WO2014010934A1 - Adhesive composition for optical film - Google Patents

Adhesive composition for optical film Download PDF

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Publication number
WO2014010934A1
WO2014010934A1 PCT/KR2013/006128 KR2013006128W WO2014010934A1 WO 2014010934 A1 WO2014010934 A1 WO 2014010934A1 KR 2013006128 W KR2013006128 W KR 2013006128W WO 2014010934 A1 WO2014010934 A1 WO 2014010934A1
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WIPO (PCT)
Prior art keywords
meth
adhesive composition
acrylate
pressure
sensitive adhesive
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PCT/KR2013/006128
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French (fr)
Korean (ko)
Inventor
박은경
손지희
윤찬오
이재관
김장순
Original Assignee
(주)엘지하우시스
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Application filed by (주)엘지하우시스 filed Critical (주)엘지하우시스
Priority to JP2015520075A priority Critical patent/JP5947985B2/en
Priority to CN201380037167.9A priority patent/CN104471005B/en
Publication of WO2014010934A1 publication Critical patent/WO2014010934A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition for an optical film, and more particularly to a pressure-sensitive adhesive composition containing a hydrophilic functional group-containing monomer content is limited to a monomer of a certain component.
  • a liquid crystal cell in which both surfaces of a polarizing film such as a polyvinyl alcohol-based film imparted with polarization are sandwiched by a liquid crystal component in which a polarizing plate coated with a cellulose-based film such as a triacetic cellulose film is oriented between two glass plates. It is carried out by laminating
  • a polarizing film such as a polyvinyl alcohol-based film imparted with polarization
  • 10-0988185 discloses a pressure-sensitive adhesive composition comprising an acrylic polymer composed of a certain component, although the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition shows an excellent effect in peel force or durability, before and after peeling Due to the relationship between the pressure-sensitive adhesive layer and the adherend and the rework function of the adherend, nothing is described, which still implies the conventional problem of the remaining of foreign matter or residue after peeling off the pressure-sensitive adhesive layer.
  • the present invention is that the pressure-sensitive adhesive composition used for the optical film is neatly peeled off from the adherend of glass and plastic after water absorption, to impart a function that the adherent can be reworked (rework).
  • the purpose is that the pressure-sensitive adhesive composition used for the optical film is neatly peeled off from the adherend of glass and plastic after water absorption, to impart a function that the adherent can be reworked (rework).
  • the adhesive composition of this invention is characterized by including 25 weight part or more of hydrophilic functional group containing monomers with respect to 100 weight part of (meth) acrylic acid ester monomers.
  • the other object may include an adhesive layer formed by including the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition of the present invention can absorb a predetermined level or more water by containing a predetermined content or more of the hydrophilic functional group-containing monomer. Thereafter, moisture absorbed at high vacuum and high temperature is boiled, and volume expansion occurs, so that desorption with glass or plastic, to which the pressure-sensitive adhesive composition is attached, is facilitated, and the pressure-sensitive adhesive composition is neatly peeled back to the adhesive such as glass or plastic. Allow to have a rework function.
  • FIG. 1 is a diagram showing the before and after the water absorption of the pressure-sensitive adhesive composition of the present invention.
  • This invention provides the adhesive composition characterized by including 25 weight part or more of hydrophilic functional group containing monomers with respect to 100 weight part of (meth) acrylic acid ester monomers.
  • the pressure-sensitive adhesive composition of the present invention enables the peeling of the pressure-sensitive adhesive composition to be adhered to glass or plastic by including a hydrophilic functional group-containing monomer. More specifically, the hydrophilic functional group-containing monomer absorbs a certain level of water so that water exists through condensation in the pressure-sensitive adhesive composition.
  • liquid crystal displays such as glass or plastic, specifically, LCDs, which are detached from the pressure-sensitive adhesive composition, may have a rework function.
  • the hydrophilic functional group-containing monomer includes 25 parts by weight or more based on 100 parts by weight of the (meth) acrylic acid ester monomer, and when less than 25 parts by weight, the hydrophilic functional group-containing monomer is insufficient to sufficiently retain water. This becomes insufficient and the cohesion force between hydrophilic functional group containing monomers becomes low, and there exists a possibility that a destruction of superposition
  • the upper limit of the content ratio of the hydrophilic functional group-containing monomer is not limited, but in order to have a strong cohesive force and to be peeled off at any interface, it is preferable to include 80 parts by weight or more.
  • the said hydrophilic functional group containing monomer is 1 or more types chosen from a hydroxyl group containing monomer, an amino group containing monomer, a carboxyl group containing monomer, a sulfone group containing monomer, a morpholine group containing monomer, and a glycidyl group containing monomer.
  • hydroxyl-containing monomer 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, for example (Meth) acrylic acid hydroxyalkyl esters, such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and capro Caprolactone-modified monomers such as lactone-modified 2-hydroxyethyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, N-hydroxyethyl ( Primary hydroxyl group-containing monomers such as meta) acrylamide; 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy
  • hydroxyl group-containing monomers it is particularly preferable to use 2-hydroxyethyl (meth) acrylate because it contains little impurities such as di (meth) acrylate and is easy to manufacture.
  • amino-group containing monomer dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. are mentioned, for example.
  • carboxyl group-containing monomers examples include acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, and Michael adducts of (meth) acrylic acid (e.g., acrylic acid). Dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer and the like), 2- (meth) acryloyloxyethyldicarboxylic acid monoester (e.g.
  • sulfone group-containing monomers examples include olefin sulfones such as ethylene sulfone, allyl sulfone, and metaallyl sulfone, 2-acrylamide-2-methylpropane sulfone, styrene sulfone or salts thereof.
  • 4-methylmorpholine (4-Methylmorpholine) and the said glycidyl-group containing monomer are glycidyl (meth) acrylate, allyl glycidyl ether, etc. are mentioned as said morpholine group containing monomer.
  • the pressure-sensitive adhesive composition of the present invention can achieve the object of the present invention that can increase the moisture absorption by containing the hydrophilic functional group-containing monomer to rework the adherend after peeling off the pressure-sensitive adhesive composition.
  • the polymer molecular weight of the said (meth) acrylic acid ester monomer and the said hydrophilic functional group containing monomer is 1 million-1.2 million, It is characterized by the above-mentioned. If the polymer molecular weight exceeds 1.2 million, there is a problem that the specific gravity of the pressure-sensitive adhesive composition is increased, and if the polymer molecular weight is less than 1 million, durability may be weak.
  • the kind of (meth) acrylic acid ester monomer contained in the pressure-sensitive adhesive composition of the present invention is not particularly limited, and for example, alkyl (meth) acrylate can be used.
  • alkyl (meth) acrylate can be used.
  • Tg glass transition temperature
  • adhesion may be difficult to control, and thus the alkyl group having 1 to 14 carbon atoms ( It is preferable to use a meta) acrylic acid ester monomer.
  • the (meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t -Butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) At least one selected from the group consisting of acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate and tetradecyl (meth) acrylate.
  • a crosslinkable functional group may be provided, and in this case, the pressure-sensitive adhesive composition to be formed in the present invention may be a monomer mixture including a (meth) acrylic acid ester monomer, a hydrophilic functional group-containing monomer, and a crosslinkable monomer. May be a polymer of
  • the adhesive composition of this invention makes it possible to harden an adhesive composition by active energy ray irradiation, such as an ultraviolet-ray for a very short time, and can adjust the molecular weight of an adhesive composition.
  • active energy ray irradiation such as an ultraviolet-ray for a very short time
  • the pressure-sensitive adhesive composition is cured by heating, and the curing speed is slow, and there is difficulty in controlling the molecular weight of the pressure-sensitive adhesive composition, but both may be used in combination if necessary.
  • photoinitiator For example, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4- (2-hydroxyethoxy) Phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2- Acetophenones such as dimethylamino-1- (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; Benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone
  • the adhesive composition of this invention can further contain 0.5-1.0 weight part of photoinitiators with respect to 100 weight part of said (meth) acrylic acid ester monomers.
  • the photopolymerization initiator is out of the above range, many molecules having a short bond length may be generated, and thus durability may be weak.
  • electron rays, proton rays, neutral magnetic rays, and the like may be used in addition to electromagnetic waves such as ultraviolet rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, X-rays, and ⁇ -rays. Curing by ultraviolet irradiation is advantageous from the ease of obtaining the apparatus, the price, and the like.
  • a high pressure mercury lamp As the light source for the ultraviolet irradiation, a high pressure mercury lamp, an electrodeless lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a black light, and the like are used.
