). For example, the monomer may be at least one selected from the group consisting of (meth) acryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane. It may include, but is not limited thereto. The monomer having a vinyl group and a silane group may be included in an amount of about 0-10% by weight, preferably about 1-10% by weight in the pressure-sensitive adhesive composition.

The vinyl monomer having the aromatic group is not particularly limited as long as it is a (meth) acrylate having a substituted or unsubstituted aryl group, aryloxy group, or aralkyl group having 6 to 20 carbon atoms. For example, benzyl (meth) acrylate, phenoxy (meth) acrylate, 2-ethylphenoxy (meth) acrylate, phenyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 2-phenyl Propyl (meth) acrylate, 4-phenylbutyl (meth) acrylate, 2-2-methylphenylethyl (meth) acrylate, 2-3-methylphenyl (meth) acrylate, 2-4-methylphenylethyl (meth) acrylic Late, 2- (4-propylphenyl) ethyl (meth) acrylate, 2- (4- (1-methylethyl) phenyl) ethyl (meth) acrylate, 2- (4-methoxyphenyl) ethyl (meth) Acrylate, 2- (4-cyclohexylphenyl) ethyl (meth) acrylate, 2- (2-chlorophenyl) ethyl (meth) acrylate, 2- (3-chlorophenyl) ethyl (meth) acrylate, 2 -(4-chlorophenyl) ethyl (meth) acrylate, 2- (4-bromophenyl) ethyl (meth) acrylate, 2- (3-phenylphenyl) ethyl (meth) acrylate, 2- (4- Benzylphenyl) ethyl (meta) It may include a methacrylate, or a mixture thereof, but is not limited to these.

개시제Initiator

The initiator can be a photoinitiator. The photoinitiator can be used without limitation as long as it can exhibit excellent photoreaction in the ultraviolet wavelength range of about 150-500nm. For example, one or more selected from the group consisting of α-hydroxyketone series, benzophenone series and phenylglyoxylate series can be used, but is not limited thereto. For example, benzophenone, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4 , 4'-bis (dimethylamino) benzophenone, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,4,6- Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloro Romethyl) -s-triazine, thioxanthone, 2-methyl thioxanthone, benzoin or benzoin methyl ether and the like can be used.

In this embodiment, the initiator may be included in about 0.1-5% by weight, preferably about 0.5-2% by weight of the pressure-sensitive adhesive composition on a solids basis. Within the above range, the film after curing under UV exposure may exhibit high elongation and low curing shrinkage.

The pressure-sensitive adhesive composition may further include one or more selected from the group consisting of UV absorbers and antioxidants.

The ultraviolet absorber serves to improve the optical stability of the pressure-sensitive adhesive film after curing. The ultraviolet absorber may include one or more selected from the group consisting of benzotriazole-based, benzophenone-based and triazine-based, but is not limited thereto. For example, the ultraviolet absorber is 2- (benzotriazol-2-yl) -4- (2,4,4-trimethylpentan-2-yl) phenol, 2- (2'-hydroxy-5'- Methylphenyl) benzotriazole, 2- [2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- (2'-hydroxy-3', 5 ' -Di-t-butylphenyl) benzotriazole, 2,4-hydroxybenzophenone, 2,4-hydroxy-4-methoxybenzophenone, 2,4-hydroxy-4-methoxybenzophenone-5 -Sulfonic acid, 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4 -Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine or 2,4- Diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine and the like can be used.

UV absorbers may be included in about 0.1-1% by weight, preferably about 0.1-0.5% by weight of the pressure-sensitive adhesive composition on a solids basis. Yellowing of the surface of the film after curing within the above range can be prevented.

Antioxidant serves to improve the thermal stability by preventing the oxidation of the optical pressure-sensitive adhesive film after curing. The antioxidant may include, but is not limited to, one or more selected from the group consisting of phenolic compounds, quinone compounds, amine compounds, and phosphite compounds. For example, antioxidants include tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, tris (2,4-di-tert-butylphenyl) phosphite, and the like. Can be mentioned.

Antioxidant may be included in about 0.1-1% by weight of the adhesive composition on a solids basis. Preferably about 0.1-0.5% by weight. It is possible to prevent the aging of the film after curing within the above range, and exhibit excellent thermal stability.

The photocurable pressure-sensitive adhesive composition may further include a solvent commonly used in the field of photocurable pressure-sensitive adhesive composition. The solvent may be included in the balance in the pressure-sensitive adhesive composition.

The photocurable pressure-sensitive adhesive composition may have a curing shrinkage of about 2% or less. Within this range, it is possible to prevent the occurrence of leakage of the edge of the display screen, especially in a large size display. Preferably about 1.5% or less.

The curing shrinkage is determined by applying the specific gravity of the liquid composition and the photocurable pressure sensitive adhesive composition onto a release film containing PET (polyethylene terephthalate) and curing to about 3000-5000 mJ / cm ² before curing. Can be calculated. Hardening shrinkage is calculated | required by following formula (1).

The photocurable pressure-sensitive adhesive composition may be about 35-60kgf adhesion to the glass plate. The method of measuring the adhesive force is not particularly limited. For example, the size of the lower glass is 2cm x 2cm x 1mm, the size of the upper glass is 1.5cm x 1.5cm x 1mm, and the photocurable pressure-sensitive adhesive composition is coated to a thickness of 500㎛, 200kgf at 25 ℃ It can be measured by the force peeling off the upper glass from the side with the force of.

The photocurable pressure sensitive adhesive composition may have a viscosity of about 500-2,000 cps at 25 ° C. In order to improve processability and shorten time during dispensing, the viscosity of the liquid resin may be in the above range, thereby improving flow spreadability and reducing the shrinkage rate.

The photocurable pressure-sensitive adhesive composition may be coated on a release film containing PET (polyethylene terephthalate) and the like and dried to form a optical pressure-sensitive adhesive film.

After curing the optical pressure-sensitive adhesive film may have an elongation of about 400% or more, preferably about 400-800% with respect to the film thickness of 500㎛. Within this range, it is possible to prevent the occurrence of leakage of the edge of the display screen, especially in a large size display. The curing may be performed at about 3000-5000mJ / cm ² , but is not limited thereto.

Elongation can be fabricated and evaluated by ASTM D368 method. Specifically, the photocurable pressure-sensitive adhesive composition to form a film on a release film containing polyethylene terephthalate (PET), etc., coated and cured to 3000mJ / cm ² instron Series 1X / s Automated materials tester- for a film thickness of 500㎛ 3343 can be used to measure the distance at which a specimen breaks.

In a second embodiment of the photocurable pressure-sensitive adhesive composition, the composition may include a binder, a noncurable compound, a photocurable monomer, and an initiator.

바인더bookbinder

The binder may be a urethane (meth) acrylate copolymer, butadiene rubber, isoprene rubber or mixtures thereof. Preferably it may be an isoprene-based rubber or a mixture containing the same.

Details of the binder are as described above.

In the above embodiment, the binder may be included in about 35 to 75% by weight, preferably about 50 to 70% by weight of the photocurable pressure-sensitive adhesive composition on a solids basis. Outdoor visibility can be improved within the above range, showing high elongation, low tensile strength, and low cure shrinkage.

비경화성 화합물Non-curable compound

Details of the non-curable compound are as described above.

Preferably, the non-curable compound may be xylene-formaldehyde resin. The xylene-formaldehyde resin has the advantage of no migration. In addition, xylene-formaldehyde resin has elasticity, heat resistance, optical properties and low shrinkage properties.

The non-curable compound may include the structure of Formula 1 or may have a structure of Formulas 1-1, 1-2, 1a to 1e. These may be applied alone or in combination of two or more, preferably two or more of them are mixed:

In embodiments, the xylene-formaldehyde resin may have an Mw of about 100 g / mol-50,000 g / mol. Mixing properties with the isoprene-based rubber in the above range is good, there is an advantage that the viscosity and modulus can be easily adjusted.

The xylene-formaldehyde resin may have a hydroxyl value of about 20 to 500 mg / KOHmg, preferably about 20 to 40 mg / KOHmg. In the above range, there is an advantage in that the adhesion to the glass substrate is good.

The xylene-formaldehyde resin may have a polydispersity (PDI) of about 1-5. There is an advantage in that the physical properties of each part of the coating film in the above range.

The xylene-formaldehyde resin may be included in about 2 to 30% by weight, preferably about 5 to 30% by weight, more preferably about 10-30% by weight of the photocurable pressure-sensitive adhesive composition on a solids basis. It has a low shrinkage within the above range, it can have a good balance of elongation and adhesion.

The content ratio of the isoprene rubber to the xylene-formaldehyde resin may be more than 1, preferably about 1.1 to 10, more preferably about 1.5-7. In the above range, there is an advantage of excellent light curing properties.

The content between the binder and the xylene-formaldehyde resin may be higher in the binder. For example, the weight ratio between the binder and the xylene-formaldehyde resin may be about 60:40 to 95: 5. Excellent photocuring properties in the above range, there is one advantage.

In embodiments, the sum of the binder and the xylene-formaldehyde resin may be about 65-85% by weight of the pressure-sensitive adhesive composition on a solids basis. It is easy to control the shrinkage in the above range, and there is an advantage in that the optical properties are good even when mixing. Preferably about 70-85% by weight.

광경화형 모노머Photocurable Monomer

The photocurable monomer is a vinyl monomer having an aromatic group, a monomer having a vinyl group or a silane group, a vinyl monomer having an alicyclic group, a (meth) acrylic monomer having an alicyclic hetero ring, a vinyl monomer having an alkyl group, or a vinyl having a hydroxyl group Monomers, vinyl monomers having a carboxyl group, and the like can be used.

Preferably, the photocurable monomer is a vinyl monomer having an aromatic group, a monomer having a vinyl group and a silane group, a (meth) acrylate having a monocyclic or heterocyclic alicyclic group, and a monocyclic alicyclic ring having nitrogen, oxygen or sulfur It may be a mixture of (meth) acrylic monomers having a group hetero ring.

For example, the photocurable monomer may be a (meth) acrylate having a substituted or unsubstituted aryl group, aryloxy group or aralkyl group having 6 to 20 carbon atoms; (Meth) acrylates having a monocyclic or heterocyclic alicyclic ring having 10 to 20 carbon atoms; (Meth) acrylic monomers having a monocyclic alicyclic hetero ring having 4 to 6 carbon atoms and having nitrogen, oxygen or sulfur; And monomers having vinyl groups and silane groups or mixtures thereof may be used, but are not necessarily limited thereto.

The vinyl monomer having the aromatic group is not particularly limited as long as it is a (meth) acrylate having a substituted or unsubstituted aryl group, aryloxy group, or aralkyl group having 6 to 20 carbon atoms. For example, benzyl (meth) acrylate, phenoxy (meth) acrylate, 2-ethylphenoxy (meth) acrylate, phenyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 2-phenyl Propyl (meth) acrylate, 4-phenylbutyl (meth) acrylate, 2-2-methylphenylethyl (meth) acrylate, 2-3-methylphenyl (meth) acrylate, 2-4-methylphenylethyl (meth) acrylic Late, 2- (4-propylphenyl) ethyl (meth) acrylate, 2- (4- (1-methylethyl) phenyl) ethyl (meth) acrylate, 2- (4-methoxyphenyl) ethyl (meth) Acrylate, 2- (4-cyclohexylphenyl) ethyl (meth) acrylate, 2- (2-chlorophenyl) ethyl (meth) acrylate, 2- (3-chlorophenyl) ethyl (meth) acrylate, 2 -(4-chlorophenyl) ethyl (meth) acrylate, 2- (4-bromophenyl) ethyl (meth) acrylate, 2- (3-phenylphenyl) ethyl (meth) acrylate, 2- (4- Benzylphenyl) ethyl (meta) It may include a methacrylate, or a mixture thereof, but is not limited to these. The vinyl monomers having the aromatic groups may be used alone or in combination of two or more thereof. Vinyl-based monomer having an aromatic group may be included in about 1-40% by weight, preferably about 10-30% by weight of the photocurable monomer.

The monomer having a vinyl group and a silane group can increase the adhesion to glass. The detail about the monomer which has a vinyl group and a silane group is as above-mentioned. The monomer having a vinyl group and a silane group may be included in about 1-30% by weight, preferably about 2-15% by weight of the photocurable monomer. Within this range, workability during coating is easy and low shrinkage results upon curing.

Details of the vinyl monomer having the alicyclic group are as described above. Vinyl-based monomer having an alicyclic group may be included in about 1-70% by weight, preferably about 50-70% by weight of the photocurable monomer. It is easy to workability when coating in the above range, it is possible to obtain a result of low shrinkage rate when curing.

Details of the (meth) acrylic monomer having the alicyclic hetero ring are as described above. The (meth) acrylic monomer having an alicyclic hetero ring may be included in about 1-30% by weight, preferably about 2-15% by weight of the photocurable monomer. It is easy to workability when coating in the above range, it is possible to obtain a result of low shrinkage rate when curing.

Details of the vinyl monomer having the hydroxy group are as described above. The monomer having a hydroxy group may be included in about 0-20% by weight, preferably about 1-15% by weight of the photocurable monomer. The desired modulus can be obtained after curing within the above range.

Details of the vinyl monomer having the alkyl group are as described above. The monomer having an alkyl group may be included in about 0-20% by weight, preferably about 2-17% by weight of the photocurable monomer. It is easy to workability when coating in the above range, it is possible to obtain a result of low shrinkage rate when curing.

Details of the monomer having a carboxylic acid group are as described above. The monomer having a carboxylic acid group may be included in about 0-6% by weight, preferably about 1-5% by weight of the photocurable monomer. Within this range, workability during coating is easy and low shrinkage results upon curing.

In the above embodiment, the photocurable monomer may be included in about 12 to 40% by weight, preferably about 12 to 38% by weight, more preferably about 12 to 27% by weight of the photocurable pressure-sensitive adhesive composition on a solids basis. Within this range, the curing is effected effectively during photocuring, and facilitates the viscosity control of the photocurable material.

개시제Initiator

The initiator can be a photoinitiator. Although the photoinitiator can use 1 or more types chosen from the group which consists of a benzophenone type, an acetophenone type, a triazine type, a thioxanthone type, a benzoin type, or an oxime type compound, It is not limited to these. Details are as described above.

In this embodiment, the initiator may be included in about 1 to 5% by weight, preferably, about 1.5 to 4.5% by weight of the photocurable pressure-sensitive adhesive composition. Within this range, the photocuring is made smooth, and the viscosity of the photocurable material does not occur.

The composition may further include one or more additives such as ultraviolet absorbers and antioxidants.

The ultraviolet absorbent serves to improve the optical stability of the pressure-sensitive adhesive composition. The ultraviolet absorber may include one or more selected from the group consisting of benzotriazole-based, benzophenone-based and triazine-based, but is not limited thereto. Details of the ultraviolet absorbent are as described above.

In the above embodiment, the ultraviolet absorbent may be included in about 0.1 to 1% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, the hardening by the weak ultraviolet rays is prevented and the storage stability of the photocurable material is improved.

The antioxidant serves to improve thermal stability by preventing oxidation of the pressure-sensitive adhesive composition as a heat stabilizer. The antioxidant may include one or more selected from the group consisting of phenolic compounds, quinone compounds, amine compounds, and phosphite compounds, but is not limited thereto.

Details of the antioxidant are as described above.

In the above embodiment, the antioxidant may be included in about 0.1 to 1% by weight of the adhesive composition on a solids basis. Within this range, it is possible to prevent the material from being deteriorated by heat, thereby increasing the storage stability of the material.