  • the said high pressure mercury lamp it is performed on condition of 5-3000mJ / cm ⁇ 2>, Preferably it is 10-1000mJ / cm ⁇ 2>.
  • the electrodeless lamp for example, it is carried out under a condition of 2 to 1500 mJ / cm 2, preferably 5 to 500 mJ / cm 2.
  • the irradiation time varies depending on the type of light source, the distance between the light source and the coated surface, the coating thickness, and other conditions, but usually several seconds to several tens of seconds, and in some cases, one second of water.
  • the pressure-sensitive adhesive composition of the present invention may absorb water for 48 hours in an environment of temperature 25 °C, humidity 50%, and dried for 1 hour at a temperature of 100 °C can absorb more than 5.0% by weight of water compared to the weight of the pressure-sensitive adhesive composition. .
  • the amount of water absorbed by the pressure-sensitive adhesive composition may be specifically 7.0 wt% or more.
  • the moisture moisture is not sufficiently ranged, so that there is not enough water particles to induce expansion in the inside under high temperature and vacuum conditions, resulting in the moisture of the pressure-sensitive adhesive composition.
  • peeling becomes difficult after absorption, and there exists a possibility of causing moisture condensation in use with an adhesive composition.
  • the water vapor transmission rate of the pressure-sensitive adhesive composition of the present invention is characterized in that 110g / m 2 ⁇ 24hr or less under the conditions of temperature 40 °C, relative humidity 70%.
  • Moisture permeability refers to the degree of water vapor permeation through the paper, and refers to the amount of water vapor transmitted through the surface area of 1 m 2 of paper under a certain condition in g in g.
  • the moisture permeability exceeds 110 g / m 2 ⁇ 24hr at a temperature of 40 ° C. and a relative humidity of 70%, the network capable of moving moisture may not be dense, and in this case, the content of the hydrophilic functional group-containing monomer is insufficient. There is little interaction with and the moisture permeability is increased, on the contrary, the pressure-sensitive adhesive composition has a problem in that the cohesive force is low because the content of the hydrophilic functional group-containing monomer is low.
  • the water vapor transmission rate may be 100 g / m 2 ⁇ 24hr or more, but the lower limit thereof is not limited.
  • the adhesive composition of the present invention is characterized in that the peel force after water absorption is smaller than the peel force before water absorption. Due to the reduced peel force after water absorption, the pressure-sensitive adhesive composition is neatly peeled from the adherend, whereby the adherend can be used again.
  • the adhesive of the pressure-sensitive adhesive composition may be glass or plastic, for example, may be attached between a touch screen panel (TSP) and a liquid crystal display (LCD). .
  • FIG. 1 is a schematic diagram showing before and after water absorption of the pressure-sensitive adhesive composition of the present invention.
  • the pressure-sensitive adhesive composition is laminated between the TSP and the LCD to firmly adhere the adhesive.
  • the present invention allows the adhesive composition to be removed without debris or residue after desorption of the adhesive composition and the LCD, containing a certain amount of hydrophilic functional group in the adhesive composition in order to give the LCD rework (rework) function Monomers.
  • the hydrophilic functional group-containing monomer can impregnate a certain level of water, and vapor bubbles inside the water particles in which the hydrophilic functional group-containing monomer is impregnated at low pressure after vacuum / high temperature conditions. Is generated and vaporized, the volume expansion occurs, the peeling force of the pressure-sensitive adhesive composition to the adherend becomes small.
  • the pressure-sensitive adhesive composition attached to the LCD can be detached without residue or foreign matter due to the increased peeling force, and the pressure-sensitive adhesive composition can be easily removed compared to the conventional LCD. Can be reworked.
  • the peeling force before water absorption of the pressure-sensitive adhesive composition may be characterized in that 1,500 ⁇ 2,000g / in, peeling force after water absorption is 800 ⁇ 1,100g / in.
  • peeling force before water absorption of the pressure-sensitive adhesive composition is out of the above range, there is a fear of detachment from the adherend by the external environment or impact.
  • peeling force after the water absorption of the pressure-sensitive adhesive composition is out of the above range does not peel the pressure-sensitive adhesive composition at the interface with the adhesive, there is a problem that the adhesive is torn when peeling off by twisting arbitrarily.
  • the present invention provides a pressure-sensitive adhesive layer characterized in that the pressure-sensitive adhesive composition is formed, and further, the pressure-sensitive adhesive layer can be used for the optical member.
  • the thickness of the said adhesive layer is not specifically limited, 5-300 micrometers is preferable, Especially 10-50 micrometers is preferable, Furthermore, 12-30 micrometers is preferable.
  • the thickness of the pressure-sensitive adhesive layer is too thin, there is a tendency that the adhesive physical properties are difficult to stabilize, and when too thick, the thickness of the entire optical member to which the pressure-sensitive adhesive layer can be applied tends to increase excessively.
  • optical film used suitably for image display apparatuses, such as a liquid crystal display device, an organic electroluminescence display, and a PDP, for example, a polarizing plate, a retardation plate, an elliptical polarizing plate, an optical compensation film, And luminance-enhanced films, and those in which they are laminated.
  • Example 1 Except for obtaining a polymer having a molecular weight of about 1.2 million including 25 parts by weight of 2-hydroxyethyl acrylate in Example 1, a pressure-sensitive adhesive composition was prepared as in Example 1.
  • a pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for obtaining a polymer having a molecular weight of about 1 million by including 30 parts by weight of acrylic acid based on 100 parts by weight of 2-ethylhexyl acrylate in Example 1.
  • the pressure-sensitive adhesive composition was prepared in the same manner as in Example 3 except that 25 parts by weight of acrylic acid was obtained to obtain a polymer having a molecular weight of about 1.1 million.
  • a pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for obtaining a polymer having a molecular weight of about 1.1 million by including 30 parts by weight of glycidyl methacrylate with respect to 100 parts by weight of 2-ethylhexyl acrylate in Example 1. .
  • a pressure-sensitive adhesive composition was prepared in the same manner as in Example 5 except that 25 parts by weight of glycidyl methacrylate was obtained to obtain a polymer having a molecular weight of about 1.2 million.
  • a pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 1 except that 20 parts by weight of 2-hydroxyethyl acrylate was obtained to obtain a polymer having a molecular weight of about 1.2 million.
  • the pressure-sensitive adhesive composition of Examples and Comparative Examples of Table 1 was cured to prepare a pressure-sensitive adhesive layer having a thickness of 100 ⁇ m, and then the pressure-sensitive adhesive layer was attached between the TSP and the LCD. At this time, the water absorption of the pressure-sensitive adhesive layer, moisture permeability, peel strength, and LCD reuse (rework) The availability was measured.
  • Moisture absorption amount The pressure-sensitive adhesive layer containing moisture for 48 hours in an environment of temperature 25 °C, 50% humidity is dried for 1 hour at 100 °C temperature weight of the adhesive layer through a moisture analyzer (Moisture analyzer Ohus MB45) The rate of reduction was calculated and the moisture uptake was measured.
  • Peeling force A pressure of 300 g per 1 cm 2 was applied to the pressure-sensitive adhesive layer adhered to the LCD surface to bring the adhesive force into close contact. Thereafter, some of the ends of the pressure-sensitive adhesive layer were peeled at a peel rate of 300 mm / min at a peel angle of 180 degrees to measure its peel strength.
  • LCD reworkability Heat the product at 70 °C under 50 Torr vacuum for more than 30 minutes under 50 Torr vacuum after allowing it to be absorbed by high temperature, high humidity (85/85) for 2 days with adhesive layer attached between TSP and LCD. Then, the pressure-sensitive adhesive layer was taken out and twisted to observe whether the LCD could be reworked after desorption with the LCD.
  • Table 2 shows the results of the above water absorption, water vapor permeability, peel strength, and LCD rework.
  • the pressure-sensitive adhesive composition of Examples 1 to 6 containing 25 parts by weight or more of the hydrophilic functional group-containing monomer, it was found that it had a water absorption of 5% or more and a water vapor transmission rate of 110 g / m 2 ⁇ 24hr or less.
  • the water absorption amount and the moisture permeability of the above values include a smaller peeling force after water absorption than before water absorption, so that the LCD and the pressure-sensitive adhesive composition can be easily detached and peeled off without leaving any residue or impurities. (rework) is possible.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provides an adhesive composition comprising 25 parts by weight or more of a monomer comprising a hydrophilic functional group on the basis of 100 parts by weight of a (meth)acrylate-based monomer. In addition, the present invention can comprise an adhesive layer formed by comprising an adhesive composition comprising 25 parts by weight or more of a monomer comprising a hydrophilic functional group on the basis of 100 parts by weight of a (meth)acrylate-based monomer.

Description

광학필름용 점착제 조성물Adhesive composition for optical film
본 발명은 광학필름용 점착제 조성물에 관한 것으로, 보다 상세하게는 일정성분의 모노머에 함량이 한정된 친수성 관능기 함유 단량체를 포함하고 있는 점착제 조성물에 관한 것이다. The present invention relates to a pressure-sensitive adhesive composition for an optical film, and more particularly to a pressure-sensitive adhesive composition containing a hydrophilic functional group-containing monomer content is limited to a monomer of a certain component.
종래에는 편광 필름, 예컨대 편광성이 부여된 폴리비닐알코올계 필름 등의 양면이, 셀룰로오스계 필름, 예컨대 트리아세트산셀룰로오스 필름으로 피복된 편광판을, 2장의 유리판 사이에 배향한 액정 성분을 협지시킨 액정 셀의 표면에 적층하여, 액정 표시판으로 하는 것이 행해지고 있고, 이 액정 셀면에의 적층은, 편광판 표면에 형성한 점착제층을 상기 액정 셀면에 접촉하여, 눌러 붙임으로써 행해지는 것이 통상이다.Conventionally, a liquid crystal cell in which both surfaces of a polarizing film such as a polyvinyl alcohol-based film imparted with polarization are sandwiched by a liquid crystal component in which a polarizing plate coated with a cellulose-based film such as a triacetic cellulose film is oriented between two glass plates. It is carried out by laminating | stacking on the surface of and making a liquid crystal display panel, and lamination | stacking on this liquid crystal cell surface is normally performed by contacting and pressing the adhesive layer formed in the polarizing plate surface to the said liquid crystal cell surface.
그러나, 상기의 점착제층을 형성한 광학 부재를 액정 셀에 접합시키고, 다시 박리 시킨 후에 점착제층과 점착되었던 LCD면 등에 이물 혼입이나 손상, 접착 미스 등이 발생할 수 있어, LCD를 다시 사용(rework)하는 데에는 어려움이 있었다. 또한 대한민국등록특허 제 10-0988185호에서는 일정성분으로 구성된 아크릴계 중합체를 포함하는 점착제 조성물이 개시되어 있고, 상기 점착제 조성물을 포함하는 점착제층이 박리력 또는 내구성에서 우수한 효과를 보이고 있기는 하나, 박리 전후로 인한 점착제층과 피착제와의 관계 및 피착제의 재사용(rework) 기능에 대해서는 어떠한 사항도 기재되어 있지 않아 점착제층의 박리 후에 이물질 또는 찌꺼기의 잔존에 대한 종래의 문제점을 여전히 내포하고 있다. However, after the optical member on which the pressure-sensitive adhesive layer is formed is bonded to the liquid crystal cell and peeled again, foreign matters may be mixed or damaged, or adhesive miss may occur on the LCD surface, which has been adhered to the pressure-sensitive adhesive layer, and the LCD may be reworked. There was a difficulty. In addition, the Republic of Korea Patent No. 10-0988185 discloses a pressure-sensitive adhesive composition comprising an acrylic polymer composed of a certain component, although the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition shows an excellent effect in peel force or durability, before and after peeling Due to the relationship between the pressure-sensitive adhesive layer and the adherend and the rework function of the adherend, nothing is described, which still implies the conventional problem of the remaining of foreign matter or residue after peeling off the pressure-sensitive adhesive layer.
상기의 문제점을 해결하기 위하여, 본 발명은 광학필름용으로 사용되는 점착제 조성물이 수분흡수 후 유리 및 플라스틱의 피착제 등으로부터 깔끔하게 박리되어, 상기 피착제가 재사용(rework)될 수 있는 기능을 부여하는 것을 목적으로 한다. In order to solve the above problems, the present invention is that the pressure-sensitive adhesive composition used for the optical film is neatly peeled off from the adherend of glass and plastic after water absorption, to impart a function that the adherent can be reworked (rework). The purpose.
상기 하나의 목적을 달성하기 위해서 본 발명의 점착제 조성물은 (메타) 아크릴산 에스테르계 단량체 100중량부에 대하여, 친수성 관능기 함유 단량체를 25중량부 이상 포함하는 것을 특징으로 한다.In order to achieve the said one objective, the adhesive composition of this invention is characterized by including 25 weight part or more of hydrophilic functional group containing monomers with respect to 100 weight part of (meth) acrylic acid ester monomers.
또한, 상기 다른 목적을 달성하기 위해서 상기 점착제 조성물을 포함하여 형성되는 점착제층을 포함할 수 있다. In addition, in order to achieve the other object may include an adhesive layer formed by including the pressure-sensitive adhesive composition.
본 발명의 점착제 조성물은 친수성 관능기 함유 단량체를 일정함량 이상 포함함으로써, 일정수준 이상의 수분을 흡수할 수 있다. 그 후, 고진공, 고온에서 흡수된 수분이 끓게 되어 부피팽창이 일어나면서 점착제 조성물이 부착되었던 유리 또는 플라스틱 등과의 탈착이 용이하게 되고, 점착제 조성물이 깔끔하게 박리됨으로써 상기 유리 또는 플라스틱 등의 피착제에 다시 사용(rework) 기능을 가질 수 있게 한다.The pressure-sensitive adhesive composition of the present invention can absorb a predetermined level or more water by containing a predetermined content or more of the hydrophilic functional group-containing monomer. Thereafter, moisture absorbed at high vacuum and high temperature is boiled, and volume expansion occurs, so that desorption with glass or plastic, to which the pressure-sensitive adhesive composition is attached, is facilitated, and the pressure-sensitive adhesive composition is neatly peeled back to the adhesive such as glass or plastic. Allow to have a rework function.
도 1은 본 발명인 점착제 조성물의 수분흡수 전, 후를 도식화하여 나타낸 것이다.1 is a diagram showing the before and after the water absorption of the pressure-sensitive adhesive composition of the present invention.
본 발명의 이점 및 특징, 그리고 그것들을 달성하는 방법은 함께 상세하게 후술되어 있는 실시예들을 참조하면 명확해 질것이다. 그러나, 본 발명은 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 것이며, 단지 본 실시예들은 본 발명의 개시가 완전하도록 하며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이며, 본 발명은 청구항의 범주에 의해 정의될 뿐이다. 명세서 전체에 걸쳐 동일 참조 부호는 동일 구성요소를 지칭한다.Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, only the present embodiments to make the disclosure of the present invention complete, and common knowledge in the art to which the present invention pertains. It is provided to fully inform the person having the scope of the invention, which is defined only by the scope of the claims. Like reference numerals refer to like elements throughout.
이하, 본 발명에 대하여 자세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 (메타) 아크릴산 에스테르계 단량체 100중량부에 대하여, 친수성 관능기 함유 단량체를 25중량부 이상 포함하는 것을 특징으로 하는 점착제 조성물을 제공한다. This invention provides the adhesive composition characterized by including 25 weight part or more of hydrophilic functional group containing monomers with respect to 100 weight part of (meth) acrylic acid ester monomers.
본 발명의 점착제 조성물은 친수성 관능기 함유 단량체를 포함함으로써 유리 또는 플라스틱에 접착하는 점착제 조성물의 박리를 가능하게 한다. 보다 구체적으로 상기 친수성 관능기 함유 단량체가 일정수준의 수분을 흡수하여 점착제 조성물 내부에서 응축을 통해 수분이 존재하도록 한다. The pressure-sensitive adhesive composition of the present invention enables the peeling of the pressure-sensitive adhesive composition to be adhered to glass or plastic by including a hydrophilic functional group-containing monomer. More specifically, the hydrophilic functional group-containing monomer absorbs a certain level of water so that water exists through condensation in the pressure-sensitive adhesive composition.
그 후, 고진공 고온에서 흡수된 상기 수분이 끓게 되어 점착제 조성물의 부피팽창이 일어나게 되는바, 상기 부피팽창으로 인해 점착제 조성물이 유리 또는 플라스틱 등의 피착제에서 찌꺼기나 이물질 없이 탈착이 가능하게 된다. 이로 인하여, 점착제 조성물에 대하여 탈착된 유리 또는 플라스틱, 구체적으로는 LCD등의 액정 표시장치들이 재사용(rework)기능을 가질 수 있게 된다. Thereafter, the moisture absorbed at a high vacuum high temperature is boiled to cause volume expansion of the pressure-sensitive adhesive composition. The volume expansion enables the pressure-sensitive adhesive composition to be detached from the adherend such as glass or plastic without residue or foreign matter. As a result, liquid crystal displays, such as glass or plastic, specifically, LCDs, which are detached from the pressure-sensitive adhesive composition, may have a rework function.