The composition may further comprise urethane acrylate, polyester acrylate and acrylic acrylate oligomer. The oligomer should be excellent compatibility with the butadiene rubber binder, it can achieve a viscosity control and adhesion. For example, the oligomer is Mw about 100 ~ 5000g / mol, characterized in that the polypropylene glycol has an acrylate having an isocyanate group and a silane having an isocyanate group. The oligomer may be included in about 0 to 20% by weight of the adhesive composition on a solids basis. Within this range, it is easy to adjust the viscosity of the photocurable composition, it is possible to raise the adhesion with the glass. It is also effective in reducing shrinkage after photocuring.

The photocurable pressure-sensitive adhesive composition may have a curing shrinkage of about 3% or less, preferably about 0.1-2.6%, and more preferably about 1.3-2.6%. The curing shrinkage ratio is calculated according to the above formula 1.

The photocurable pressure-sensitive adhesive composition has a pH of about 4 or more, for example, about 4-8. As such, since the pH is about 4 or more, corrosion of the substrate can be minimized.

The photocurable pressure-sensitive adhesive composition may be an elongation of about 400 to 800%, preferably about 410-550% by ASTM D412.

The photocurable pressure-sensitive adhesive composition may have a modulus of about 10 kPa-50 kPa, preferably about 20 kPa-40 kPa. The modulus is irradiated to the pressure-sensitive adhesive composition at 2000mJ / cm ² , the cured to a thickness of about 500um, 25mm in diameter to make a film, and then the pre-concierge to 1rad with ARES model name ARES-G2 (TAinstrument), temperature It is the value measured, heating up at a speed from 25 degreeC to 100 degreeC (10 degreeC / min).

The photocurable pressure-sensitive adhesive composition may be preferably applied to the liquid pressure-sensitive adhesive used in the optical film or the substrate of the display device. In particular, it is useful for adhesion between the cover window and the transparent electrode film such as ITO.

In a third embodiment of the photocurable pressure-sensitive adhesive composition, the composition is a urethane bond and -SiX ₁ X ₂ X ₃ (X ₁ , X ₂ and X ₃ are the same or different from each other, hydrogen, hydroxyl groups, alkyl groups of 1-10 carbon atoms, carbon atoms Aromatic compounds containing an alkoxy group having 1-10 or an aryl group having 6-20 carbon atoms (hereinafter referred to as an 'non-curable urethane silane compound').

The pressure-sensitive adhesive composition may further include a binder, a photocurable monomer and an initiator in addition to the non-curable urethane silane compound.

비경화성 우레탄 실란 화합물Non-curable Urethane Silane Compound

The non-curable urethane silane compound may include a compound formed from the above-mentioned non-curable compound.

The non-curable urethane silane compound may be prepared by a urethane reaction of a non-curable compound, preferably an aromatic compound, and an isocyanate-containing silane compound. The reaction of the hydroxyl group of the aromatic alcohol compound with the isocyanate group of the isocyanate-containing silane compound forms a urethane bond.

The aromatic alcohol compound is a non-curable compound, and may have a structure of Chemical Formulas 1, 1-1, 1-2, 1a to 1e.

Preferably, the aromatic alcohol compound may have a structure of Formula 3 below.

(In the above, R ₁₁ to R ₂₈ are the same or different, hydrogen, linear or branched alkyl group having 1 to 10 carbon atoms, hydroxyl group, substituted alkyl group having 1 to 10 carbon atoms,-(-CH _2- ) sO- [-CH ₂ -CH ₂ O-] t-CH ₂ CH ₂ OH (s is an integer of about 0-5, t is an integer of about 0-5),

At least one of R ₁₁ to R ₂₈ is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group, or-(-CH _2- ) sO-[-CH ₂ -CH ₂ O-] t-CH ₂ CH ₂ OH (s is an integer from about 0-5, t is an integer from about 0-5).

More preferably, the aromatic alcohol compound may have a structure of formula (4).

The aromatic alcohol compound may be synthesized, but a commercially available xylene resin (X-11, Anhui China) may be used.

The isocyanate-containing silane compound can be used without limitation as long as it is a compound having an isocyanate group and -SiX1X2X3. For example, the silane compound may have a structure of Formula 5 below.

(Wherein X ₁ , X2 and X ₃ are the same or different and are hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and u is about 0-5 Is an integer of)

Preferably u is an integer from about 1-5

The isocyanate-containing silane compound may preferably be isocyanatopropyltrialkoxysilane, more preferably 3-isocyanatopropyltriethoxysilane.

Most preferably, the non-curable urethane silane compound may have a structure of Formula 6 below.

(Wherein X ₁ , X ₂ , X ₃ are the same or different and are hydrogen, a hydroxyl group, an alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms or an aryl group having 6-20 carbon atoms, u being about 0- Is an integer of 5)

An aromatic alcohol compound and an isocyanate containing silane compound can form a non-curable urethane silane compound by a normal urethane coupling reaction. For example, it may be prepared by reacting at about 40 ℃-80 ℃. The aromatic alcohol compound: isocyanate containing silane compound in the urethane bond reaction may be included in a molar ratio of about 1: 0.8 to 1: 1.

The urethane bonding reaction can be carried out using a catalyst such as dibutyltin dilaurate (DBTDL).

The Mw of the non-curable urethane silane compound may be about 500-40,000 g / mol.

The viscosity of the non-curable urethane silane compound may be about 40-60,000 cps at 25 ℃.

In this embodiment, the non-curable urethane silane compound may be included in about 1-30% by weight, preferably about 5-20% by weight of the adhesive composition on a solids basis. In the above range, the initial adhesive force is lowered to increase the reworking property, but may increase the adhesive strength when further cured.

바인더bookbinder

The binder may be a urethane (meth) acrylate copolymer, butadiene rubber, isoprene rubber or mixtures thereof. Preferably it may be a urethane (meth) acrylate copolymer, butadiene rubber or a mixture thereof.

The viscosity of the urethane (meth) acrylate copolymer may be about 1,000-100,000 cps, preferably about 5,000-50,000 cps at 25 ° C. Within this range, the curing shrinkage rate can be reduced.

The Mw of the urethane (meth) acrylate copolymer can be about 2,000-40,000 g / mol. Within this range, the durability, adhesion, elongation, heat resistance, and moisture resistance of the optical adhesive may be good. Preferably about 2,000 to 40,000 g / mol, more preferably about 10,000 to 26,000 g / mol.

The PDI of the urethane (meth) acrylate copolymer can be about 1.0-2.5. Within the above range, the molecular weight distribution of the urethane (meth) acrylate copolymer is small, there may be an effect that the physical properties of the copolymer is equivalent.

The detail of the manufacturing process of a polyol, a diisocyanate type compound, a (meth) acrylate monomer, and a urethane (meth) acrylate copolymer is as above-mentioned.

The details of the butadiene rubber and the isoprene rubber are as described above.

In this embodiment, the binder may be included in about 25-83.8% by weight, preferably about 50-70% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, it is possible to adjust the viscosity of the material to improve workability and to exhibit a low cure shrinkage value.

광경화형 모노머Photocurable Monomer

The photocurable monomer is a vinyl monomer having a hydroxy group, a vinyl monomer having an alkyl group, a vinyl monomer having an alicyclic group and a (meth) acrylic monomer having an alicyclic hetero ring, a vinyl monomer having a carboxylic acid group, a vinyl group and a silane group A monomer, a vinyl monomer having an aromatic group, or a mixture thereof can be used.

Preferably, the photocurable monomer may be a mixture of a vinyl monomer having a hydroxy group, a vinyl monomer having an alicyclic group, a (meth) acrylic monomer having an alicyclic hetero ring, and a vinyl monomer having an alkyl group.

In this embodiment, the photocurable monomer may be included in about 15-40% by weight, preferably about 18-39% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, the viscosity can be adjusted to improve workability and exhibit low shrinkage values.

Details of the vinyl monomer having a hydroxy group are as described above. The vinyl monomer having a hydroxy group may be included in an amount of about 1-20 wt%, preferably about 8-18 wt%, in the pressure-sensitive adhesive composition.

Details of the vinyl monomer having an alkyl group are as described above. Vinyl-based monomer having an alkyl group may be included in about 1-10% by weight, preferably about 1-5% by weight in the pressure-sensitive adhesive composition. It is possible to obtain a result that can solve the stress stress within the above range.

Details of the vinyl monomer having an alicyclic group are as described above. Vinyl-based monomer having an alicyclic group may be included in about 4-20% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, a result of facilitating workability during coating by adjusting the viscosity of the optical pressure-sensitive adhesive can be obtained.

Details of the (meth) acrylic monomer having an alicyclic hetero ring are as described above. The (meth) acrylic monomer having an alicyclic hetero ring may be included in an amount of about 1-10% by weight, preferably about 1-5% by weight, in the pressure-sensitive adhesive composition. Within this range, a result of increasing adhesion between the optical adhesive and the transparent electrode film such as glass or ITO film can be obtained.

Details of the vinyl monomer having a carboxylic acid group are as described above. Vinyl-based monomer having a carboxylic acid group may be included in about 0-20% by weight, preferably about 1-20% by weight of the pressure-sensitive adhesive composition on a solids basis.

The detail about the monomer which has a vinyl group and a silane group is as above-mentioned. Monomer having a vinyl group and a silane group may be included in about 0-20% by weight, preferably about 1-20% by weight of the pressure-sensitive adhesive composition on a solids basis.

Details of the vinyl monomer having an aromatic group are as described above.

개시제Initiator

The initiator can be a photoinitiator. The photoinitiator can be used without limitation as long as it can exhibit excellent photoreaction in the ultraviolet wavelength range of about 150nm-500nm. For example, one or more types selected from the group consisting of phosphine oxide series and phenylglyoxylate series can be used, but the present invention is not limited thereto. Specifically, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide (TPO), bisacryl phosphine oxide (BAPO), oxy-phenyl-acetic acid 2- [2 oxo-2-phenyl-acetoxy-e. Oxy] -ethyl ester, oxy-phenyl-acetic 2- [2-hydroxy-ethoxy] -ethyl ester, or mixtures thereof.

In this embodiment, the initiator may be included in about 0.1-5% by weight, preferably about 0.5-3% by weight of the adhesive composition on a solids basis. Within the above range, the film after curing under UV exposure may exhibit high elongation and low curing shrinkage.

In the above embodiment, the pressure-sensitive adhesive composition may further include a UV absorber.

자외선 흡수제UV absorbers

The ultraviolet absorber serves to improve the optical stability of the pressure-sensitive adhesive film after curing. The ultraviolet absorber may include one or more selected from the group consisting of benzotriazole-based, benzophenone-based and triazine-based, but is not limited thereto. Details of the ultraviolet absorbent are as described above.

In this embodiment, the ultraviolet absorber may be included in about 0.1-1% by weight, preferably about 0.1-0.5% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, yellowing of the surface of the film after curing can be prevented.

When the photocurable pressure-sensitive adhesive composition is cured, the initial adhesive strength measured for the pressure-sensitive adhesive film thickness of 200 μm is A, and the adhesive strength measured after leaving the film at 70 ° C. for 1 hour is B, and B / A is about 2 or more. This can be Preferably, it may be about 2-5.

Initial adhesive force A can be measured by a conventional method. For example, the photocurable pressure-sensitive adhesive composition for film formation is coated between glass (for example, the size of the lower glass is 2 cm x 2 cm x 1 mm, and the size of the upper glass is 1.5 cm x 1.5 cm x 1 mm). After hardening at 3,000 mJ / cm <^2> (for example, 94% or more of hardening rate), the sample containing the film of 200 micrometers in thickness is produced. For the prepared samples, the force of peeling the upper glass was pushed away from the side with a force of 200 kgf at 25 ° C. with a dage series 4000 PXY, which is an adhesive force measuring instrument. The initial adhesion may be about 18 kgf or less, preferably about 10-18 kgf.

Adhesion B after being left at 70 ° C. for 1 hour to prepare a sample in the same manner as the initial adhesion measurement. The prepared sample is left at 70 ° C. for 1 hour and then the adhesion is measured in the same manner. After 1 hour at 70 ° C., the adhesion may be about 50 kgf or more, preferably about 60-70 kgf.

The film made of the photocurable pressure-sensitive adhesive composition has a low initial adhesive force. On the other hand, a film made of the photocurable pressure-sensitive adhesive composition can significantly increase the adhesive strength by maintaining at about 65-85 ° C., preferably at about 70 ° C. for about 30 minutes-2 hours, preferably about 1 hour. As a result, the film can facilitate the rework when a failure occurs initially, and if there is no initial failure, it is possible to increase the adhesive strength by performing a constant treatment can increase the usability of the pressure-sensitive adhesive film.

The film made of the pressure-sensitive adhesive composition may increase the adhesive strength even when the film is left at about 25 ° C. for a predetermined time even without heat curing at about 65-85 ° C.

The photocurable pressure-sensitive adhesive composition may have a curing shrinkage of about 2% or less. Preferably about 1.5% or less, and more preferably about 0.7 to 1.3%.

Cure shrinkage rate can be measured by a conventional method. Specific gravity is measured before hardening about a liquid photocurable adhesive composition. The pressure-sensitive adhesive composition is coated on a PET release film and cured at about 3000-5000mJ / cm ² to prepare an optical pressure-sensitive adhesive film having a thickness of 200 μm of the adhesive layer. The release film is removed and specific gravity is measured for the optical pressure-sensitive adhesive film having a thickness of 200 μm. Hardening shrinkage is computed according to Formula 1 mentioned above.

After curing the photocurable pressure-sensitive adhesive composition may have a tensile strength of about 1gf / mm ² or less, preferably about 0.1 ~ 1gf / mm ² with respect to the pressure-sensitive adhesive film thickness 500㎛.

Tensile strength can be measured by a conventional method. For example, according to ASTM D638 method, the pressure-sensitive adhesive composition is coated on a release PET film and cured to about 1000-6000 mJ / cm ² . Tensile strength at break of the specimen was measured using an instron Series 1X / s Automated materials tester-3343 for a film thickness of 500 μm.

In a fourth embodiment of the photocurable pressure sensitive adhesive composition, the composition comprises (A) a binder, (B) a photocurable monomer, (C) a noncurable compound, and (D) a photoinitiator, wherein the photoinitiator has an absorption wavelength of about 350 nm. A photoinitiator (D1) having an excess of 400 nm or less and a photoinitiator (D2) having an absorption wavelength of about 200 nm or more and 350 nm or less may be included in a weight ratio of about 1: 0.5 to 1: 5.

바인더bookbinder

As the binder, a urethane (meth) acrylate copolymer, butadiene rubber, isoprene rubber or a mixture thereof can be used.

In this embodiment, the binder may be included in about 25-83.3% by weight of the adhesive composition on a solids basis. Within this range, it is possible to adjust the viscosity of the material to improve the workability and to exhibit a low curing shrinkage value. Preferably about 40 to 60% by weight, more preferably about 45 to 56% by weight.

The Mw of the urethane (meth) acrylate copolymer may be about 2,000-50,000 g / mol, preferably about 2,000-40,000 g / mol. Within this range, the durability, adhesion, elongation, heat resistance, and moisture resistance of the optical adhesive may be good.

The PDI of the urethane (meth) acrylate copolymer can be about 1.0-3.0. Within the above range, the molecular weight distribution of the urethane (meth) acrylate copolymer is small, there may be an effect that the physical properties of the copolymer is equivalent.

The urethane (meth) acrylate copolymer can be prepared by first polymerizing a polyol and an isocyanate compound to produce a urethane oligomer, and further polymerizing the (meth) acrylate monomer.

The urethane (meth) acrylate copolymer may use a mixture of two or more urethane (meth) acrylate copolymers. Preferably, a mixture of a urethane (meth) acrylate copolymer (A1) polymerized with a diol-based polyol and a urethane (meth) acrylate copolymer (A2) polymerized with a triol-based polyol can be used. When used in combination, the adhesion can be increased. As the diols, polypropylene diol, polypropylene glycol diol, butanediol and the like can be used. As the triols, polypropylene triol, polypropylene glycol triol and the like can be used.

The urethane (meth) acrylate copolymer (A2) using triols as polyols may be included in about 3-8% by weight, preferably about 4-6% by weight in the photocurable pressure-sensitive adhesive composition. Within this range, it is possible to increase the adhesion and prevent the adhesive from becoming a hard type due to excessive use.

In the photocurable pressure sensitive adhesive composition, (A1) :( A2) may be included in a weight ratio of about 4.5: 1 to 10.5: 1. In the above range, the adhesion may be good. Preferably in a weight ratio of about 8: 1 to 10.5: 1.

The details of the butadiene rubber are as described above.

Details of the isoprene rubber are as described above.

광경화형 모노머Photocurable Monomer

Preferably, the photocurable monomer may be a mixture of a vinyl monomer having a hydroxy group, a vinyl monomer having an alicyclic group, and a (meth) acrylic monomer having an alicyclic hetero ring.

In this embodiment, the photocurable monomer may be included in about 15-40% by weight, preferably about 25-40% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, the viscosity of the material can be adjusted to improve workability and exhibit low shrinkage values.

Details of the vinyl monomer having an alicyclic group are as described above. Vinyl-based monomer having an alicyclic group may be included in about 4-20% by weight, preferably about 4-15% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, a result of facilitating workability during coating by adjusting the viscosity of the optical pressure-sensitive adhesive can be obtained.

Details of the (meth) acrylic monomer having an alicyclic hetero ring are as described above. The (meth) acrylic monomer having an alicyclic hetero ring may be included in an amount of about 1-20 wt%, preferably about 5-15 wt%, based on the solid content. Within this range, a result of increasing adhesion between the optical adhesive and the transparent electrode film such as glass or ITO film can be obtained.

Details of the vinyl monomer having an alkyl group are as described above. Vinyl-based monomer having an alkyl group may be included in about 0-10% by weight, preferably about 1-5% by weight in the pressure-sensitive adhesive composition. It is possible to obtain a result that can solve the stress stress within the above range.

Details of the vinyl monomer having a carboxylic acid group, the monomer having a vinyl group and a silane group, and the vinyl monomer having an aromatic group are as described above.

비경화성 화합물Non-curable compound

Details of the non-curable compound are as described above.

The non-curable compound may include the above Formula 1 or may have a structure of Formulas 1-1, 1-2, 1a to 1e.

In the above embodiment, the non-curable compound may be included in about 1 to 30% by weight of the adhesive composition on a solids basis. Within this range, the curing shrinkage rate can be lowered. Preferably about 10-30% by weight, more preferably about 10-25% by weight, most preferably about 14-25% by weight.

광개시제Photoinitiator

The photoinitiator comprises a photoinitiator (D1) having an absorption wavelength of greater than about 350 nm to 400 nm or less and a photoinitiator (D2) having an absorption wavelength of about 200 nm to 350 nm or less in a weight ratio of (D1) :( D1) of about 1: 0.5 to 1: 5. It may be a mixture.

The photoinitiator (D1) may include a photoinitiator having an absorption wavelength of greater than about 350 nm and up to 400 nm. Preferably, the absorption wavelength may be about 360 nm to 400 nm.

The photoinitiator (D1) may include, but is not limited to, mono acrylic phosphine oxide series or mixtures thereof. Preferably, a mono acryl phosphine oxide series of formula (7) may be used.

(In the above, R ₆ , R ₇ , R ₈ is hydrogen, hydroxy group, halogen, substituted or unsubstituted C 1-5 alkyl group, substituted or unsubstituted C 6-10 aryl group, n is 1 to 5 Is an integer of)

The substituent for the alkyl group or aryl group may be an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxy group or a halogen.

Preferably, R ₆ is hydrogen, R ₈ is an aryl group having 6-10 carbon atoms, R ₇ may be an aryl group having 6-10 carbon atoms substituted with an alkyl group having 1-5 carbon atoms.

The photoinitiator (D1) may be synthesized by a conventional synthetic method, or may be purchased and used in a commercially available product. For example, (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide (TPO) can be used, but is not limited thereto.

The photoinitiator (D2) may include a photoinitiator having an absorption wavelength of about 200 nm to 350 nm. Preferably the absorption wavelength may be about 280nm ~ 340nm.

The photoinitiator (D2) may be, but is not limited to, alpha-hydroxyarylketone series, phenylglyoxylate series, or mixtures thereof. Preferably, a mixture of alpha-hydroxyaryl ketone series represented by the following formula (8) and phenylglyoxylate series represented by the formula (9) may be used.

(In the above, R ₉ , R ₁₀ , R ₁₁ are hydrogen, hydroxy group, halogen, substituted or unsubstituted C1-5 alkyl group, substituted or unsubstituted C6-10 aryl group, or R ₁₀ and R ₁₁ are connected to each other to form an alicyclic group having 5 to 10 carbon atoms, m is an integer of about 1-5)

(In the above, R ₁₃ is hydrogen, an alkyl group having 1-5 carbon atoms, R ₁₂ is an ethoxy ethyl group having a phenylglyoxylate group or an ethoxy group having a hydroxy group, and p is an integer of about 1-5.)

Preferably, R ₉ is hydrogen, R ₁₀ and R ₁₁ may be connected to each other to form an alicyclic group having 5 to 10 carbon atoms.

In the photoinitiator (D2), the initiator of Formula 8 may be prepared by synthesis by a conventional synthetic method, or may be purchased and used in a commercially available product. For example, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) or the like can be used, but is not limited thereto.

In the photoinitiator (D2), the initiator of formula (9) may be prepared by synthesis by a conventional synthetic method, or may be prepared by oxy phenyl acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy phenyl Mixtures of acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester (Irgacure 754) and the like can be used.

In the photoinitiator (D2), initiator (D21) of formula (8): initiator (D22) of formula (9) may be included in a weight ratio of about 1: 0.5 to 1: 2.

The photoinitiators (D1) and (D2) may include (D1) :( D2) in a weight ratio of about 1: 0.5 to 1: 5 in the photocurable pressure-sensitive adhesive composition. If the weight ratio is less than 0.5, there may be a disadvantage that the curing rate is low, and if the weight ratio is more than 5, there may be a problem in durability because the initiator remains after curing. Preferably, (D1) :( D2) may be included in a weight ratio of about 1: 0.6 to 1: 3.

Photoinitiator (D1) may be included in about 0.1-1.5% by weight, preferably about 0.4-1% by weight of the adhesive composition on a solids basis. In the above range, there may be an effect that the curing proceeds quickly.

Photoinitiator (D2) may be included in about 0.1-1.5% by weight, preferably about 0.6-1.2% by weight of the adhesive composition on a solids basis. In this range, the internal curing may proceed sufficiently.

The photoinitiator may include, in addition to the photoinitiators (D1) and (D2), photoinitiators that are commonly used. For example, it may include an alpha-amino ketone series, a bis acryl phosphine oxide series, a metallocene series or a mixture thereof.

In the above embodiment, the photoinitiator may be included in about 0.1 to 5% by weight of the adhesive composition on a solids basis. In the above range, the film after curing under UV exposure may exhibit high elongation and low cure shrinkage. Preferably about 1.0-3.0% by weight more preferably about 1.0-2.0% by weight.

In the above embodiment, the pressure-sensitive adhesive composition may further include one or more selected from the group consisting of UV absorbers and antioxidants.

자외선 흡수제UV absorbers

The ultraviolet absorber serves to improve the optical stability of the pressure-sensitive adhesive composition. The ultraviolet absorber may include one or more selected from the group consisting of benzotriazole-based, benzophenone-based and triazine-based, but is not limited thereto. Details are as described above.

In this embodiment, the ultraviolet light absorber may be included in about 0.1-2% by weight, preferably about 0.1-1% by weight of the photocurable pressure-sensitive adhesive composition on a solids basis. It is possible to prevent the yellowing of the surface of the film after curing within the above range.

산화 방지제Antioxidant

Antioxidant serves to prevent oxidation of the pressure-sensitive adhesive composition to improve thermal stability. Details are as described above.

In this embodiment, the antioxidant may be included in about 0.01-2% by weight, preferably about 0.01-1% by weight of the photocurable pressure-sensitive adhesive composition on a solids basis. It prevents the aging of the film after curing within the above range, and shows excellent thermal stability.

The composition may be cured with a curing energy of about 50-500 mJ / m ² at a coating film thickness of about 100 μm-600 μm. Existing photocurable pressure-sensitive adhesive composition could be cured at a curing energy of about 1000-7000mJ / cm ² at a coating film thickness of about 100㎛ ~ 600㎛. However, the photocurable pressure-sensitive adhesive composition of the present invention can be sufficiently hardened even by irradiation of lower curing energy.

The composition may have a curing rate of about 96% or more even at a curing energy of about 200 mJ / cm ² at a coating film thickness of about 100 μm to 600 μm. Preferably, the cure rate may be about 96-100%.

Curing rate can be measured by a conventional method. For example, it can be obtained from the intensity (area in the peak) of the peak in the range of wave numbers 1640-Xcm ^-1 to 1640 + Xcm ^-1 (X is 0 to 5), which appears in the FT-IR measurement before and after curing. . Preferably it can be calculated | required from the intensity | strength in 1635 cm <^-1> -1645 cm <^-1> .

Specifically, FT-IR is photographed about the container containing 1 g of adhesive compositions, and IR spectrum is calculated | required. The intensity (B _o ) of the reference peak in the IR spectrum and the intensity (h ₀ , area within the peak) of 1635 cm ⁻¹ to 1645 cm ⁻¹ are obtained. 1 g of the pressure-sensitive adhesive composition is coated on a release PET film and dried to prepare a film having a thickness of 100 μm. A curing energy of 200 mJ / m ² is irradiated to a container containing a film having a coating thickness of 100 μm. FT-IR is taken on the container in the same manner as above to find the IR spectrum. The intensity (B ₁ ) of the reference peak in the IR spectrum and the intensity (h ₁ , area within the peak) of 1635 cm ⁻¹ to 1645 cm ⁻¹ are obtained. The hardening rate is computed according to following formula 2.

(In the above, B is B _o / B ₁ )

The composition may have a cure shrinkage of about 3% or less.

The curing shrinkage measures the specific gravity of the liquid composition before curing the photocurable pressure-sensitive adhesive composition. The photocurable pressure-sensitive adhesive composition is coated on a release film containing PET (polyethylene terephthalate) and cured to about 3000-5000mJ / cm ² to prepare an optical adhesive film having a thickness of 200 μm. The release film is removed and specific gravity is measured for the optical pressure-sensitive adhesive film having a thickness of 200 μm. The cure shrinkage rate is obtained according to Equation 1 described above. Preferably, the cure shrinkage rate may be about 1.9-2.0%.

The curing method of the composition comprises coating a photocurable pressure-sensitive adhesive composition on a release film and drying to prepare a film having a coating film thickness of about 100㎛ ~ 600㎛; And irradiating an energy of about 50 mJ / m ² ˜500 mJ / m ² .

In a fifth embodiment of the photocurable pressure sensitive adhesive composition, the composition may have a viscosity of about 2,000-4,000 cps at 25 ° C. If the viscosity is less than 2,000 cps, there may be a problem that it is difficult to clean the materials coming out after curing due to the overflow of the liquid material out of the lamination region before curing. If the viscosity is more than 4,000 cps, the dispersing process may be problematic because the spreading property of the liquid material is poor when the cover window and the touch panel are laminated. Preferably about 2500-3000 cps, more preferably about 2750-3000 cps.

Viscosity is stored for 24 hours in a thermostat (25 ℃) photocurable pressure-sensitive adhesive composition. The viscosity of the photocurable pressure-sensitive adhesive composition is measured at 25 ° C. using a viscosity meter (Brookfield DV-III).

The photocurable pressure-sensitive adhesive composition may have a curing shrinkage of about 1.5% or less. Within this range, it is possible to prevent the occurrence of leakage of the edge of the display display screen, especially when used in a large size display. Preferably about 1.3% or less.

Cure shrinkage rate can be measured by a conventional method. The specific gravity of the liquid composition is measured before curing. The photocurable pressure-sensitive adhesive composition is coated on a release film containing, for example, PET (polyethylene terephthalate). Curing at 3000-5000mJ / cm ² to obtain a 200㎛ thick optical pressure-sensitive adhesive film is measured its specific gravity. Hardening shrinkage is calculated | required according to said Formula 1.

The composition may comprise a binder.

바인더bookbinder

The binder may be a urethane (meth) acrylic copolymer, butadiene rubber, isoprene rubber or a mixture thereof. Preferably a mixture of urethane (meth) acrylate copolymers having a specific molecular weight range may be included as binder.

The composition comprises a urethane (meth) acrylate copolymer having (A1) Mw of about 30,000 g / mol or more and 60,000 g / mol or less and a urethane (meth) acryl having (A2) Mw of about 5,000 g / mol or more and less than 30,000 g / mol Mixtures of latex copolymers.

When (A1) Mw contains only urethane (meth) acrylate copolymers of about 30,000 g / mol or more and 60,000 g / mol or less, an excess amount of the photocurable monomer is used to lower the crude liquid viscosity of the high viscosity (meth) acrylate copolymer. This increases the curing shrinkage, which can cause leakage at the edge of the display screen when used for large size displays.

(A2) When Mw contains only a urethane (meth) acrylate copolymer having a content of about 5,000 g / mol or more but less than 30,000 g / mol, peeling may occur between the laminated window and the touch panel due to poor durability, resulting in peeling between the laminated window and heat resistance and heat resistance. Problems with poor habits can occur.

Preferably, the (A1) urethane (meth) acrylate copolymer may have an Mw of about 35,000 g / mol to 45,000 g / mol.

Preferably, the (A2) urethane (meth) acrylate copolymer has a urethane (acrylate) air of Mw of about 10,000 g / mol-20,000 g / mol, more preferably about 17,000 g / mol-20,000 g / mol. And mixtures of coalesces.

(A1) and (A2) may have a PDI of about 1-5. Preferably about 1.3-1.9.

The weight ratio of (A2) to (A1) in the mixture of urethane (meth) acrylate copolymers may be about 1.01-6. Within this range, the impact resistance can be enhanced by securing a low storage modulus and a low elastic modulus after curing the composition. The weight ratio of (A2) to (A1) may preferably be about 2-5, more preferably about 2.5-4.5.

(A1) may be included in less than about 25% by weight of the adhesive composition on a solids basis. Within this range, the storage modulus and the elastic modulus can be low to impart impact resistance. Preferably (A1) may be included in about 5-20% by weight, more preferably about 10-15% by weight of the composition.

The mixture of urethane (meth) acrylate copolymers may comprise about 10-45 weight percent (A1) and about 55-90 weight percent (A2). Preferably, about 15-30 weight percent (A1) and about 70-85 weight percent (A2).

The viscosity of the urethane (meth) acrylate copolymer can be about 25,000-400,000 cps at 25 ° C. Within this range, the curing shrinkage of the pressure-sensitive adhesive composition can be reduced.