상기 친수성 관능기 함유 단량체는 (메타) 아크릴산 에스테르계 단량체 100중량부에 대하여 25중량부 이상을 포함하는바, 25중량부 미만을 포함하는 경우 친수성 관능기 함유 단량체가 부족하여 수분이 충분히 정체될 수 있는 영역이 부족해지고, 친수성 관능기 함유 단량체 사이의 응집력이 낮아지기 때문에 중합의 파괴가 일어나 고습 조건 후에 박리가 용이해지지 않을 우려가 있다. 상기 친수성 관능기 함유 단량체 포함비율의 상한에 제한이 있는 것은 아니나, 강한 응집력을 가지도록 하여 어느 한 계면에서 박리되도록 하기 위해서는 80중량부 이상을 포함하는 것이 바람직하다. The hydrophilic functional group-containing monomer includes 25 parts by weight or more based on 100 parts by weight of the (meth) acrylic acid ester monomer, and when less than 25 parts by weight, the hydrophilic functional group-containing monomer is insufficient to sufficiently retain water. This becomes insufficient and the cohesion force between hydrophilic functional group containing monomers becomes low, and there exists a possibility that a destruction of superposition | polymerization may occur and peeling may not become easy after high humidity conditions. The upper limit of the content ratio of the hydrophilic functional group-containing monomer is not limited, but in order to have a strong cohesive force and to be peeled off at any interface, it is preferable to include 80 parts by weight or more.
상기 친수성 관능기 함유 단량체가 수산기 함유 단량체, 아미노기 함유 단량체, 카르복실기 함유 단량체, 설폰기 함유 단량체, 모르폴린기 함유 단량체, 글리시딜기 함유 단량체로부터 선택되는 1종 이상인 것을 특징으로 한다.The said hydrophilic functional group containing monomer is 1 or more types chosen from a hydroxyl group containing monomer, an amino group containing monomer, a carboxyl group containing monomer, a sulfone group containing monomer, a morpholine group containing monomer, and a glycidyl group containing monomer.
상기 수산기 함유 단량체로서는 예컨대, 2-히드록시에틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 5-히드록시펜틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 8-히드록시옥틸(메타)아크릴레이트, 10-히드록시데실(메타)아크릴레이트, (4-히드록시메틸시클로헥실)메틸(메타) 아크릴레이트 등의 (메타)아크릴산히드록시알킬에스테르, 카프로락톤 변성 2-히드록시에틸(메타)아크릴레이트 등의 카프로락톤 변성 모노머, 2-아크릴로일옥시에틸-2-히드록시에틸프탈산, N-메틸올(메타)아크릴아미드, N-히드록시에틸(메타)아크릴아미드 등의 1급 수산기 함유 모노머; 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 2-히드록시-3-페녹시프로필(메타)아크릴레이트, 3-클로로-2-히드록시프로필(메타)아크릴레이트, 2-히드록시-3-페녹시프로필(메타)아크릴레이트 등의 2급 수산기 함유 모노머; 2,2-디메틸-2-히드록시에틸(메타)아크릴레이트 등의 3급 수산기 함유 모노머를 들 수 있다. As said hydroxyl-containing monomer, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, for example (Meth) acrylic acid hydroxyalkyl esters, such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and capro Caprolactone-modified monomers such as lactone-modified 2-hydroxyethyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, N-hydroxyethyl ( Primary hydroxyl group-containing monomers such as meta) acrylamide; 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) Secondary hydroxyl group-containing monomers such as acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; Tertiary hydroxyl group containing monomers, such as 2, 2- dimethyl- 2-hydroxyethyl (meth) acrylate, are mentioned.
상기 수산기 함유 단량체 중에서도, 2-히드록시에틸(메타)아크릴레이트를 사용하는 것이, 디(메타)아크릴레이트 등의 불순물이 적고, 제조하기 쉬운 점에서 특히 바람직하다. Among the hydroxyl group-containing monomers, it is particularly preferable to use 2-hydroxyethyl (meth) acrylate because it contains little impurities such as di (meth) acrylate and is easy to manufacture.
상기 아미노기 함유 단량체로서는, 예컨대, 디메틸아미노에틸(메타) 아크릴레이트, 디에틸아미노에틸(메타)아크릴레이트 등을 들 수 있다.As said amino-group containing monomer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. are mentioned, for example.
상기 카르복실기 함유 단량체로서는, 예컨대, 아크릴산, 메타크릴산, 크로톤산, 말레산, 무수말레산, 이타콘산, 푸마르산, 아크릴아미드 N-글리콜산, 계피산, (메타)아크릴산의 마이클 부가물(예컨대, 아크릴산 다이머, 메타크릴산 다이머, 아크릴산 트라이머, 메타크릴산 트라이머, 아크릴산 테트라머, 메타크릴산 테트라머 등), 2-(메타)아크릴로일옥시에틸디카르복실산모노에스테르(예컨대, 2-아크릴로일옥시에틸숙신산모노에스테르, 2-메타크릴로일옥시에틸숙신산모노에스테르, 2-아크릴로일옥시에틸프탈산모노에스테르, 2-메타크릴로일옥시에틸프탈산모노 에스테르, 2-아크릴로일옥시에틸헥사히드로프탈산모노에스테르, 2-메타크릴로일옥시에틸헥사히드로프탈산모노에스테르 등) 등을 들 수 있다.Examples of the carboxyl group-containing monomers include acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, and Michael adducts of (meth) acrylic acid (e.g., acrylic acid). Dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer and the like), 2- (meth) acryloyloxyethyldicarboxylic acid monoester (e.g. 2- Acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxy Ethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester, etc.) etc. are mentioned.
상기 설폰기 함유 단량체로서는, 예컨대, 에틸렌설폰, 알릴설폰, 메타알릴설폰 등의 올레핀설폰, 2-아크릴아미드-2-메틸프로판설폰, 스티렌설폰 또는 그의 염 등을 들 수 있다. 상기 모르필린기 함유 단량체로서는 4-메틸모르필린(4-Methylmorpholine), 상기 글리시딜기 함유 단량체로서는, 예컨대, 글리시딜(메타) 아크릴레이트, 알릴글리시딜에테르 등을 들 수 있다.Examples of the sulfone group-containing monomers include olefin sulfones such as ethylene sulfone, allyl sulfone, and metaallyl sulfone, 2-acrylamide-2-methylpropane sulfone, styrene sulfone or salts thereof. 4-methylmorpholine (4-Methylmorpholine) and the said glycidyl-group containing monomer are glycidyl (meth) acrylate, allyl glycidyl ether, etc. are mentioned as said morpholine group containing monomer.
본 발명의 점착제 조성물은 상기 친수성 관능기 함유 단량체를 포함함으로써 수분 흡수율을 높여 상기 점착제 조성물의 박리 후에 피착제를 재사용(rework) 할 수 있는 본 발명의 목적을 달성할 수 있다.The pressure-sensitive adhesive composition of the present invention can achieve the object of the present invention that can increase the moisture absorption by containing the hydrophilic functional group-containing monomer to rework the adherend after peeling off the pressure-sensitive adhesive composition.
이 때, 상기 (메타) 아크릴산 에스테르계 단량체 및 상기 친수성 관능기 함유 단량체의 중합체 분자량이 100만~120만인 것을 특징으로 한다. 상기 중합체 분자량이 120만을 초과하는 경우 점착제 조성물의 비중이 커지는 문제점이 있고, 100만 미만인 경우 내구성이 취약할 우려가 있다. At this time, the polymer molecular weight of the said (meth) acrylic acid ester monomer and the said hydrophilic functional group containing monomer is 1 million-1.2 million, It is characterized by the above-mentioned. If the polymer molecular weight exceeds 1.2 million, there is a problem that the specific gravity of the pressure-sensitive adhesive composition is increased, and if the polymer molecular weight is less than 1 million, durability may be weak.
본 발명의 점착제 조성물이 포함하는 (메타) 아크릴산 에스테르계 단량체의 종류는 특별히 한정되지 않으며, 예를 들면 알킬 (메타)아크릴레이트를 사용할 수 있다. 이 때, 단량체에 포함되는 알킬기가 지나치게 장쇄가 되면, 상기 점착제 조성물의 응집력이 저하되고, 유리전이온도(Tg) 및 점착성의 조절이 어려워질 우려가 있으므로, 탄소수가 1 내지 14인 알킬기를 갖는 (메타)아크릴산 에스테르계 단량체를 사용하는 것이 바람직하다. The kind of (meth) acrylic acid ester monomer contained in the pressure-sensitive adhesive composition of the present invention is not particularly limited, and for example, alkyl (meth) acrylate can be used. At this time, when the alkyl group contained in the monomer is too long, the cohesive force of the pressure-sensitive adhesive composition may be lowered, and the glass transition temperature (Tg) and the adhesion may be difficult to control, and thus the alkyl group having 1 to 14 carbon atoms ( It is preferable to use a meta) acrylic acid ester monomer.