The urethane (meth) acrylate copolymer can be prepared by first polymerizing a polyol and a diisocyanate compound to produce a urethane oligomer, and further polymerizing a (meth) acrylate monomer.

The detail about the manufacturing method of a polyol, a diisocyanate type compound, a (meth) acrylate monomer, and a urethane (meth) acrylate copolymer is as above-mentioned.

The urethane (meth) acrylate copolymers (A1) and (A2) can be obtained by adjusting the weight average molecular weight and content or reaction conditions of the polyol. For example, the polyol may use a weight average molecular weight of about 3000-4000 g / mol, but is not limited thereto.

The details of butadiene rubber and isoprene rubber are as described above.

The mixture of binders, particularly urethane (meth) acrylate copolymers, may comprise about 25-83.7 weight percent of the pressure-sensitive adhesive composition on a solids basis. In the above range, it is possible to improve the workability by adjusting the viscosity of the pressure-sensitive adhesive composition, lower the curing shrinkage rate, lower the storage modulus and the elastic modulus. Preferably about 25-80% by weight, more preferably about 50-55% by weight.

Photocurable pressure-sensitive adhesive composition It may further include a photocurable monomer and an initiator.

광경화형 모노머Photocurable Monomer

The photocurable monomer is a vinyl monomer having a hydroxy group, a vinyl monomer having an alkyl group, a vinyl monomer having an alicyclic group, a (meth) acrylic monomer having an alicyclic hetero ring, a vinyl monomer having a carboxylic acid group, or a vinyl having an aromatic group. Monomers, monomers having vinyl groups and silane groups, and the like can be used.

Preferably, the photocurable monomer may include a vinyl monomer having a hydroxy group, a vinyl monomer having an alicyclic group, and a (meth) acrylic monomer having an alicyclic hetero ring.

In the above embodiment, the photocurable monomer may be included in about 5-70% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, the viscosity of the material can be adjusted to improve workability and exhibit low shrinkage values. Preferably about 10-45% by weight, more preferably about 25-45% by weight.

Details of the vinyl monomer having a hydroxy group are as described above. Vinyl-based monomer having a hydroxyl group may be included in about 1-10% by weight, preferably about 5-10% by weight of the pressure-sensitive adhesive composition on a solids basis.

Details of the vinyl monomer having an alicyclic group are as described above. Vinyl-based monomer having an alicyclic group may be included in about 5-25% by weight, preferably about 10-25% by weight of the pressure-sensitive adhesive composition on a solids basis. By adjusting the viscosity of the optical pressure-sensitive adhesive within the above range can be obtained a result of ease of workability during coating.

Details of the vinyl monomer having an aromatic group and the monomer having a vinyl group and a silane group are as described above.

개시제Initiator

The initiator can be a photoinitiator. The photoinitiator can be used without limitation as long as it can exhibit excellent photoreaction in the ultraviolet wavelength range of about 150nm-500nm. For example, the photoinitiator may be used one or more selected from the group consisting of phosphine oxide series and phenylglyoxylate series, but is not limited thereto. Details of the photoinitiator are as described above.

In this embodiment, the initiator may be included in about 0.1-5% by weight, preferably about 0.5-4% by weight of the pressure-sensitive adhesive composition on a solids basis. Within the above range, the film after curing under UV exposure may exhibit high elongation and low curing shrinkage.

In the above embodiment, the photocurable pressure-sensitive adhesive composition may further comprise a non-curable compound, ultraviolet absorbent, antioxidant or a mixture thereof.

비경화성 화합물Non-curable compound

Details of the non-curable compound are as described above.

The non-curable compound may include, but is not limited to, one or more selected from the group consisting of the compounds represented by Formula 1 or Formula 1-1, 1-2, 1a to 1e.

In the above embodiment, the non-curable compound may be included in about 1-30% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, it is possible to prevent the hardening defects from occurring in the liquid phase without remaining in the film that is the hardened product upon curing. Preferably about 5-30% by weight, more preferably about 10-30% by weight, most preferably about 15-18% by weight.

자외선 흡수제UV absorbers

The ultraviolet absorber serves to improve the optical stability of the pressure-sensitive adhesive film after curing. The ultraviolet absorber may include one or more selected from the group consisting of benzotriazole-based, benzophenone-based and triazine-based, but is not limited thereto. Details are as described above.

In this embodiment, the ultraviolet absorber may be included in about 0.1-2% by weight, preferably about 0.1-1% by weight of the pressure-sensitive adhesive composition on a solids basis. Yellowing of the surface of the film after curing within the above range can be prevented.

산화 방지제Antioxidant

Antioxidant serves to improve the thermal stability by preventing the oxidation of the optical pressure-sensitive adhesive film after curing. The antioxidant may include, but is not limited to, one or more selected from the group consisting of phenolic compounds, quinone compounds, amine compounds, and phosphite compounds. Details are as described above.

In this embodiment, the antioxidant may be included in about 0.1-2% by weight of the adhesive composition on a solids basis. Preferably about 0.1-1% by weight. It is possible to prevent the aging of the film after curing within the above range, and exhibit excellent thermal stability.

The compositions according to the first to fifth embodiments described above may further include a silane coupling agent to enhance adhesion to the glass. The silane coupling agent can use what is known as a normal silane coupling agent, For example, the silane coupling agent containing a vinyl group or a mercapto group can be used. For example, polymerizable fluorine-containing silicon compounds, such as 3-methacryloxypropyl trimethoxysilane, trimethoxy silane, and vinyl triethoxy silane; Silicon compounds having an epoxy structure, such as 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propylmethyl dimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane; Amino group-containing silicon compounds such as 3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyl dimethoxysilane ; And 3-chloro propyl trimethoxysilane and the like may include one or more selected from the group consisting of, but is not limited thereto. The silane coupling agent may be included in about 1 to 5% by weight, preferably about 1 to 3% by weight of the pressure-sensitive adhesive composition on a solids basis. Within this range, the adhesion to the glass substrate is excellent, and even after a certain time, the adhesion of the material is further increased to maintain high adhesion after production.

The compositions according to the first to fifth embodiments described above may be used as a liquid optical clear adhesive (OCA) composition.

A display device according to another aspect of the present invention may include the photocurable composition or an adhesive layer made of the composition. For example, it may be used for adhesion between a cover window of a display and a transparent electrode film such as an ITO film.

Specifically, the device may include a touch screen panel (TSP) including a window glass including a cover glass, a transparent electrode film including ITO, and an adhesive layer between the cover glass and the transparent electrode film. have. 1 is a cross-sectional view of a display device of the present invention. According to FIG. 1, the adhesive layer 100 may be laminated between the window glass 400 including the cover glass 200 and the touch screen panel 500 including the transparent conductive film 300.

The transparent electrode film may be, but is not limited to, a film of tin oxide, indium oxide, carbon black, carbon nanotubes, platinum, gold, silver, conductive polymers or mixtures thereof.

In addition, the transparent electrode film may be at least one of indium tin oxide (ITO), fluorinated tin oxide (FTO), aluminum dopped zinc oxide (AZO), carbon nanotube (CNT), Ag nanowire, and graphene. This may be a laminated film, but is not limited thereto.

In one embodiment, the adhesive layer may be formed by coating the composition with a thickness of 500 μm and curing at 3000-5000mJ / cm ² , but is not limited thereto.

Preferably, the pressure-sensitive adhesive layer may be formed of a pressure-sensitive adhesive composition according to the fifth embodiment.

The adhesive layer may have an elastic modulus of less than about 0.01 kgf / mm ² for an adhesive layer thickness of 500 μm. When mounted to the display in the above range can be improved impact resistance. Preferably, it may be about 0.001 to 0.009 kgf / mm ² .

Elastic modulus can be measured according to ASTM D638. The photocurable pressure-sensitive adhesive composition is coated on a release PET film and cured to 3000 mJ / cm ^2, and then the modulus when the specimen is ruptured is measured using an Instron series IX / s Automated materials Tester 3343 for a film thickness of 500 μm.

The adhesive layer may have a storage modulus of about 6 × 10 ³ to 1 × 10 ⁴ Pa with respect to the thickness of the adhesive layer 500 μm. Within this range, impact resistance can be improved when mounted on a display. Preferably about 7 x 10 ³ to 9 x 10 ³ Pa.

Storage modulus can be measured by a conventional method. For example, 2000mJ / cm <^2> is irradiated to the photocurable adhesive composition. An optical pressure-sensitive adhesive film having a thickness of 500 µm and a diameter of 25 mm is obtained. Using ARES G2 (TA Instrument Co., Ltd.), a 1 sweep, 25mm cone, 25mm plate, 0.1% strain, frequency 2Hz and 25 ℃ conditions are measured by a frequency sweep.

The adhesive layer may have an elongation of about 500% or more, preferably about 500-800%, with respect to the thickness of the adhesive layer 500 μm. Within this range, it is possible to prevent the occurrence of leakage of the edge of the display screen, especially in a large size display.

Another aspect of the invention relates to a module assembly method. Module assembly method may include using the photocurable pressure-sensitive adhesive composition.

Specifically, the module assembly method comprises the steps of temporarily curing the photocurable pressure-sensitive adhesive composition in a laminate filled with a photocurable pressure-sensitive adhesive composition between the transparent electrode film layer and the window glass layer; Irradiating a light source from the side of the laminate; And it may include the step of curing the cured pressure-sensitive adhesive composition.

Preferably, in the module assembly method, the photocurable pressure-sensitive adhesive composition according to the fourth embodiment can be used.

Figure 2 shows the step of curing the photocurable pressure-sensitive adhesive composition. According to FIG. 1, a laminate is manufactured by filling a photocurable pressure-sensitive adhesive composition 3 between a transparent electrode film layer 1 and a window glass layer 2. Then, the photocurable pressure-sensitive adhesive composition is temporarily cured in a conventional manner including the UV lamp 4. The curing conditions are not limited but may be irradiated with an energy of about 500-6,000 mJ / cm ² .

3 and 4 show the step of irradiating the light source from the side of the laminate including the provisionally cured pressure-sensitive adhesive composition (3 '). The light source 5 can be irradiated from the side of the laminate, preferably from the side of the cured photocurable pressure-sensitive adhesive composition. In order to prevent the overflow of the photocurable pressure-sensitive adhesive composition, as shown in FIG. 3, the light source may be irradiated in a region where overflow may occur in the window glass layer. As a light source, as long as it can irradiate about 320nm-400nm light, it can use without limitation. For example, LED lamps can be used. The light source can be irradiated for about 1 to 15 seconds with an energy of about 50-6000 mJ / cm ² .

Figure 5 shows the step of curing the photocurable pressure-sensitive adhesive composition (3 ") cured outside the transparent electrode film, such as ITO film. According to Figure 4, the transparent electrode in a conventional manner including a UV lamp (4) The cured photocurable pressure-sensitive adhesive composition 3 ″ is cured. The present curing conditions are not limited but can be irradiated for about 5 seconds to 150 seconds with an energy of about 500-6,000 mJ / cm ² .

In the conventional module assembly method, in the step of curing the photocurable pressure-sensitive adhesive composition, the photocurable pressure-sensitive adhesive composition is pressed by the pressure caused by the air pressure formed between the window glass layer and the light source, the photocurable pressure-sensitive adhesive composition on the transparent electrode film, the window glass layer The overflow phenomenon occurred. This required the step (cleaning process) of removing the overflowing photocurable adhesive composition using a wiper etc.

On the other hand, the module assembly method of the present invention by curing the photocurable pressure-sensitive adhesive composition under the light source irradiation including the LED light source, so that the overflow phenomenon does not occur so that the module can be assembled without a conventional cleaning process.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

(1) Specific specifications of the components used in Examples 1-5 and Comparative Example 1 are as follows.

(A) urethane (meth) acrylate copolymer: urethane (meth) acrylate copolymer prepared in Preparation Example 1-3

(B) Reactive monomers: 4-hydroxybutyl acrylate (4-HBA), 2-hydroxyethyl methacrylate (2-HEMA), isobornyl acrylate (IBXA), acryloyl morpholine (ACMO) Isooctyl acrylate (IOA)

(C) Compound: Xylene resin (X-11) (Anhui Co.)

(D) Initiator: TPO, Irgacure 754

(E) UV absorbers: Tinuvin 384-2

(F) Antioxidant: Irganox 1010

제조예 1: 우레탄 (메타)아크릴레이트 공중합체의 제조Preparation Example 1: Preparation of Urethane (meth) acrylate Copolymer

80 g of polypropylenediol PPG300 was added to a 2 L four-necked flask, and a reflux condenser, thermometer, and dropping funnel were installed. The temperature of the flask solution was raised to 60 ° C. 0.1 g of dibutyltin dilaurate (DBTDL) diluted to 10% in toluene was added thereto, 8.5 g of IPDI (isophorone diisoyanate) was added thereto, and the temperature of the flask solution was maintained at 75 ° C. After confirming that the NCO-group was completely reacted, the mixture was cooled to 60 ° C., and 1.4 g of 2-hydroxyethyl methacrylate (HEMA) was added thereto. 0.4 g of MeOH was added after maintaining 60 ° C. for 2 hours. After maintaining 60 ° C. for 5 hours, the NCO-group disappeared by IR and cooled to 40 ° C. to prepare a urethane (meth) acrylate copolymer. The viscosity, Mw, PDI of the prepared copolymer was measured and the results are shown in Table 1.

제조예 2-3: 우레탄 (메타)아크릴레이트 공중합체의 제조Preparation Example 2-3 Preparation of Urethane (meth) acrylate Copolymer

Except for changing the content of each component in Preparation Example 1 was carried out in the same manner to prepare a urethane (meth) acrylate copolymer.

Table 1

		Preparation Example 1	Preparation Example 2	Preparation Example 3
Polyol (g)	PPG3000	80	80	80
Diisocyanate (g)	IPDI	8.5	8	7.5
Polymerization catalyst (g)	DBTDL	0.1	0.1	0.1
Alcohol (g)	MeOH	0.4	0.3	0.2
(Meth) acrylate type (g)	HEMA	1.4	1.3	1.2
Viscosity (cps, 25 ℃)		28,000	48,000	84,700
Solids (wt /%)		100	100	100
Mw		16.8K	19.0K	25.5K
PDI		1.3	1.4	1.8

실시예 1-5와 비교예 1:광경화형 점착제 조성물의 제조Example 1-5 and Comparative Example 1: Preparation of photocurable pressure-sensitive adhesive composition

The composition was prepared by mixing each component and stirring for 1 hour to the content described in Table 2 (unit: parts by weight) without a solvent.

TABLE 2

		Example 1	Example 2	Example 3	Example 4	Example 5	Comparative Example 1
(A)	Preparation Example 1	60	-	-	50	50	65
	Preparation Example 2	-	60	-	-	-	-
	Preparation Example 3	-	-	60	-	-	-
(B)	4-HBA	3	3	3	0	3	3
	2-HEMA	3	3	3	6	3	3
	IBXA	16.3	16.3	16.3	16.3	6.3	21.3
	ACMO	3	3	3	3	3	3
	IOA	3	3	3	3	3	3
(C)	X-11	10	10	10	20	30	-
(D)	TPO	One	One	One	One	One	One
(D)	Irgacure754	0.5	0.5	0.5	0.5	0.5	0.5
(E)	Tinuvin 384-2	0.1	0.1	0.1	0.1	0.1	0.1
(F)	Irganox 1010	0.1	0.1	0.1	0.1	0.1	0.1
all		100	100	100	100	100	100

The physical properties of the adhesive compositions prepared in Examples and Comparative Examples were measured, and the results are shown in Table 3 below.