상기 (메타) 아크릴산 에스테르계 단량체는 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, n-프로필 (메타)아크릴레이트, 이소프로필 (메타)아크릴레이트, n-부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, sec-부틸 (메타)아크릴레이트, 펜틸 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, 2-에틸부틸 (메타)아크릴레이트, n-옥틸 (메타)아크릴레이트, 이소옥틸 (메타)아크릴레이트, 이소노닐 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트 및 테트라데실 (메타)아크릴레이트로 이루어진 군으로부터 선택된 하나 이상일 수 있다. The (meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t -Butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) At least one selected from the group consisting of acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate and tetradecyl (meth) acrylate.
상기 점착제 조성물을 형성하는데 있어서, 가교성 관능기가 부여되어 있을 수 있으며, 이 경우 본 발명에서 형성하고자 하는 점착제 조성물은 (메타)아크릴산 에스테르계 단량체, 친수성 관능기 함유 단량체 및 가교성 단량체를 포함하는 단량체 혼합물의 중합체일 수 있다,In forming the pressure-sensitive adhesive composition, a crosslinkable functional group may be provided, and in this case, the pressure-sensitive adhesive composition to be formed in the present invention may be a monomer mixture including a (meth) acrylic acid ester monomer, a hydrophilic functional group-containing monomer, and a crosslinkable monomer. May be a polymer of
본 발명의 점착제 조성물은 광중합 개시제를 추가로 포함함으로써, 매우 단시간의 자외선 등의 활성 에너지선 조사에 의해 점착제 조성물을 경화할 수 있게 하고, 점착제 조성물의 분자량을 조절할 수 있다. 열중합 개시제를 사용하는 경우 가열에 의해 점착제 조성물을 경화하는 것으로, 경화 속도가 느리고, 점착제 조성물의 분자량 조절에 어려움이 있으나, 필요에 따라 양방을 병용할 수 있다.By further including a photoinitiator, the adhesive composition of this invention makes it possible to harden an adhesive composition by active energy ray irradiation, such as an ultraviolet-ray for a very short time, and can adjust the molecular weight of an adhesive composition. In the case of using a thermal polymerization initiator, the pressure-sensitive adhesive composition is cured by heating, and the curing speed is slow, and there is difficulty in controlling the molecular weight of the pressure-sensitive adhesive composition, but both may be used in combination if necessary.
상기 광중합 개시제로서는, 특별히 한정되는 것은 아니며, 예컨대, 디에톡시아세토페논, 2-히드록시-2-메틸-1-페닐프로판-1-온, 벤질디메틸케탈, 4-(2-히드록시에톡시)페닐-(2-히드록시-2-프로필)케톤, 1-히드록시시클로헥실페닐 케톤, 2-메틸-2-모르폴리노(4-티오메틸페닐)프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)부타논, 2-히드록시-2-메틸-1-[4-(1-메틸비닐)페닐]프로파논 올리고머 등의 아세토페논류; 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르, 벤조인이소부틸에테르 등의 벤조인류; 벤조페논, o-벤조일벤조산메틸, 4-페닐벤조페논, 4-벤조일-4'-메틸-디페닐술파이드, 3,3',4,4'-테트라(t-부틸퍼옥시카르보닐)벤조페논, 2,4,6-트리메틸벤조페논, 4-벤조일-N,N-디메틸-N-[2-(1-옥소-2-프로페닐옥시)에틸]벤젠메탄아미늄브로마이드, (4-벤조일벤질)트리메틸암모늄클로라이드 등의 벤조페논류; 2-이소프로필티오크산톤, 4-이소프로필티오크산톤, 2,4-디에틸티오크산톤, 2,4-디클로로티오크산톤, 1-클로로-4-프로폭시티오크산톤, 2-(3-디메틸아미노-2-히드록시)-3,4-디메틸-9H-티오크산톤-9-온메소클로라이드 등의 티오크산톤류; 2,4,6-트리메틸벤조일-디페닐포스핀옥사이드, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸-펜틸포스핀옥사 이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드 등의 아실포스폰옥사이드류; 등을 들 수 있다. 또, 이들 광중합 개시제는 하나만이 단독으로 이용되어도 되고, 하나 이상이 병용되어도 된다.It does not specifically limit as said photoinitiator, For example, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4- (2-hydroxyethoxy) Phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2- Acetophenones such as dimethylamino-1- (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; Benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzo Phenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethanealuminum bromide, (4-benzoyl Benzophenones such as benzyl) trimethylammonium chloride; 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, 2- ( Thioxanthones, such as 3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H- thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl Acyl phosphon oxides such as) -phenylphosphine oxide; Etc. can be mentioned. Moreover, only one of these photoinitiators may be used independently, and one or more may be used together.
또한, 이들의 조제로서, 트리에탄올아민, 트리이소프로판올아민, 4,4'-디메틸아미노벤조페논(미힐러 케톤), 4,4'-디에틸아미노벤조페논, 2-디메틸아미노에틸벤조산, 4-디메틸아미노벤조산에틸, 4-디메틸아미노벤조산(n-부톡시)에틸, 4-디메틸아미노벤조산이소아밀, 4-디메틸아미노벤조산 2-에틸헥실, 2,4-디에틸티오크산톤, 2,4-디이소프로필티오크산톤 등을 병용하는 것도 가능하다.As these preparations, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Mihiler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethyl Ethyl aminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,4-diethylthioxanthone, 2,4- It is also possible to use diisopropyl thioxanthone together.
이들 중에서도, 벤질디메틸케탈, 1-히드록시시클로헥실페닐케톤, 벤조일이소프로필에테르, 4-(2-히드록시에톡시)-페닐(2-히드록시-2-프로필)케톤, 2-히드록시-2-메틸-1-페닐프로판-1-온을 이용하는 것이 바람직하다.Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy- Preference is given to using 2-methyl-1-phenylpropan-1-one.
상기 광중합 개시제의 함유량에 있어서, 본 발명의 점착제 조성물은 상기 (메타) 아크릴산 에스테르계 단량체 100중량부에 대하여, 광중합 개시제 0.5~1.0중량부를 추가로 포함할 수 있다. 상기 광중합 개시제가 상기 범위를 벗어나는 경우, 결합길이가 짧은 분자들이 많이 생성되어 내구성이 취약할 우려가 있다. In content of the said photoinitiator, the adhesive composition of this invention can further contain 0.5-1.0 weight part of photoinitiators with respect to 100 weight part of said (meth) acrylic acid ester monomers. When the photopolymerization initiator is out of the above range, many molecules having a short bond length may be generated, and thus durability may be weak.
본 발명의 점착제 조성물을 경화함에 있어서, 원자외선, 자외선, 근자외선, 적외선 등의 광선, X선, γ선 등의 전자파외에, 전자선, 프로톤선, 중성 자선 등을 이용할 수 있으나, 경화 속도, 조사 장치의 입수의 용이성, 가격 등으로부터 자외선 조사에 의한 경화가 유리하다. In curing the pressure-sensitive adhesive composition of the present invention, electron rays, proton rays, neutral magnetic rays, and the like may be used in addition to electromagnetic waves such as ultraviolet rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, X-rays, and γ-rays. Curing by ultraviolet irradiation is advantageous from the ease of obtaining the apparatus, the price, and the like.
그리고, 상기 자외선 조사를 행할 때의 광원으로서는, 고압 수은등, 무전극 램프, 초고압 수은등 카본 아크등, 크세논등, 메탈핼라이드 램프, 케미컬 램프, 블랙라이트 등이 이용된다. 상기 고압 수은 램프의 경우에는, 예컨대, 5∼3000mJ/㎠, 바람직하게는 10~1000mJ/㎠의 조건에서 행해진다. 또한, 상기 무전극 램프의 경우에는, 예컨대, 2∼1500mJ/㎠, 바람직하게는 5∼500mJ/㎠의 조건에서 행해진다. As the light source for the ultraviolet irradiation, a high pressure mercury lamp, an electrodeless lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a black light, and the like are used. In the case of the said high pressure mercury lamp, it is performed on condition of 5-3000mJ / cm <2>, Preferably it is 10-1000mJ / cm <2>. In the case of the electrodeless lamp, for example, it is carried out under a condition of 2 to 1500 mJ / cm 2, preferably 5 to 500 mJ / cm 2.