1. Curing shrinkage rate: The pressure-sensitive adhesive composition prepared in Examples and Comparative Examples was cured. Before curing, the specific gravity of the liquid composition and the pressure-sensitive adhesive composition were coated on a release film containing PET, and the specific gravity of the optical pressure-sensitive adhesive film cured at 3000 mJ / cm ² was measured with a digital solid-state hydrometer DME-220E (Shinko Co., Ltd.). Calculated according to.

2. Elongation: The specimen was fabricated and evaluated by the ASTM D638 method. When the test piece was broken using Instron series IX / s Automated materials Tester-3343 for a film thickness of 500 μm after coating the pressure-sensitive adhesive composition prepared in Examples and Comparative Examples on a release PET film and curing at 3000 mJ / cm ² . The distance of was measured by elongation.

3. Adhesive force: Measure the adhesive force between glass and glass. The force of peeling was measured by pushing the upper glass from the side with a force of 200kgf at 25 ° C. with the dage series 4000PXY, which is an adhesive force measuring instrument. The lower glass had a size of 2 cm x 2 cm x 1 mm, the upper glass had a size of 1.5 cm x 1.5 cm x 1 mm, and the thickness of the pressure-sensitive adhesive composition was 200 μm.

4. Viscosity: The pressure-sensitive adhesive composition was stored in a thermostat (25 ° C.) for 24 hours and then measured using a viscometer (Brookfield DV-III).

5. Elastic modulus: It measured by the same method as the said elongation measurement.

6. Transmittance: Measured in the 400-800nm region with a Lambda 950 (perkin elmer) instrument.

7. Refractive index: It was measured by ASTM D1218 method, coated on a release PET film to have a thickness of 200 μm, cured at 3000 mJ / cm ² , and the refractive index was measured by an ABBE5 (Bellingham / stanley Ltd) instrument.

8. Reworkability: The visual inspection was performed. The case where no residue remained on the surface after the rework was indicated by (circle), partly by the case where △ was left, and by the case where a lot was left by ×.

9. Curability: The case where no liquid phase remained after curing at 3000mJ / cm ² was marked with ○, the case of remaining.

TABLE 3

	Example 1	Example 2	Example 3	Example 4	Example 5	Comparative Example 1
Hardening Shrinkage (%)	1.2	1.2	1.2	1.0	0.8	2.7
Elongation (%)	530	590	615	750	506	560
Adhesive force (kgf)	42	50	60	45	45	30
Viscosity (cps)	830	1160	1600	750	800	750
Elastic Modulus (kgf / mm ² )	0.001	0.002	0.004	0.001	0.002	0.002
Transmittance (%)	98	98	97	98	97	98
Refractive index	1.49	1.49	1.49	1.49	1.49	1.46
Reworkability	○	○	○	○	○	△
Curable	○	○	○	○	○	○

As shown in Table 3, the photocurable pressure-sensitive adhesive composition comprising the non-curable compound of the present invention can minimize the curing shrinkage during curing, and showed excellent physical properties in elongation and adhesion.

(2) Specific specifications of the components used in Examples 6-11 and Comparative Examples 2-6 are as follows.

(A) Isoprene-based rubber: (A1) UC-102 (Kuraray America, Inc.), (A2) Mw is 17000g / mol, Tg is -60 ° C, and 93% visible light transmittance at 400-800 nm. UC-203 (Kuraray America, Inc.) with 35000g / mol, Tg of -60 ℃ and 93% visible light transmittance at 400 ~ 800nm

(B) Non-curable compound: (B1) xylene-formaldehyde resin K-11 (Cheil Industries), having 100 to 3000 g / mol of Mw, 1 to 5, and a hydroxyl value of 20 to 40 mg / KOHmg. B2) Xylene-formaldehyde resin K-21 (Cheil Industries), Mw of 5000-20000 g / mol, PDI 1-5, hydroxy value 20-40 mg / KOHmg, (B3) Mw 50000-150000 g / mol, xylene-formaldehyde resin K-31 with PDI of 1-5 and hydroxy value of 20-40 mg / KOHmg (Cheil Industries)

(C) acrylic acid: LG Chem, purity above 99%, moisture below 0.3%

(D) Photocurable monomer: 20 weight% of benzyl acrylate, 10 weight% of 3-methacryloxypropyl trimethoxysilane (KBM-503, Shin-Etsu Silicone), 60 weight of isobornyl acrylate (Osaka Organic Chemicals) %, A mixture of 10% by weight of acryloyl morpholine (Kozin)

(E) Initiator: 1-hydroxy-cyclohexyl-phenyl-ketone (IC-184, Ciba chemical)

(F) UV absorbers: 95% Benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-, C7-9-branched and linear alkyl esters and 5% 1-methoxy-2-propyl acetate (Tinuvin 384-2) (BASF)

실시예 6-11과 비교예 2-6:광경화형 점착제 조성물 및 점착제 필름의 제조Example 6-11 and Comparative Example 2-6: Preparation of photocurable pressure-sensitive adhesive composition and pressure-sensitive adhesive film

Under the UV protection lamp, it was added in the amount described in Table 4 (unit: parts by weight) and stirred at 400 rpm and 25 ° C. for 20 minutes. After stirring, the filter was filtered through a 200 mesh filter and left at 25 ° C. for 48 hours. After leaving for 2 days, the bubbles were completely removed and coated with a polyethylene terephthalate film, which is a release film, at 400 μm and cured by giving an energy of 5000 mJ / cm ² . After curing, the physical properties were evaluated by the following method.

Table 4

		Example						Comparative example
		6	7	8	9	10	11	2	3	4	5	6
(A)	(A1)	50	-	50	70	-	70	60	-	-	-	50
(A)	(A2)	-	50	-	-	70	-	-	30	60	-	-
(B)	(B1)	10	-	10	5	5	5	-	-	18.5	20	10
	(B2)	10	10	10	-	5	5	-	-	18.5	20	10
	(B3)	-	10	10	5	5	-	-	-	-	-	-
(C)		-	-	-	-	-	-	-	-	-	-	3
(D)		27	27	17	17	12	17	37	67	-	57	24
(E)		2.5	2.5	2.5	2.5	2.5	2.5	2.5	2.5	2.5	2.5	2.5
(F)		0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
all		100	100	100	100	100	100	100	100	100	100	100

The physical properties of the films prepared in Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Tables 5 and 6, respectively.

1. Hardening shrinkage: The hardening shrinkage was calculated by measuring the specific gravity of the liquid composition before photocuring, the specific gravity of the solid after curing and the specific gravity of the liquid with a digital solid hydrometer DME-220E (Shinko, Japan). The hardening shrinkage is calculated according to the above formula 1.

2. Adhesive force (kgf): As a method for measuring the adhesion between the glass and the glass, the adhesive force was measured in the same manner as the method of measuring the die shear strength. The force of peeling was measured by pushing the upper glass from the side with a force of 200kgf at 25 ° C. with the dage series 4000PXY, which is an adhesive force measuring instrument. The size of the lower glass was 2 cm x 2 cm x 1 mm, the size of the upper glass was 1.5 cm x 1.5 cm x 1 mm, and the thickness of the adhesive layer was 500 μm.

3. Tensile strength and elongation: The specimen was fabricated and evaluated by ASTM D412 method. The adhesive composition was coated on a release polyethylene terephthalate film with a thickness of 500 μm, cured to 6000 mJ / cm 2, and the elongation was measured using the Instron series IX / s Automated materials Tester-3343 by the distance until the specimen broke. Tensile strength of (gf / mm ² ) was measured at the same time.

4. Refractive index: measured by ASTM D1218 method, the composition was coated on a release polyethylene terephthalate film with a thickness of 500㎛ and cured to 6000mJ / cm ² , the refractive index of the produced film was measured by ABBE5 (Bellingham / Stanley Ltd) instrument .

5. Visible light transmittance: Visible light transmittance in the 550 nm region was measured with a Lambda 950 (Perkin elmer) instrument for the prepared film.

6. Appearance after curing: The photocured film was placed on a paper with a white background, and visually confirmed stickiness and appearance abnormality.

7.Module: Irradiate light quantity at 2000mJ / cm ² , harden to thickness of 500um and diameter of 25mm to make a film, and then make preconciliity 1rad with ARES model name ARES-G2 (TAinstrument) and temperature from 25 ℃ It measured by the method, heating up to 100 degreeC (10 degreeC / min).

8. Liquid spreadability: 1g of the sample was dropped on a 10cm x 10cm x 1mm glass plate at a temperature of about 25 degrees Celsius, and the extent of spread was measured by the change of the area.

9.pH: 10g of the sample was dissolved in 100g of methyl ethyl ketone organic solvent and measured by reading the value after standing until the pH value did not move with a pH meter (Mettler toledo inlab Routine Pro).

Table 5

	Example 6	Example 7	Example 8	Example 9	Example 10	Example 11
Hardening Shrinkage (%)	2.6	2.5	1.3	2.3	2.0	2.3
Adhesive force (kgf)	24	27	21	37	35	37
Tensile Strength (gf / mm ² )	22	22	18	42	40	41
Elongation (%)	430	430	410	550	540	550
After hardening	Good	Good	Good	Good	Good	Good
Liquidity	Good	Good	Good	Good	Good	Good
Modulus (Pa)	24000	22000	21000	28000	31000	28800
pH	4.9	4.8	4.6	4.6	4.7	4.6

Table 6

	Comparative Example 2	Comparative Example 3	Comparative Example 4	Comparative Example 5	Comparative Example 6
Hardening Shrinkage (%)	4.2	5.5	1.9	4.8	2.6
Adhesive force (kgf)	41	45	7	-	53
Tensile Strength (gf / mm ² )	31	18	32	6	50
Elongation (%)	480	310	470	220	380
After hardening	Good	Good	Good	Bad	Good
Liquidity	Good	Bad	Bad	Bad	Good
Modulus (Pa)	26400	14000	18200	7400	36400
pH	4.3	4.8	5.4	4.3	3.2

As shown in Tables 5 and 6, Comparative Example 2, which does not apply the xylene-formaldehyde resin, has a high shrinkage rate and a very high adhesive force, thereby decreasing rework performance. In Comparative Example 3, in which the xylene-formaldehyde resin was not applied, a phenomenon in which shrinkage was greatly increased after photocuring occurred and adhesion was very high, resulting in poor rework performance. In Comparative Example 4, in which the photocurable monomer was not applied, the adhesive strength was remarkably decreased, and the liquid spreadability was not good. In addition, in Comparative Example 5, in which isoprene-based rubber was not applied, shrinkage was greatly increased after photocuring, and tensile strength, appearance and hardening property after curing were significantly reduced. In contrast, the pressure-sensitive adhesive composition of the present invention has a low shrinkage rate, high visibility in the open air, and particularly has excellent elongation and adhesion, tensile strength, appearance and balance of the modulus, pH can be confirmed that 4 or more.

(3) Specific specifications of the components used in Examples 12-17 and Comparative Examples 7-10 are as follows.

(A) binder: (A1) urethane (meth) acrylate copolymer prepared in Preparation Example 4, (A2) butadiene rubber (UC-103, Kurary japan), (A3) UV reactive acrylic polymer (LG Chemical)

(B) Photocurable monomers: (B1) 4-hydroxybutyl acrylate (4-HBA) (LG Chemistry), (B2) 2-hydroxyethyl methacrylate (2-HEMA) (Three Chemicals), (B3 ) Isobornyl acrylate (IBXA) (Mitsubishi Rayon), (B4) acryloyl morpholine (ACMO) (Kohjin, JAPAN), (B5) isooctylacrylate (IOA) (Arkema, France);

(C) non-curable urethane silane compound: the compound prepared in Preparation Example 5 below

(C ′) non-curable compound: xylene resin (X-11, Anhui China);

(D) initiators: (D1) 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO, CIBA), (D2) phenylglyoxylate-based Irgacure 754;

(E) UV absorbers: Irganox 1520;

(F) Silane coupling agent: 3-isocyanatopropyltriethoxysilane was used.

제조예 4: 우레탄 (메타)아크릴레이트 공중합체의 제조Preparation Example 4 Preparation of Urethane (meth) acrylate Copolymer

Into a 2 L four-necked flask, 80 g of polypropylene glycol and 10 g of 1,4-butanediol were added first, a reflux condenser on one side, a thermometer on the other, and a dropping funnel on the other. The temperature of the flask solution was raised to 60 ° C. 1.3 g of dibutyltin dilaurate (DBTDL) diluted to 10% was added to toluene. 9 g of isophorone diisocyanate were thrown in sequentially, and the temperature of the solution was raised to 75 degreeC. It was confirmed that the NCO group completely reacted, and the temperature of the solution was cooled to 50 ° C. 3 g of 2-hydroxyethyl methacrylate was added thereto. After the temperature was maintained at 50 ° C., the NCO group was completely reacted with IR, and cooled to 40 ° C. to give a urethane (meth) acrylate copolymer (Mw: 20,000 g / mol, viscosity: 50,000 cps at 25 ° C.). Was prepared.

제조예 5:비경화성 우레탄 실란 화합물의 제조Preparation Example 5 Preparation of Non-Curable Urethane Silane Compound

Into a 2 L four-necked flask, 68.22 g of xylene resin (X-11, Anhui China) was added and raised to 60 ° C. 0.25 g of DBTDL diluted to 10% was added to toluene. 17.15 g of 3-isocyanatepropyltriethoxysilane (KBE-9007, Shin-etsu) was added thereto. The temperature of the solution was raised to 70 ° C. It was confirmed that the NCO group was completely reacted and cooled to 40 ℃ to prepare a non-curable urethane silane compound.

실시예 12-17과 비교예 7-10:광경화형 점착제 조성물의 제조Example 12-17 and Comparative Example 7-10: Preparation of a photocurable pressure-sensitive adhesive composition

(B), (C), (D), (E) and (F) were added to the contents (unit: parts by weight) described in Table 7 below, and stirred at 25 ° C. for 1 hour and 30 minutes. (A) was added in the amount shown in Table 7 and stirred at 25 ° C. for 2 hours to prepare a photocurable pressure-sensitive adhesive composition.

TABLE 7

		Example						Comparative example
		12	13	14	15	16	17	7	8	9	10
(A)	(A1)	60	60	60	50	70	-	80	70	65	-
	(A2)	-	-	-	-	-	60	-	-	-	-
	(A3)	-	-	-	-	-	-	-	-	-	60
(B)	(B1)	3	3	3	8	3	3	3	3	3	3
	(B2)	5	5	5	10	5	5	5	5	5	5
	(B3)	4.4	14.4	19.4	14.4	9.4	14.4	4.4	14.4	19.4	14.4
	(B4)	3	3	3	3	3	3	3	3	3	3
	(B5)	3	3	3	3	3	3	3	3	3	3
(C)		20	10	5	10	5	10	-	-	-	-
(C ')		-	-	-	-	-	-	-	-	-	5
(D)	(D1)	One	One	One	One	One	One	One	One	One	One
(D)	(D2)	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
(E)		0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1
(F)		-	-	-	-	-	-	-	-	-	5
all		100	100	100	100	100	100	100	100	100	100

The physical properties of the photocurable pressure-sensitive adhesive compositions prepared in Examples and Comparative Examples were measured and the results are shown in Table 8 below.