그리고, 조사시간은, 광원의 종류, 광원과 도포면과의 거리, 도공 두께, 그 외의 조건에 따라서도 다르지만, 통상은, 수초∼수십초, 경우에 따라서는 수분의 1초여도 된다. The irradiation time varies depending on the type of light source, the distance between the light source and the coated surface, the coating thickness, and other conditions, but usually several seconds to several tens of seconds, and in some cases, one second of water.
본 발명의 점착제 조성물은 온도 25℃, 습도 50%의 환경에서 48시간 동안 수분을 흡수하고, 온도 100℃에서 1시간 동안 건조한 결과 상기 점착제 조성물 중량과 대비하여 5.0중량%이상의 수분을 흡수할 수 있다. 상기 점착제 조성물이 흡수하는 수분의 양은 구체적으로 7.0중량%이상이 될 수 있다. 상기 점착제 조성물이 아크릴산 에스테르계 단량체 100중량부에 대하여, 친수성 관능기 함유 단량체를 25중량부 이상 포함함으로써, 상기 친수성 관능기 함유 단량체로 인하여 일정수준의 수분 흡수량을 확보 할 수 있다.The pressure-sensitive adhesive composition of the present invention may absorb water for 48 hours in an environment of temperature 25 ℃, humidity 50%, and dried for 1 hour at a temperature of 100 ℃ can absorb more than 5.0% by weight of water compared to the weight of the pressure-sensitive adhesive composition. . The amount of water absorbed by the pressure-sensitive adhesive composition may be specifically 7.0 wt% or more. By the pressure-sensitive adhesive composition containing 25 parts by weight or more of the hydrophilic functional group-containing monomer with respect to 100 parts by weight of the acrylic acid ester monomer, it is possible to ensure a certain level of water absorption due to the hydrophilic functional group-containing monomer.
상기 점착제 조성물이 흡수하는 수분의 양이 5.0중량%미만인 경우 수분 함습이 충분히 이루어지지 않는 범위이므로 고온 및 진공조건에서 내부에 머금고 있는 팽창을 유도할만한 수분입자가 충분치 못하여, 결과적으로 점착제 조성물의 수분흡수 후 박리가 어려워진다는 문제점이 있고, 점착제 조성물로의 사용에 있어서 수분 결로를 유발할 우려가 있다. 바람직하게는 5.0중량%이상, 가장 바람직하게는 7.0중량%이상으로 할 수 있으나, 상기 점착제 조성물의 수분흡수량의 상한에 제한이 있는 것은 아니다. If the amount of water absorbed by the pressure-sensitive adhesive composition is less than 5.0% by weight, the moisture moisture is not sufficiently ranged, so that there is not enough water particles to induce expansion in the inside under high temperature and vacuum conditions, resulting in the moisture of the pressure-sensitive adhesive composition. There exists a problem that peeling becomes difficult after absorption, and there exists a possibility of causing moisture condensation in use with an adhesive composition. Preferably at least 5.0% by weight, most preferably at least 7.0% by weight, but the upper limit of the water absorption of the pressure-sensitive adhesive composition is not limited.
추가적으로, 본 발명의 점착제 조성물의 투습도가 온도 40℃, 상대 습도 70%의 조건에서 110g/m2·24hr이하인 것을 특징으로 한다. 투습도는 종이에 수증기가 투과되는 정도를 나타내는 것으로, 일정 조건 아래에서 1m2의 종이의 표면적인 24시간 동안 투과하는 수증기양을 g으로 나타내는 것을 일컫는다.In addition, the water vapor transmission rate of the pressure-sensitive adhesive composition of the present invention is characterized in that 110g / m 2 · 24hr or less under the conditions of temperature 40 ℃, relative humidity 70%. Moisture permeability refers to the degree of water vapor permeation through the paper, and refers to the amount of water vapor transmitted through the surface area of 1 m 2 of paper under a certain condition in g in g.
온도 40℃, 상대 습도 70%의 조건에서 상기 투습도가 110g/m2·24hr를 초과하는 경우 수분이 이동할 수 있는 네트워크가 조밀하지 않을 수 있고, 이 경우 친수성 관능기 함유 단량체의 함량이 부족하여 물입자와의 상호작용이 거의 없어서 투습도가 상승하는 것으로, 이와 반대로 점착제 조성물로써는 친수성 관능기 함유 단량체의 함량이 낮기 때문에 응집력이 낮다는 문제점이 있다. 바람직하게 온도 40℃, 상대 습도 70%의 조건에서 상기 투습도는 100g/m2·24hr이상이 될 수 있으나, 그 하한에 제한이 있는 것은 아니다. If the moisture permeability exceeds 110 g / m 2 · 24hr at a temperature of 40 ° C. and a relative humidity of 70%, the network capable of moving moisture may not be dense, and in this case, the content of the hydrophilic functional group-containing monomer is insufficient. There is little interaction with and the moisture permeability is increased, on the contrary, the pressure-sensitive adhesive composition has a problem in that the cohesive force is low because the content of the hydrophilic functional group-containing monomer is low. Preferably, at 40 ° C. and 70% relative humidity, the water vapor transmission rate may be 100 g / m 2 · 24hr or more, but the lower limit thereof is not limited.
본 발명의 점착제 조성물은 수분흡수 후 박리력이 수분흡수 전 박리력보다 더 작은 것을 특징으로 한다. 수분흡수 후 작아진 박리력으로 인하여 상기 점착제 조성물은 피착제로부터 깔끔하게 박리되고 이로 인하여, 상기 피착제를 다시 사용할 수 있다. 이 때, 상기 점착제 조성물의 피착제는 유리 또는 플라스틱이 될 수 있는바, 예를 들어, 터치스크린패널(Touch Screen Panel, TSP)과 액정표시장치(Liquid Crystal Display, LCD) 사이에 부착할 수 있다. The adhesive composition of the present invention is characterized in that the peel force after water absorption is smaller than the peel force before water absorption. Due to the reduced peel force after water absorption, the pressure-sensitive adhesive composition is neatly peeled from the adherend, whereby the adherend can be used again. At this time, the adhesive of the pressure-sensitive adhesive composition may be glass or plastic, for example, may be attached between a touch screen panel (TSP) and a liquid crystal display (LCD). .
도 1은 본 발명인 점착제 조성물의 수분흡수 전, 후를 도식화 하여 나타낸 것이다. 도 1을 참조하면, 수분흡수 전에는 점착제 조성물이 TSP와 LCD사이에 라미네이트 되어 상기 피착제의 접착을 견고하게 한다. 이 때, 본 발명은 상기 점착제 조성물과 LCD를 탈착한 후에 이물질이나 찌거기 없이 상기 점착제 조성물이 제거될 수 있도록 하여, LCD에 다시 사용(rework)기능을 부여하기 위해서 점착제 조성물에 일정함량의 친수성 관능기 함유 단량체를 포함한다. 1 is a schematic diagram showing before and after water absorption of the pressure-sensitive adhesive composition of the present invention. Referring to FIG. 1, before the water absorption, the pressure-sensitive adhesive composition is laminated between the TSP and the LCD to firmly adhere the adhesive. At this time, the present invention allows the adhesive composition to be removed without debris or residue after desorption of the adhesive composition and the LCD, containing a certain amount of hydrophilic functional group in the adhesive composition in order to give the LCD rework (rework) function Monomers.
수분흡수 전과 달리, 고온고습/저온고습 후에는 상기 친수성 관능기 함유 단량체가 일정수준의 수분을 함습할 수 있고, 진공/고온 조건 후에 낮은 압력에서 친수성 관능기 함유 단량체가 함습하고 있는 수분 입자 내부에서 증기 기포가 생겨 기화되면서, 부피팽창이 일어나, 상기 점착제 조성물이 피착제에 대한 박리력이 작아지게 된다. Unlike before and after water absorption, after the high temperature, high temperature and low temperature and high humidity, the hydrophilic functional group-containing monomer can impregnate a certain level of water, and vapor bubbles inside the water particles in which the hydrophilic functional group-containing monomer is impregnated at low pressure after vacuum / high temperature conditions. Is generated and vaporized, the volume expansion occurs, the peeling force of the pressure-sensitive adhesive composition to the adherend becomes small.
수분흡수 전에 TSP 또는 LCD등과 부착되어 있던 점착제 조성물과 상이하게, 커진 박리력으로 인해 LCD에 부착되어 있는 점착제 조성물이 찌꺼기 또는 이물질 없이 탈착이 가능하고, 종래에 비해 점착제 조성물의 제거가 용이하게 되어 LCD의 재사용(rework)이 가능하게 된다. Unlike the pressure-sensitive adhesive composition attached to TSP or LCD before water absorption, the pressure-sensitive adhesive composition attached to the LCD can be detached without residue or foreign matter due to the increased peeling force, and the pressure-sensitive adhesive composition can be easily removed compared to the conventional LCD. Can be reworked.
보다 구체적으로, 상기 점착제 조성물의 수분흡수 전 박리력은 1,500~2,000g/in, 수분흡수 후 박리력은 800~1,100g/in인 것을 특징으로 할 수 있다. 상기 점착제 조성물의 수분흡수 전 박리력이 상기 범위를 벗어나는 경우 외부 환경 또는 충격에 의해 피착제로부터의 탈착 우려가 있다. 또한, 상기 점착제 조성물의 수분흡수 후 박리력이 상기의 범위를 벗어나는 경우 피착제와의 계면에서 점착제 조성물의 박리가 되지 않아, 임의로 비틀어서 박리하는 경우 피착제가 찢어지는 문제점이 있다. More specifically, the peeling force before water absorption of the pressure-sensitive adhesive composition may be characterized in that 1,500 ~ 2,000g / in, peeling force after water absorption is 800 ~ 1,100g / in. When the peeling force before water absorption of the pressure-sensitive adhesive composition is out of the above range, there is a fear of detachment from the adherend by the external environment or impact. In addition, when the peeling force after the water absorption of the pressure-sensitive adhesive composition is out of the above range does not peel the pressure-sensitive adhesive composition at the interface with the adhesive, there is a problem that the adhesive is torn when peeling off by twisting arbitrarily.
본 발명은 상기의 점착제 조성물을 포함하여 형성되는 것을 특징으로 하는 점착제층을 제공하여, 나아가 상기 점착제층은 광학부재에 사용될 수 있다. The present invention provides a pressure-sensitive adhesive layer characterized in that the pressure-sensitive adhesive composition is formed, and further, the pressure-sensitive adhesive layer can be used for the optical member.
상기 점착제층의 두께는, 특별히 한정되지 않으나, 5∼300㎛가 바람직하고, 특히 10∼50㎛가 바람직하며, 나아가서는 12∼30㎛가 바람직하다. 이 점착제층의 두께가 지나치게 얇으면 점착 물성이 안정되기 어려운 경향이 있고, 지나치게 두꺼우면 점착제층이 적용될 수 있는 광학부재 전체의 두께가 지나치게 증가해 버리는 경향이 있다.Although the thickness of the said adhesive layer is not specifically limited, 5-300 micrometers is preferable, Especially 10-50 micrometers is preferable, Furthermore, 12-30 micrometers is preferable. When the thickness of the pressure-sensitive adhesive layer is too thin, there is a tendency that the adhesive physical properties are difficult to stabilize, and when too thick, the thickness of the entire optical member to which the pressure-sensitive adhesive layer can be applied tends to increase excessively.
본 발명에서의 광학 부재로서는, 특별히 한정되지 않고서, 액정 표시 장치, 유기 EL 표시 장치, PDP 등의 화상표시 장치에 적합하게 이용되는 광학 필름, 예컨대, 편광판이나 위상차판, 타원 편광판, 광학 보상 필름, 휘도향상 필름, 나아가서는 이들이 적층되어 있는 것 등을 들 수 있다.As an optical member in this invention, it does not specifically limit, The optical film used suitably for image display apparatuses, such as a liquid crystal display device, an organic electroluminescence display, and a PDP, for example, a polarizing plate, a retardation plate, an elliptical polarizing plate, an optical compensation film, And luminance-enhanced films, and those in which they are laminated.
<실시예 및 비교예> <Examples and Comparative Examples>
실시예1Example 1
2-에틸헥실아크릴레이트 100 중량부에 대해서 2-히드록시에틸아크릴레이트 30중량부를 1리터 유리 반응기에서 열중합시켜 분자량이 약 100만인 중합체를 얻었다. 상기 열중합된 수지 100 중량부에 대해 광개시제로서 이가큐어-651 (a,a-메톡시-a- 하이드록시아세토페논) 0.5중량부, 가교제로서 1,6-헥산디올 디아크릴레이트 (HDDA) 0.35중량부를 첨가한 후 충분히 교반하여 점착제 조성물을 제조하였다. 30 parts by weight of 2-hydroxyethyl acrylate was thermally polymerized in a 1 liter glass reactor to 100 parts by weight of 2-ethylhexyl acrylate to obtain a polymer having a molecular weight of about 1 million. 0.5 parts by weight of Igacure-651 (a, a-methoxy-a-hydroxyacetophenone) as a photoinitiator, and 1,6-hexanediol diacrylate (HDDA) 0.35 as a crosslinking agent based on 100 parts by weight of the thermally polymerized resin. After adding the parts by weight, the mixture was sufficiently stirred to prepare an adhesive composition.
실시예2Example 2
상기 실시예 1에서 2-히드록시에틸아크릴레이트 25중량부를 포함하여 분자량이 약 120만인 중합체를 얻는 것을 제외하고는 상기 실시예 1과 같이 점착제 조성물을 제조하였다. Except for obtaining a polymer having a molecular weight of about 1.2 million including 25 parts by weight of 2-hydroxyethyl acrylate in Example 1, a pressure-sensitive adhesive composition was prepared as in Example 1.
실시예3Example 3
상기 실시예 1에서 2-에틸헥실아크릴레이트 100중량부에 대해서 아크릴산 30중량부를 포함하여 분자량이 약 100만인 중합체를 얻는 것을 제외하고는 상기 실시예 1과 같이 점착제 조성물을 제조하였다.A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for obtaining a polymer having a molecular weight of about 1 million by including 30 parts by weight of acrylic acid based on 100 parts by weight of 2-ethylhexyl acrylate in Example 1.
실시예4Example 4
상기 실시예 3에서 아크릴산를 25중량부를 포함하여 분자량이 약 110만인 중합체를 얻는 것을 제외하고는 상기 실시예 3과 같이 점착제 조성물을 제조하였다.The pressure-sensitive adhesive composition was prepared in the same manner as in Example 3 except that 25 parts by weight of acrylic acid was obtained to obtain a polymer having a molecular weight of about 1.1 million.
실시예5Example 5
상기 실시예 1에서 2-에틸헥실아크릴레이트 100중량부에 대해서 글리시딜메타아크릴레이트 30중량부를 포함하여 분자량이 약 110만인 중합체를 얻는 것을 제외하고는 상기 실시예 1과 같이 점착제 조성물을 제조하였다.A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except for obtaining a polymer having a molecular weight of about 1.1 million by including 30 parts by weight of glycidyl methacrylate with respect to 100 parts by weight of 2-ethylhexyl acrylate in Example 1. .
실시예6Example 6
상기 실시예 5에서 글리시딜메타아크릴레이트를 25중량부를 포함하여 분자량이 약 120만인 중합체를 얻는 것을 제외하고는 상기 실시예 5와 같이 점착제 조성물을 제조하였다.A pressure-sensitive adhesive composition was prepared in the same manner as in Example 5 except that 25 parts by weight of glycidyl methacrylate was obtained to obtain a polymer having a molecular weight of about 1.2 million.
비교예1Comparative Example 1
2-에틸헥실아크릴레이트 100 중량부에 대해서 2-히드록시에틸아크릴레이트 15중량부를 1리터 유리 반응기에서 열중합시켜 분자량이 약 100만인 중합체를 얻었다. 상기 열중합된 수지 100 중량부에 대해 광개시제로서 이가큐어-651 (a,a-메톡시-a- 하이드록시아세토페논) 0.5중량부, 가교제로서 1,6-헥산디올 디아크릴레이트 (HDDA) 0.35중량부를 첨가한 후 충분히 교반하여 점착제 조성물을 제조하였다. 15 parts by weight of 2-hydroxyethyl acrylate was thermally polymerized in a 1 liter glass reactor with respect to 100 parts by weight of 2-ethylhexyl acrylate to obtain a polymer having a molecular weight of about 1 million. 0.5 parts by weight of Igacure-651 (a, a-methoxy-a-hydroxyacetophenone) as a photoinitiator, and 1,6-hexanediol diacrylate (HDDA) 0.35 as a crosslinking agent based on 100 parts by weight of the thermally polymerized resin. After adding the parts by weight, the mixture was sufficiently stirred to prepare an adhesive composition.