1. Initial adhesive force (kgf): The adhesive force between the upper glass and the lower glass of the pressure-sensitive adhesive film made of the pressure-sensitive adhesive composition is measured. The size of the bottom glass is 2cm x 2cm x 1mm, and the size of the top glass is 1.5cm x 1.5cm x 1mm. The photocurable pressure-sensitive adhesive composition is coated on the lower glass, the upper glass is covered, and cured at 3000 mJ / cm ² , thereby preparing a pressure-sensitive adhesive film sample having a thickness of 200 μm. For the prepared samples, the force of peeling the upper glass was pushed from the side with a constant force of 200 kgf at 25 ° C. with a dage series 4000 PXY, which is an adhesive force measuring instrument.

Adhesion (kgf) after 1 hour at 2.70 ° C .: The pressure-sensitive adhesive film sample of (1) is left at 70 ° C. for 1 hour. In the same manner, the upper glass is pushed to measure the peeling force.

3. Curing shrinkage rate (%): Specific gravity is measured before hardening with respect to a liquid photocurable adhesive composition. The pressure-sensitive adhesive composition is coated on a PET release film to a thickness of 200 μm and cured at 3000 mJ / cm ² to form an optical pressure-sensitive adhesive film having a thickness of 200 μm. The release film was removed, and specific gravity was measured with a digital solid-state hydrometer DME-220E (Shinko Co., Ltd.) on the optical adhesive film having a thickness of 200 μm. The hardening shrinkage is calculated according to the above formula 1.

4. Initial reworkability: The visual inspection was performed. The case where no residue remained on the surface after the rework was indicated by ○, the part remaining by △, and the case by which a lot remained by ×.

Elongation (%): The specimen was prepared and evaluated by the ASTM D638 method. The photocurable pressure-sensitive adhesive composition prepared in Examples and Comparative Examples was coated on a release PET film, cured to 3000 mJ / cm ² , and the specimen was broken using an Instron series IX / s Automated materials Tester-3343 for a film thickness of 500 μm. The distance at the time of measurement was measured by elongation.

6. Tensile strength (gf / mm ² ): The specimen was fabricated and evaluated by ASTM D638 method. After the adhesive composition was coated on the release PET film and cured at 3000 mJ / cm ² , the tensile strength of the specimen when the specimen was broken using an instron Series 1X / s Automated materials tester-3343 was measured for a film thickness of 500 μm.

7. Refractive index: It measured according to ASTM D1218 method. After coating on a release PET film and curing at 3000mJ / cm ² to prepare a pressure-sensitive adhesive film of 200㎛ thickness. The release film was removed and the refractive index was measured with an ABBE5 (Bellingham / stanley Ltd) instrument for a 200 μm thick adhesive film.

8. Visible light transmittance (%): After coating on a release PET film and cured at 3000mJ / cm ² to prepare a 200㎛ thick adhesive film. The release film was removed and measured in a 400-800 nm region with a Lambda 950 (perkin elmer) instrument for a 200 μm thick adhesive film.

Table 8

	Example						Comparative example
	12	13	14	15	16	17	7	8	9	10
Initial Adhesion (A) (kgf)	15	17	18	17	14	16	24	21	19	34
Adhesion (B) (kgf) at 70 ℃ for 1 hour	65	62	60	61	63	62	25	23	23	44
B / A	4.33	3.65	3.33	3.59	4.5	3.875	1.04	1.10	1.21	1.29
Hardening Shrinkage (%)	0.7	0.9	1.1	1.0	1.3	1.0	2.4	3.4	4.1	1.8
Initial reworkability	○	○	○	○	○	○	○	○	○	△
Elongation (%)	610	600	620	640	680	610	620	650	670	580
Tensile Strength (gf / mm ² )	0.1	0.5	One	One	One	One	24	34	4	1.2
Refractive index	1.49	1.48	1.48	1.48	1.48	1.48	1.47	1.47	1.47	1.47
Visible light transmittance (%)	93	93	92	92	92	92	93	92	93	93

As shown in Table 8, the photocurable pressure-sensitive adhesive composition of the present invention has a low initial adhesive strength, but the adhesive strength was significantly increased after 1 hour at 70 ℃. Moreover, the photocurable adhesive composition of this invention had low hardening shrinkage rate. On the other hand, the pressure-sensitive adhesive composition containing no non-curable urethane silane compound had high initial adhesive strength, and even after 1 hour at 70 ° C., the extent of adhesive strength increase was narrow. Moreover, hardening shrinkage was large (refer comparative example 7-9). In addition, the composition including the xylene resin, which is a non-curable resin, and the silane coupling agent separately has a high initial adhesive force, so that the film is not removed on the surface after the rework, and the reworkability after the temperature rise is also poor. 10).

(4) Specific specifications of the components used in Examples 18-20 and Comparative Examples 11-12 are as follows.

(A) binder: (A1) urethane acrylate copolymer prepared in Preparation Example 6, (A2) urethane acrylate copolymer prepared in Preparation Example 7

(B) Photocurable monomers: (B1) 4-hydroxybutyl acrylate (4-HBA), (B2) isobornyl acrylate (IBXA), (B3) acryloyl morpholine (ACMO)

(C) non-curable compound: Y-1000 (Kohjin, Japan);

(D) initiators: (D1) TPO (BASF), (D21) Irgacure 184 (BASF), (D22) Irgacure 754 (BASF);

(E) ultraviolet absorbers; Tinuvin 384-2 (CIBA)

(F) antioxidants; Irganox 1010 (CIBA)

제조예 6: 우레탄 (메타)아크릴레이트 공중합체 제조Preparation Example 6 Preparation of Urethane (meth) acrylate Copolymer

80 g of polypropylenediol and 10 g of 1,4-butanediol were added to a 2 L four-necked flask, a reflux condenser was installed on one side, a thermometer was installed on the other side, and a dropping funnel was installed on the other side. After raising the temperature of the flask solution to 60 ℃, 1.3g of DBTDL (dibutyltin dilaurate) diluted to 10% concentration in toluene was added. 9 g of isophorone diisocyanate was sequentially added and reacted at 75 ° C. After confirming that the remaining isocyanate group disappeared by IR, the temperature was lowered to 50 ° C., and 3 g of 2-hydroxyethyl methacrylate was added thereto. The urethane (meth) acrylate copolymer was prepared by confirming that the isocyanate group remaining by IR disappeared after holding for 2 hours at 50 ° C.

제조예 7: 우레탄 (메타)아크릴레이트 공중합체 제조Preparation Example 7 Preparation of Urethane (meth) acrylate Copolymer

78.21 g of polypropylenetriol was first introduced into a 2 L four-necked flask, followed by a reflux condenser on one side, a thermometer on the other, and a dropping funnel on the other. After raising the temperature of the flask solution to 60 ° C, 1.3 g of DBTDL diluted to 10% in toluene was added thereto. 13.04 g of isophorone diisocyanate were added and reacted at 75 ° C. After confirming that the remaining isocyanate group disappeared by IR, the temperature was lowered to 50 ° C. and 8.63 g of 4-hydroxybutyl acrylate was added thereto. The urethane (meth) acrylate copolymer was prepared by confirming that the isocyanate group remaining by IR disappeared after holding for 2 hours at 50 ° C.

실시예 18-20과 비교예 11-12: 광경화형 점착제 조성물의 제조Example 18-20 and Comparative Example 11-12: Preparation of Photocurable Adhesive Composition

Each component was mixed in the amounts described in Table 9 (unit: parts by weight) and stirred for 1 hour or more to prepare an adhesive composition.

Table 9

		Example 18	Example 19	Example 20	Comparative Example 11	Comparative Example 12
(A)	(A1)	50.30	40.30	50.30	50.30	55.30
(A)	(A2)	5	5	5	5	5
(B)	(B1)	10	10	10	10	11
	(B2)	7.9	7.9	7.9	7.9	7.9
	(B3)	10	10	10	10	5
(C)		14.1	24.1	14.1	13.1	14.0
(D)	(D1)	One	One	0.4	2	0.1
	(D2)	(D21)	0.2	0.2	0.8	0.2	0.2
	(D2)	(D22)	0.4	0.4	0.4	0.4	0.4
(E)		One	One	One	One	One
(F)		0.1	0.1	0.1	0.1	0.1
all		100	100	100	100	100

In the above Examples and Comparative Examples The physical properties of the photocurable pressure-sensitive adhesive composition was measured and the results are shown in Table 10 below.

1. Hardening rate: Hardening rate is measured using FT-IR. FT-IR is photographed about the container containing 1g of adhesive compositions, and IR spectrum is calculated | required. The intensity (B _o ) of the reference peak in the IR spectrum and the intensity (h ₀ , area within the peak) of 1635 cm ⁻¹ to 1645 cm ⁻¹ are obtained. 1 g of the pressure-sensitive adhesive composition is coated on a release PET film and dried to prepare a film having a thickness of 100 μm. A curing energy of 200 mJ / m 2 is irradiated to a container containing a film having a coating thickness of 100 μm. FT-IR is taken on the container in the same manner as above to find the IR spectrum. The intensity (B ₁ ) of the reference peak in the IR spectrum and the intensity (h ₁ , area within the peak) of 1635 cm ⁻¹ to 1645 cm ⁻¹ are obtained. The hardening rate is computed according to said Formula 2.

2. Whether to quickly cure: The pressure-sensitive adhesive composition is coated on a release PET film and dried to prepare a film having a thickness of 100 μm. Curing energy of 50 mJ / m 2 is investigated to determine whether or not the film is cured.

3. Whether spilled and the film state after curing: The pressure-sensitive adhesive composition is coated on an ITO film, and cured by irradiating a curing energy of 50 mJ / m ² while pressing with a window glass. The LED light source (320 nm, 50 mJ / m ² ) is irradiated for 1 second around the ITO film. It evaluates visually whether the adhesive composition overflows, and when there exists overflow, it is judged as x when there is no overflow. The LED light source is removed and main curing is performed by irradiating a curing energy of 5000 mJ / m 2. After curing, the state of the film is visually evaluated.

4. Curing shrinkage: The specific gravity is measured before curing the liquid photocurable pressure-sensitive adhesive composition. The pressure-sensitive adhesive composition is coated on a PET release film to a thickness of 200 μm and cured at 3000 mJ / cm ² to form an optical pressure-sensitive adhesive film having a thickness of 200 μm. The release film was removed, and specific gravity was measured with a digital solid-state hydrometer DME-220E (Shinko Co., Ltd.) on the optical adhesive film having a thickness of 200 μm. The hardening shrinkage is calculated according to the above formula 1.

5. Adhesive force: The adhesive force between the upper glass and the lower glass of the pressure-sensitive adhesive film made of the pressure-sensitive adhesive composition is measured. The size of the bottom glass is 2cm x 2cm x 1mm, and the size of the top glass is 1.5cm x 1.5cm x 1mm. The photocurable pressure-sensitive adhesive composition is coated on the lower glass, the upper glass is covered, and cured at 3000 mJ / cm ² , thereby preparing a pressure-sensitive adhesive film sample having a thickness of 200 μm. For the prepared samples, the force of peeling the upper glass was pushed from the side with a constant force of 200 kgf at 25 ° C. with a dage series 4000 PXY, which is an adhesive force measuring instrument.

6. Refractive index: Measured by ASTM D1218 method. After coating the pressure-sensitive adhesive composition on a release PET film and cured at 3000mJ / cm ² to prepare a pressure-sensitive adhesive film of 200㎛ thickness. The release film is removed and the refractive index is measured with an ABBE5 (Bellingham / stanley Ltd) instrument for a 200 μm thick adhesive film.

7. Visible light transmittance: A pressure-sensitive adhesive film having a thickness of 200 μm is prepared after coating on a release PET film and curing at 3000 mJ / cm ² . The release film is removed and measured on a 400-800 nm region with a Lambda 950 (perkin elmer) instrument for a 200 μm thick adhesive film.

Elongation: Test and fabricate specimens using the ASTM D638 method. The photocurable pressure-sensitive adhesive composition was coated on a release PET film and cured at 3000 mJ / cm ² to obtain an optical pressure-sensitive adhesive film having a thickness of 500 μm. Measure the elongation at break of the specimen using the Instron series IX / s Automated Materials Tester-3343.

9. Tensile strength: Tensile strength is measured simultaneously in the above elongation measurement.

Table 10

	Example 18	Example 19	Example 20	Comparative Example 11	Comparative Example 12
Weight ratio of (D2) / (D1)	0.6	0.6	3	0.3	6
Curing rate (%)	98	98	97	94	95
Fast curing	○	○	○	×	×
Overflow	×	×	×	○	○
Film state after curing	Good	Good	Good	Good	Good
Hardening Shrinkage (%)	2.1	1.9	2.0	2.1	2.2
Adhesive force (kgf)	45	51	44	40	39
Refractive index	1.47	1.47	1.47	1.47	1.47
Visible light transmittance (%)	93	93	92	93	92
Elongation (%)	520	560	540	550	510
Tensile strength (kgf / mm ² )	0.002	0.003	0.004	0.004	0.003

As shown in Table 10, the photocurable pressure-sensitive adhesive composition of the present invention can be cured quickly, there is no overflow phenomenon, the adhesion was high.

(5) Specific specifications of the components used in Examples 21-24 and Comparative Examples 13-15 are as follows.

(A) urethane (meth) acrylate copolymer:

(A1) urethane (meth) acrylate copolymer prepared in Production Example 8,

(A2-1) urethane (meth) acrylate copolymer prepared in Production Example 9,

(A2-2) Urethane (meth) acrylate copolymer prepared in Production Example 10

(C) Initiator: (C1) TPO, (C2) Irgacure 754

(D) Compound: Xylene resin (X-11) (Anhui Co.)

(E) UV absorbers: Tinuvin 384-2

(F) Antioxidant: Irganox 1010

제조예 8: 우레탄 (메타)아크릴레이트 공중합체의 제조Preparation Example 8 Preparation of Urethane (meth) acrylate Copolymer

90 g of polypropylenediol PPG3000 (Mw: 3000 / g / mol) was added to a 2 L four-necked flask, and a reflux condenser, thermometer, and dropping funnel were installed. The temperature of the flask solution was raised to 60 ° C. 0.1 g of dibutyltin dilaurate (DBTDL) diluted to 10% in toluene was added, and 8.0 g of IPDI (isophorone diisoyanate) was added thereto, and the temperature of the flask solution was maintained at 75 ° C. After confirming that the NCO-group completely reacted, the mixture was cooled to 60 ° C., and then 2.0 g of 4-hydroxybutyl methacrylate (4-HBA) was added thereto. After maintaining 60 ° C. for 5 hours, the NCO-group disappeared by IR and cooled to 40 ° C. to prepare a urethane (meth) acrylate copolymer. The viscosity, Mw, PDI at 25 ° C. of the prepared copolymer was measured and the results are shown in Table 11.

제조예 9-10: 우레탄 (메타)아크릴레이트 공중합체의 제조Preparation Example 9-10 Preparation of Urethane (meth) acrylate Copolymer

Except for changing the content (unit: parts by weight) of each component in Preparation Example 8 was carried out in the same manner to prepare a urethane (meth) acrylate copolymer.

Table 11

		Preparation Example 8	Preparation Example 9	Preparation Example 10
Polyol	PPG3000 (Mw: 3000g / mol)	91	89	-
Polyol	PPG4000 (Mw: 4000g / mol)	-	-	78
Isocyanate	IPDI	8	9	13
(Meth) acrylate type	4-HBA	One	2	9
catalyst	DBTDL	0.1	0.1	0.1
Mw (g / mol)		40,000	20,000	17,000
Viscosity (25 ° C, cps)		330,000	48,000	30,000
Solid content (% by weight)		100	100	100
PDI		1.9	1.4	1.3

실시예 21-24 및 비교예 13-15: 광경화형 점착제 조성물의 제조Example 21-24 and Comparative Example 13-15: Preparation of Photocurable Adhesive Composition

Each component was mixed and stirred for 1 hour to a content described in Table 12 (unit: parts by weight) without a solvent to prepare a photocurable pressure-sensitive adhesive composition.

Table 12

		Example				Comparative example
		21	22	23	24	13	14	15
(A)	(A1)	10	12	10	15	30	-	-
	(A2-1)	40	40	40	35	-	40	-
	(A2-2)	5	-	5	5	-	30	60
(B)	(B1)	10	5	5	5	20	5	5
	(B2)	23.5	13.3	13.3	13.3	38.5	13.5	13.3
	(B3)	10	10	10	10	10	10	10
(C)	(C1)	One	One	One	One	One	One	One
(C)	(C2)	0.5	0.5	0.5	0.5	0.5	0.5	0.5
(D)		-	18	15	15	-	-	10
(E)		-	0.1	0.1	0.1	-	-	0.1
(F)		-	0.1	0.1	0.1	-	-	0.1
all		100	100	100	100	100	100	100

The physical properties of the photocurable pressure sensitive adhesive compositions prepared in Examples and Comparative Examples or the pressure sensitive adhesive layers prepared therefrom were measured and the results are shown in Table 13 below.

1. Viscosity: Store the optical pressure-sensitive adhesive composition for 24 hours in a thermostat (25 ° C). In a 500 ml nalgene bottle (73.8 mm outer diameter x 169.8 mm height) with a Brookfield viscometer DV-Ⅱ + 100 rpm at 25 ° C., Spindle No. Measure with # 7.

2. Hardening shrinkage: The specific gravity of the liquid composition is measured before curing. The optical pressure-sensitive adhesive composition is coated on a PET release film and cured at 3000 mJ / cm ² to obtain an optical pressure-sensitive adhesive film having a thickness of 200 μm, and the specific gravity thereof is measured by a digital solid-state hydrometer DME-220E (Shinko). It calculates according to the said Formula 1.

3. Elastomeric Modulus: Test and fabricate the specimen using ASTM D638. The optical pressure-sensitive adhesive composition was coated on a release PET film, cured to 3000 mJ / cm ^2, and the modulus when the specimen was ruptured was measured using an Instron series IX / s Automated materials Tester 3343 for an optical pressure-sensitive adhesive film thickness of 500 μm.

4. Storage modulus: 2000mJ / cm ² is irradiated to the optical adhesive composition. An optical pressure-sensitive adhesive film having a thickness of 500 µm and a diameter of 25 mm is obtained. Using ARES G2 (TA Instrument Co., Ltd.), 1rad, strain 0.1%, frequency 2Hz, 25 ℃, 25mm cone, 25mm plate, the conditions are measured with a frequency sweep.

5. Elongation: Measured by the same method as the above elastic modulus measurement.

6. Adhesive force: Measure the adhesive force between glass and glass. The size of the lower glass was 2 cm x 2 cm x 1 mm, and the size of the upper glass was 1.5 cm x 1.5 cm x 1 mm. The optical pressure-sensitive adhesive composition is applied to the lower glass and the upper glass is placed. It irradiates with light at 3000mJ / cm <^2> and hardens | cures, and the adhesive layer of thickness 500mm diameter 3mm is manufactured. The force of peeling is measured by pulling the upper glass vertically with a force of 200 kgf using a UTM H5KT at 25 ° C.

Table 13

	Example 21	Example 22	Example 23	Example 24	Comparative Example 13	Comparative Example 14	Comparative Example 15
Viscosity (cps)	3000	2900	2750	3000	4500	3500	2500
Hardening Shrinkage (%)	1.5	1.2	1.3	1.3	2.5	2.0	1.6
Elastic modulus (kgf / mm ² )	0.004	0.004	0.002	0.003	0.015	0.012	0.010
Storage modulus (Pa)	8.5 x 10 ³	8.2 x 10 ³	7.0 x 10 ³	7.4 x 10 ³	1.50 x 10 ⁴	1.20 x 10 ⁴	1.03 x 10 ⁴
Elongation (%)	750	620	700	650	600	420	380
Vertical adhesion (N / m)	8.5	6.5	8.2	7.9	5.0	5.2	3.5

As shown in Table 13, the pressure-sensitive adhesive layer made of the photocurable pressure-sensitive adhesive composition of the present invention not only has high adhesion but also has low elastic modulus and low storage modulus. This indicates that the optical pressure-sensitive adhesive composition of the present invention can implement an adhesive layer having high adhesion and high impact resistance. On the other hand, compositions containing only one type of urethane (meth) acrylate copolymer did not have good adhesion, elastic modulus, and storage modulus.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments and can be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains has the technical idea of the present invention. However, it will be understood that other specific forms may be practiced without changing the essential features. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

A photocurable pressure-sensitive adhesive composition comprising a compound comprising a structure of Formula 1 below:

<Formula 1>

(In the above, n and m are each independently an integer of about 0-10,

Except that n and m are both 0,

Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 and Q 8 are each independently hydrogen, linear or branched carbon atoms substituted with alkyl groups, hydroxyl groups and hydroxyl groups of 1 to 10 carbon atoms. An alkyl group of -10,-(-CH 2- ) sO-[-CH 2 -CH 2 O-] t-CH 2 CH 2 OH (s is an integer of about 0-5, t is an integer of about 0-5) Is selected from the group consisting of

At least one or more of Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 and Q 8 is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group,-(-CH 2- ) sO -[-CH 2 -CH 2 O-] t-CH 2 CH 2 OH (s is an integer of about 0-5, t is an integer of about 0-5).
The photocurable pressure-sensitive adhesive composition of claim 1, wherein the compound is ultraviolet noncurable.
The photocurable pressure-sensitive adhesive composition of claim 1 or 2, wherein the compound has a structure of Formula 1-1 or 1-2:

<Formula 1-1>

A1-(-CH 2 O-) n1-(-CH 2- ) m1-A2-(-CH 2 O-) n2-(-CH 2- ) m2-A3-(-CH 2 O-) n3- ( -CH 2- ) m4-A4

<Formula 1-2>

A1-(-CH 2 O-) n1-(-CH 2- ) m1-A2-(-CH 2 O-) n2-(-CH 2- ) m2-A3-(-CH 2 O-) n3- ( -CH 2- ) m3-A4-(-CH 2 O-) n4-(-CH 2- ) m4-A5

(Wherein n1, n2, n3, n4, m1, m2, m3 and m4 are independently integers of about 0-10,

Except that n1 and m1 are all 0, n2 and m2 are all 0, n3 and m3 are all 0, and n4 and m4 are both 0,

A1 to A5 are any one of the following general formulas (a), (b), (c) or (d).

(a)

(b)

(c)

(d)

In the above, R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different from each other, and independently of each other hydrogen, linear or branched C 1-10 alkyl, hydroxyl, hydroxyl group substituted with carbon atoms 1- An alkyl group of 10,-(-CH 2- ) sO-[-CH 2 -CH 2 O-] t-CH 2 CH 2 OH (s is an integer of about 0-5, t is an integer of about 0-5) Is selected from the group consisting of

At least one of R 1 , R 2 , R 3 , R 4 and R 5 may be a hydroxyl group, an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group, or-(-CH 2- ) sO-[-CH 2 -CH 2 O-]. t-CH 2 CH 2 OH (s is an integer from about 0-5, t is an integer from about 0-5).
The photocurable pressure-sensitive adhesive composition of claim 1, wherein the compound comprises about 1-30% by weight of the composition.
The photocurable pressure sensitive adhesive composition according to any one of claims 1 to 4, wherein the composition further comprises a binder, a photocurable monomer, and an initiator.
The photocurable pressure-sensitive adhesive composition of claim 5, wherein the binder is a urethane (meth) acrylate copolymer, butadiene rubber, isoprene rubber, or a mixture thereof.
The photocurable pressure-sensitive adhesive composition of claim 6, wherein the binder is a urethane (meth) acrylate copolymer.
The photocurable monomer according to claim 5, wherein the photocurable monomer is a vinyl monomer having a hydroxy group, a vinyl monomer having an alkyl group, a vinyl monomer having an alicyclic group, a (meth) acrylic monomer having an alicyclic hetero ring, or a vinyl having a carboxyl group. Photocurable pressure-sensitive adhesive composition comprising at least one selected from the group consisting of monomers and monomers having a silane group and a vinyl group.
The composition of claim 5, wherein the composition comprises about 25-83.7 wt% of the binder, about 1-30 wt% of the compound, about 15-40 wt% of the photocurable monomer, and about 0.1-5 wt% of the initiator. Photocurable pressure-sensitive adhesive composition comprising.
The photocurable pressure-sensitive adhesive composition of claim 5, wherein the composition further comprises at least one member selected from the group consisting of ultraviolet absorbers and antioxidants.
The composition of claim 10, wherein the composition comprises about 25-83.7 wt% of the binder, about 1-30 wt% of the compound, about 15-40 wt% of the photocurable monomer, about 0.1-5 wt% of the initiator, A photocurable pressure-sensitive adhesive composition comprising about 0.1-1% by weight of the ultraviolet absorber and about 0.1-1% by weight of the antioxidant.
Comprising a compound comprising the structure of formula 1 of claim 1,

A photocurable pressure-sensitive adhesive composition having a cure shrinkage ratio of about 2% or less represented by the following Formula 1:

<Equation 1>
Comprising a compound comprising the structure of formula 1 of claim 1,

A photocurable pressure-sensitive adhesive composition having an adhesion of about 35-60 kgf to a 5 cm x 1.5 cm glass plate.
Comprising a compound comprising the structure of formula 1 of claim 1,

An optical adhesive film having an elongation of about 400-800% for a film thickness of 500 μm after curing.
Photocurable pressure-sensitive adhesive composition comprising a binder, a compound comprising the structure of formula 1 of claim 1, a photocurable monomer and an initiator.
A photocurable pressure-sensitive adhesive composition comprising a binder and a compound comprising the structure of Formula 1 of claim 1, wherein the pH is at least about 4 and the adhesion is at least about 20 kgf.
A photocurable pressure-sensitive adhesive composition comprising a binder and a compound comprising the structure of Formula 1, wherein the curing shrinkage is about 3% or less and the elongation after curing according to ASTM D638 is about 400 to 800%.
The photocurable pressure sensitive adhesive composition according to any one of claims 15 to 17, wherein the binder is a urethane (meth) acrylate copolymer, butadiene rubber, isoprene rubber, or a mixture thereof.
The photocurable pressure-sensitive adhesive composition of claim 18, wherein the binder is isoprene-based rubber.
The method according to claim 15, wherein the pressure-sensitive adhesive composition is about 35 to 75% by weight of the binder, about 2 to 30% by weight of the compound comprising the structure of Formula 1, about 12 to 40% by weight of the photocurable monomer and the Photocurable pressure-sensitive adhesive composition comprising about 1 to 5% by weight of the initiator.
The photocurable pressure sensitive adhesive composition according to any one of claims 15 to 17, wherein the content weight ratio of the binder to the compound including the structure of Formula 1 in the composition is about 1.1 to 10.
The photocurable pressure sensitive adhesive composition according to any one of claims 15 to 17, wherein the sum of the binder and the compound comprising the structure of Chemical Formula 1 is about 65-85% by weight of the pressure-sensitive adhesive composition based on solids.
The photocurable pressure-sensitive adhesive composition according to claim 18 or 19, wherein the isoprene-based rubber contains a vinyl group at its terminal.
20. The method of claim 18 or 19, wherein the isoprene rubber has a weight average molecular weight of about 10,000 to 50,000 g / mol photocurable pressure-sensitive adhesive composition.
The photocurable pressure-sensitive adhesive composition of claim 18 or 19, wherein the isoprene-based rubber has a glass transition temperature of about -70 ° C to -50 ° C.
The photocurable pressure-sensitive adhesive composition of claim 18 or 19, wherein the isoprene-based rubber has a structure of Formula 2:

[Formula 2]

(Wherein R is hydrogen or an alkyl group having 1 to 3 carbon atoms, m is an integer of about 1 to 300, n is an integer of about 0 to 60, p is an integer of about 1 to 10).
The photocurable pressure-sensitive adhesive composition of any one of claims 15 to 17, wherein the compound including the structure of Chemical Formula 1 has a weight average molecular weight of about 100 to 50,000 g / mol and a polydispersity of about 1 to 5. .
The photocurable pressure-sensitive adhesive composition of claim 15, wherein the compound comprising the structure of Formula 1 has a hydroxyl value of about 20-500 mg / KOHmg.
The photocurable pressure-sensitive adhesive composition of any one of claims 15 to 17, wherein the compound including the structure of Chemical Formula 1 has a structure of Chemical Formula 1-1 or 1-2:

<Formula 1-1>

A1-(-CH 2 O-) n1-(-CH 2- ) m1-A2-(-CH 2 O-) n2-(-CH 2- ) m2-A3-(-CH 2 O-) n3- ( -CH 2- ) m4-A4

<Formula 1-2>

A1-(-CH 2 O-) n1-(-CH 2- ) m1-A2-(-CH 2 O-) n2-(-CH 2- ) m2-A3-(-CH 2 O-) n3- ( -CH 2- ) m3-A4-(-CH 2 O-) n4-(-CH 2- ) m4-A5

(Wherein n1, n2, n3, n4, m1, m2, m3 and m4 are independently integers of about 0-10,

Except that n1 and m1 are all 0, n2 and m2 are all 0, n3 and m3 are all 0, and n4 and m4 are both 0,

A1 to A5 are any one of the following general formulas (a), (b), (c) or (d).

(a)

(b)

(c)

(d)

In the above, R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different from each other, and independently of each other hydrogen, linear or branched C 1-10 alkyl, hydroxyl, hydroxyl group substituted with carbon atoms 1- An alkyl group of 10,-(-CH 2- ) sO-[-CH 2 -CH 2 O-] t-CH 2 CH 2 OH (s is an integer of about 0-5, t is an integer of about 0-5) Is selected from the group consisting of

At least one of R 1 , R 2 , R 3 , R 4 and R 5 may be a hydroxyl group, an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group, or-(-CH 2- ) sO-[-CH 2 -CH 2 O-]. t-CH 2 CH 2 OH (s is an integer from about 0-5, t is an integer from about 0-5).
16. The method according to claim 15, wherein the photocurable monomer is a (meth) acrylate having a hydroxy group, a (meth) acrylate having a monocyclic or heterocyclic alicyclic ring, a monocyclic alicyclic hetero having a nitrogen, oxygen or sulfur At least one photocurable pressure-sensitive adhesive composition selected from the group consisting of a (meth) acrylic monomer having a ring, a (meth) acrylic monomer having a carboxyl group, and a monomer having a vinyl group and a silane group.
The photocurable pressure-sensitive adhesive composition of claim 15, wherein the pressure-sensitive adhesive composition further comprises one or more additives selected from the group consisting of a silane coupling agent, an ultraviolet absorber, and an antioxidant.
18. The photocurable pressure sensitive adhesive composition of claim 15, wherein the pressure sensitive adhesive composition has a modulus of about 10 kPa to 50 kPa.
Urethane bonds and -SiX 1 X 2 X 3 (wherein X 1 , X 2 and X 3 are the same or different and are hydrogen, a hydroxyl group, an alkyl group of 1-10 carbon atoms, an alkoxy group of 1-10 carbon atoms or 6-20 carbon atoms) An aryl group), containing an aromatic compound,

The aromatic compound is a photocurable pressure-sensitive adhesive composition formed from a compound comprising the structure of Formula 1 of claim 1.
The photocurable pressure-sensitive adhesive composition of claim 33, wherein the aromatic compound is formed by reaction of an aromatic alcohol compound having a structure of Formula 3 with an isocyanate-containing silane compound of Formula 5 below:

<Formula 3>

(In the above, R 11 to R 28 are the same as or different from each other, hydrogen, linear or branched alkyl group having 1 to 10 carbon atoms, hydroxyl group, substituted with hydroxyl group having 1 to 10 carbon atoms,-(-CH 2- ) sO -[-CH 2 -CH 2 O-] t-CH 2 CH 2 OH (s is an integer of about 0-5, t is an integer of about 0-5) and is selected from R 11 to R At least one of 28 is a hydroxyl group, an alkyl group having 1-10 carbon atoms substituted with a hydroxyl group, or-(-CH 2- ) sO-[-CH 2 -CH 2 O-] t-CH 2 CH 2 OH (s is about Integer is 0-5, t is an integer of about 0-5)

<Formula 5>

(Wherein X 1 , X 2 and X 3 are the same as or different from each other and are hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and u is about 0 Is an integer of -5).
The photocurable pressure-sensitive adhesive composition of claim 34, wherein the isocyanate-containing silane compound is isocyanatopropyltrialkoxysilane.
36. The photocurable pressure-sensitive adhesive composition of any one of claims 33 to 35, wherein the aromatic compound has a structure of Formula 6:

<Formula 6>

(In the above, X 1 , X 2 , X 3 are the same as or different from each other, hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, u is about 0 Is an integer of -5).
The photocurable pressure-sensitive adhesive composition of claim 33, wherein the aromatic compound is included in an amount of about 1-30% by weight of the pressure-sensitive adhesive composition on a solids basis.
37. The photocurable pressure sensitive adhesive composition according to any one of claims 33 to 36, wherein the pressure sensitive adhesive composition further comprises a binder, a photocurable monomer and an initiator.
The photocurable pressure-sensitive adhesive composition of claim 38, wherein the binder comprises a urethane (meth) acrylate copolymer, butadiene rubber, isoprene rubber, or a mixture thereof.
The photocurable pressure sensitive adhesive according to claim 38, wherein the photocurable monomer comprises a vinyl monomer having a hydroxy group, a vinyl monomer having an alkyl group, a vinyl monomer having an alicyclic group, and a (meth) acrylic monomer having an alicyclic hetero ring. Composition.
The adhesive composition of claim 38, wherein the pressure-sensitive adhesive composition comprises about 25-83.8 wt% of a binder, about 1-30 wt% of an aromatic compound, about 15-40 wt% of a photocurable monomer, and about 0.1-5 wt% of an initiator. Photocurable adhesive composition.
39. The photocurable pressure sensitive adhesive composition of claim 38, wherein the pressure sensitive adhesive composition further comprises an ultraviolet absorber.
43. The composition of claim 42, wherein the composition comprises about 25-83.8 wt% of a binder, about 1-30 wt% of an aromatic compound, about 15-40 wt% of a photocurable monomer, about 0.1-5 wt% of an initiator, and about UV absorber about Photocurable pressure-sensitive adhesive composition comprising 0.1-1% by weight.
Urethane bonds and -SiX 1 X 2 X 3 (wherein X 1 , X 2 and X 3 are the same or different, hydrogen, a hydroxyl group, an alkyl group of 1-10 carbon atoms, an alkoxy group of 1-10 carbon atoms or of 6-20 carbon atoms) An aromatic compound containing an aryl group),

The aromatic compound is formed from a compound comprising the structure of formula 1 of claim 1,

The photocurable adhesive composition whose B / A is about 2 or more, when making initial-adhesion force A and 70 degreeC 1 hour after hardening, and hardening adhesive force B after hardening for 1 hour.
45. The photocurable pressure sensitive adhesive composition of claim 44, wherein the initial adhesion A is about 18 kgf or less.
The photocurable pressure-sensitive adhesive composition according to claim 44 or 45, wherein the adhesive force B is about 50 kgf or more after being left at 70 ° C. for 1 hour.
Urethane bonds and -SiX 1 X 2 X 3 (wherein X 1 , X 2 and X 3 are the same or different, hydrogen, a hydroxyl group, an alkyl group of 1-10 carbon atoms, an alkoxy group of 1-10 carbon atoms or of 6-20 carbon atoms) An aromatic compound containing an aryl group),

The aromatic compound is formed from a compound comprising the structure of formula 1 of claim 1,

A photocurable pressure-sensitive adhesive composition having a cure shrinkage ratio of about 2% or less represented by the following Formula 1:

<Equation 1>
(A) a binder, (B) a photocurable monomer, (C) a compound comprising the structure of formula (1), and (D) a photoinitiator, wherein the photoinitiator has an absorption wavelength of greater than about 350 nm to 400 nm A photocurable pressure-sensitive adhesive composition comprising an initiator (D1) and a photoinitiator (D2) having an absorption wavelength of about 200 nm to 350 nm or less in a weight ratio of about 1: 0.5 to 1: 5.
The photocurable pressure-sensitive adhesive composition of claim 48, wherein the photoinitiator (D1) is a mono acrylic phosphine oxide based.
The photocurable pressure-sensitive adhesive composition according to claim 48 or 49, wherein the photoinitiator (D1) is (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide.
The photocurable pressure sensitive adhesive composition according to any one of claims 48 to 50, wherein the photoinitiator (D2) is an alpha-hydroxyarylketone series, a phenylglyoxylate series, or a mixture thereof.
52. The photoinitiator (D2) according to any one of claims 48 to 51, wherein the photoinitiator (D2) is 1-hydroxycyclohexyl phenyl ketone, oxy phenyl acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -Ethyl ester, oxy phenyl acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester or mixtures thereof.
53. The photocurable pressure sensitive adhesive composition of claim 48, wherein the binder comprises a urethane (meth) acrylate copolymer, butadiene rubber, isoprene rubber or mixtures thereof.
49. The method according to claim 48, wherein the photocurable monomer comprises a mixture of a vinyl monomer having a hydroxy group, a vinyl monomer having an alkyl group, a vinyl monomer having an alicyclic group, and a (meth) acrylic monomer having an alicyclic hetero ring. Chemical pressure-sensitive adhesive composition.
The photocurable pressure-sensitive adhesive composition of claim 48, wherein the compound including the structure of Formula 1 has a structure of Formula 1-1 or 1-2:

<Formula 1-1>

A1-(-CH 2 O-) n1-(-CH 2- ) m1-A2-(-CH 2 O-) n2-(-CH 2- ) m2-A3-(-CH 2 O-) n3- ( -CH 2- ) m4-A4

<Formula 1-2>

A1-(-CH 2 O-) n1-(-CH 2- ) m1-A2-(-CH 2 O-) n2-(-CH 2- ) m2-A3-(-CH 2 O-) n3- ( -CH 2- ) m3-A4-(-CH 2 O-) n4-(-CH 2- ) m4-A5

(Wherein n1, n2, n3, n4, m1, m2, m3 and m4 are independently integers of about 0-10,

Except that n1 and m1 are all 0, n2 and m2 are all 0, n3 and m3 are all 0, and n4 and m4 are both 0,

A1 to A5 are any one of the following general formulas (a), (b), (c) or (d).

(a)

(b)

(c)

(d)

In the above, R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different from each other, and independently of each other hydrogen, linear or branched C 1-10 alkyl, hydroxyl, hydroxyl group substituted with carbon atoms 1- An alkyl group of 10,-(-CH 2- ) sO-[-CH 2 -CH 2 O-] t-CH 2 CH 2 OH (s is an integer of about 0-5, t is an integer of about 0-5) Is selected from the group consisting of

At least one of R 1 , R 2 , R 3 , R 4 and R 5 may be a hydroxyl group, an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group, or-(-CH 2- ) sO-[-CH 2 -CH 2 O-]. t-CH 2 CH 2 OH (s is an integer from about 0-5, t is an integer from about 0-5).
The photocurable pressure-sensitive adhesive composition of claim 48, wherein the pressure-sensitive adhesive composition further comprises one or more selected from the group consisting of ultraviolet absorbers and antioxidants.
57. The method according to claim 56, wherein the pressure-sensitive adhesive composition is about 25 to 83.3% by weight of the binder, about 15 to 40% by weight of the photocurable monomer, about 1 to 30% by weight of the compound including the structure of Formula 1, about 0.1 to about a photoinitiator To 5% by weight, UV absorber about 0.1 to 2% by weight and antioxidant about 0.01 to 2% by weight of the photocurable pressure-sensitive adhesive composition.
The photocurable pressure-sensitive adhesive composition of claim 48, wherein the photocurable pressure-sensitive adhesive composition has a curing rate of about 96-100% measured by the following Formula 2 at a curing energy of about 100-600 μm and a thickness of about 200 mJ / cm 2 :

<Equation 2>

(In the above, B is B o / B 1 ,

The B o and h o are the intensity and the frequency of the reference peak 1640-Xcm -1 to 1640 + Xcm -1 (X is 0, respectively) in the IR spectrum calculated when FT-IR is taken on the container containing 1 g of the pressure-sensitive adhesive composition. To 5), the intensity of the peak in the range

When B 1 and h 1 were each coated with a 1g adhesive composition on a release film and dried to irradiate curing energy of 200 mJ / m 2 in a container containing a film having a film thickness of 100 to 600 μm, and then taken FT-IR. The intensity of the reference peak and the intensity of the peak in the range 1640-Xcm -1 to 1640 + Xcm -1 (X is 0 to 5) in the calculated IR spectrum.
Including a binder,

The viscosity is about 2,000-4,000cps at 25 ° C,

A photocurable pressure-sensitive adhesive composition having a curing shrinkage ratio of about 1.5% or less represented by Formula 1 below:

<Equation 1>
60. The photocurable pressure sensitive adhesive composition of claim 59, wherein the binder comprises a urethane (meth) acrylate copolymer, butadiene rubber, isoprene rubber, or a mixture thereof.
60. The binder according to claim 59, wherein the binder (A1) has a weight average molecular weight of about 30,000 g / mol or more and 60,000 g / mol or less of urethane (meth) acrylate copolymer, and (A2) weight average molecular weight of about 5,000 g / mol Photocurable adhesive composition which is a mixture of the urethane (meth) acrylate copolymer which is more than 30,000 g / mol or less.
The photocurable pressure-sensitive adhesive of claim 61, wherein the weight average molecular weight of (A1) is about 35,000 g / mol to 45,000 g / mol, and the weight average molecular weight of (A2) is about 10,000 g / mol to 20,000 g / mol. Composition.
62. The photocurable pressure sensitive adhesive composition of claim 61, wherein the weight ratio of (A2) to (A1) in the composition is about 1.01 to 6.
62. The photocurable pressure sensitive adhesive composition of claim 61, wherein (A1) comprises less than about 25% by weight of the composition.
62. The photocurable pressure sensitive adhesive composition of claim 61, wherein the mixture comprises about 10-45 weight percent of (A1) and about 55-90 weight percent of (A2).
60. The photocurable pressure-sensitive adhesive composition of claim 59, wherein the composition further comprises a photocurable monomer and an initiator.
67. The photocurable monomer according to claim 66, wherein the photocurable monomer comprises at least one selected from the group consisting of a vinyl monomer having a hydroxy group, a vinyl monomer having an alicyclic group, and a (meth) acrylic monomer having an alicyclic hetero ring. Pressure-sensitive adhesive composition.
67. The photocurable pressure sensitive adhesive composition of claim 66, wherein the composition comprises about 25-83.7 weight% binder, about 5-70 weight% photocurable monomer, and about 0.1-5 weight% initiator.
67. The photocurable pressure sensitive adhesive composition of claim 66, wherein the composition further comprises a compound comprising the structure of Formula 1 of claim 1, an ultraviolet absorber, an antioxidant, or a mixture thereof.
The photocurable pressure-sensitive adhesive composition of claim 69, wherein the compound including the structure of Formula 1 has a structure of Formula 1-1 or 1-2:

<Formula 1-1>

A1-(-CH 2 O-) n1-(-CH 2- ) m1-A2-(-CH 2 O-) n2-(-CH 2- ) m2-A3-(-CH 2 O-) n3- ( -CH 2- ) m4-A4

<Formula 1-2>

A1-(-CH 2 O-) n1-(-CH 2- ) m1-A2-(-CH 2 O-) n2-(-CH 2- ) m2-A3-(-CH 2 O-) n3- ( -CH 2- ) m3-A4-(-CH 2 O-) n4-(-CH 2- ) m4-A5

(Wherein n1, n2, n3, n4, m1, m2, m3 and m4 are independently integers of about 0-10,

Except that n1 and m1 are all 0, n2 and m2 are all 0, n3 and m3 are all 0, and n4 and m4 are both 0,

A1 to A5 are any one of the following general formulas (a), (b), (c) or (d).

(a)

(b)

(c)

(d)

In the above, R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different from each other, and independently of each other hydrogen, linear or branched C 1-10 alkyl, hydroxyl, hydroxyl group substituted with carbon atoms 1- An alkyl group of 10,-(-CH 2- ) sO-[-CH 2 -CH 2 O-] t-CH 2 CH 2 OH (s is an integer of about 0-5, t is an integer of about 0-5) Is selected from the group consisting of

At least one of R 1 , R 2 , R 3 , R 4 and R 5 may be a hydroxyl group, an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group, or-(-CH 2- ) sO-[-CH 2 -CH 2 O-]. t-CH 2 CH 2 OH (s is an integer from about 0-5, t is an integer from about 0-5).
70. The compound of claim 69, wherein the composition comprises about 25-83.7 wt% of the binder, about 5-70 wt% of the photocurable monomer, about 0.1-5 wt% of the initiator, and the structure of Formula 1 of claim 1 A photocurable pressure-sensitive adhesive composition comprising about 1-30% by weight, ultraviolet absorber about 0.1-2% by weight and antioxidant about 0.1-2% by weight.
A display device comprising an adhesive layer made of the composition of any one of claims 59-71.
73. The apparatus of claim 72, wherein the device comprises a window glass comprising a cover glass, a touch screen panel including a transparent electrode film, and an adhesive layer between the cover glass and the transparent electrode film. Display device.
The display device of claim 72, wherein the adhesive layer has an elastic modulus of less than about 0.01 kgf / mm 2 for a thickness of 500 μm.
The display device of claim 72, wherein the adhesive layer has a storage modulus of about 6 × 10 3 to 1 × 10 4 Pa with respect to the thickness of the adhesive layer 500 μm.
The display device of claim 72, wherein the adhesive layer has an elongation of at least about 500% with respect to a thickness of the adhesive layer of 500 μm.
A display device comprising the photocurable pressure sensitive adhesive composition according to any one of claims 1 to 58 or an optical pressure sensitive adhesive film made of the photocurable pressure sensitive adhesive composition.
72. A method of temporarily curing the photocurable pressure sensitive adhesive composition in a laminate in which the photocurable pressure sensitive adhesive composition of any one of claims 1 to 71 is filled between the transparent electrode film layer and the window glass layer; Irradiating a light source from the side of the laminate; And main curing of the cured pressure-sensitive adhesive composition.
The method of claim 73 or 78, wherein the transparent electrode film is indium tin oxide (ITO), fluorinated tin oxide (FTO), aluminum dopped zinc oxide (AZO), carbon nanotube (CNT), Ag nanowire (nanowire), Module assembly method, characterized in that the film is laminated with one or more of graphene (graphene).