비교예2Comparative Example 2
상기 비교예 1에서 2-히드록시에틸아크릴레이트 20중량부를 포함하여 분자량이 약 120만인 중합체를 얻는 것을 제외하고는 상기 비교예 1과 같이 점착제 조성물을 제조하였다.A pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 1 except that 20 parts by weight of 2-hydroxyethyl acrylate was obtained to obtain a polymer having a molecular weight of about 1.2 million.
표 1
중합체 HEA함량 중합체 분자량
실시예1 EHA/HEA 30중량부 약 100만
실시예2 EHA/HEA 25중량부 약 120만
실시예3 EHA/AA 30중량부 약 100만
실시예4 EHA/AA 25중량부 약 110만
실시예5 EHA/GMA 30중량부 약 110만
실시예6 EHA/GMA 25중량부 약 120만
비교예1 EHA/HEA 15중량부 약 100만
비교예2 EHA/HEA 20중량부 약 120만
Table 1
polymer HEA content Polymer molecular weight
Example 1 EHA / HEA 30 parts by weight 1 million
Example 2 EHA / HEA 25 parts by weight 1.2 million
Example 3 EHA / AA 30 parts by weight 1 million
Example 4 EHA / AA 25 parts by weight 1.1 million
Example 5 EHA / GMA 30 parts by weight 1.1 million
Example 6 EHA / GMA 25 parts by weight 1.2 million
Comparative Example 1 EHA / HEA 15 parts by weight 1 million
Comparative Example 2 EHA / HEA 20 parts by weight 1.2 million
<실험예> - 점착제 조성물의 물리적 특성Experimental Example Physical Properties of Adhesive Composition
상기 표 1의 실시예 및 비교예의 점착제 조성물을 경화하여 두께 100um의 점착제층으로 제조 후 TSP와 LCD사이에 상기 점착제층을 부착하였고, 이때, 상기 점착제층의 수분흡수량, 투습도, 박리력 및 LCD 재사용(rework) 가능여부를 측정하였다. The pressure-sensitive adhesive composition of Examples and Comparative Examples of Table 1 was cured to prepare a pressure-sensitive adhesive layer having a thickness of 100 μm, and then the pressure-sensitive adhesive layer was attached between the TSP and the LCD. At this time, the water absorption of the pressure-sensitive adhesive layer, moisture permeability, peel strength, and LCD reuse (rework) The availability was measured.
1) 수분흡수량: 온도 25℃, 습도 50%의 환경에서 48시간 동안 수분을 머금은 상기 점착제층을 온도 100℃에서 1시간 동안 건조시켜 자동수분측정기 (Moisture analyzer Ohus MB45)를 통해 상기 점착제층의 무게 감소율을 계산하고 수분흡수량을 측정하였다. 1) Moisture absorption amount: The pressure-sensitive adhesive layer containing moisture for 48 hours in an environment of temperature 25 ℃, 50% humidity is dried for 1 hour at 100 ℃ temperature weight of the adhesive layer through a moisture analyzer (Moisture analyzer Ohus MB45) The rate of reduction was calculated and the moisture uptake was measured.
2) 투습도: 상기 점착제층을 온도 40℃, 상대 습도 70%의 항온항습조 내에 3시간 동안 방치시키고, 수분 증가량으로부터 1m2 면적당, 24시간당, 점착제층을 투과한 수분량을 산출하여 수득된 측정치로 투습도를 측정하였다.2) water vapor permeability: to the obtained measured value is allowed to stand for 3 hours in a constant temperature and humidity chamber of the pressure-sensitive adhesive layer temperature 40 ℃, relative humidity 70% and, calculating the amount of water passing through the 1m 2 per unit area, per 24 hours, the pressure-sensitive adhesive layer from the moisture increase The moisture permeability was measured.
3) 박리력: LCD면에 부착된 상기의 점착제층에 면적 1cm2 당 300g의 하중을 걸어 밀착시켰다. 그 후, 상기 점착제층의 일부 말단을 180도의 박리 각도에서 300mm/분의 박리 속도로 박리시켜 이의 박리 강도를 측정하였다.3) Peeling force: A pressure of 300 g per 1 cm 2 was applied to the pressure-sensitive adhesive layer adhered to the LCD surface to bring the adhesive force into close contact. Thereafter, some of the ends of the pressure-sensitive adhesive layer were peeled at a peel rate of 300 mm / min at a peel angle of 180 degrees to measure its peel strength.
4) LCD 다시 사용(rework) 가부: TSP와 LCD 사이에 점착제층이 부착된 상태로 고온 고습 (85/85)에 2일 방치하여 수분을 흡수하게 한 후 50Torr 진공하에서 70℃로 30분이상 가열하여, 점착제층을 꺼내어 비틀어서 LCD와의 탈착 후에 LCD의 다시 사용(rework)이 가능한지 여부를 관찰하였다.4) LCD reworkability: Heat the product at 70 ℃ under 50 Torr vacuum for more than 30 minutes under 50 Torr vacuum after allowing it to be absorbed by high temperature, high humidity (85/85) for 2 days with adhesive layer attached between TSP and LCD. Then, the pressure-sensitive adhesive layer was taken out and twisted to observe whether the LCD could be reworked after desorption with the LCD.
표 2
수분흡수량(%) 투습도(g/m2·24hr) 수분흡수전 박리력(g/in) 수분흡수후 박리력(g/in) LCD 재사용(rework) 가부
실시예1 5.943 100 1,600 1,020 가능
실시예2 5.582 105 1,700 1,000 가능
실시예3 6.237 95 2,000 800 가능
실시예4 6.012 102 1,000 1,000 가능
실시예5 5.810 97 1,900 1,100 가능
실시예6 5.365 100 1,800 900 가능
비교예1 4.968 117 1,800 1,600 불가능
비교예2 4.730 120 1,800 1,600 불가능
TABLE 2
Water absorption (%) Moisture permeability (g / m 2 · 24hr) Peeling force before water absorption (g / in) Peeling force after water absorption (g / in) LCD rework
Example 1 5.943 100 1,600 1,020 possible
Example 2 5.582 105 1,700 1,000 possible
Example 3 6.237 95 2,000 800 possible
Example 4 6.012 102 1,000 1,000 possible
Example 5 5.810 97 1,900 1,100 possible
Example 6 5.365 100 1,800 900 possible
Comparative Example 1 4.968 117 1,800 1,600 impossible
Comparative Example 2 4.730 120 1,800 1,600 impossible
상기의 수분흡수량, 투습도, 박리력 및 LCD 재사용(rework) 가부 측정의 실험결과를 상기 표 2에 나타내었다. 그 결과, 친수성 관능기 함유 단량체를 25중량부 이상 함유한 실시예 1 내지 실시예 6의 점착제 조성물의 경우, 5%이상의 수분흡수량과 110g/m2·24hr이하의 투습도를 가짐을 알 수 있었다. 상기 수치의 수분흡수량 및 투습도를 포함하는 바, 수분흡수 전보다 수분흡수 후에 더 작은 박리력을 가지게 되어, LCD와 점착제 조성물의 탈착이 쉬워지고 찌꺼기 및 불순물등이 남지 않고 박리됨으로써, 결과적으로 LCD의 재사용(rework)이 가능해진다.Table 2 shows the results of the above water absorption, water vapor permeability, peel strength, and LCD rework. As a result, in the pressure-sensitive adhesive composition of Examples 1 to 6 containing 25 parts by weight or more of the hydrophilic functional group-containing monomer, it was found that it had a water absorption of 5% or more and a water vapor transmission rate of 110 g / m 2 · 24hr or less. The water absorption amount and the moisture permeability of the above values include a smaller peeling force after water absorption than before water absorption, so that the LCD and the pressure-sensitive adhesive composition can be easily detached and peeled off without leaving any residue or impurities. (rework) is possible.
이와 반대로, 친수성 관능기 함유 단량체를 25중량부 미만을 함유한 비교예 1 및 비교예 2의 점착제 조성물의 경우, 5%이상의 수분흡수량과 110g/m2·24hr이하 의 투습도를 확보하지 못하는바, 수분흡수 전 박리력과 수분흡수 후의 박리력이 비슷하게 측정되었다. 수분흡수로 인한 박리력의 차이가 없는 점착제 조성물의 탈착에는 여전히 어려움이 있고, 박리를 한다고 하더라도 이물질 및 불순물이 여전히 존재하게 되어 LCD에 재사용(rework)이 어렵다.On the contrary, in the pressure-sensitive adhesive compositions of Comparative Examples 1 and 2 containing less than 25 parts by weight of the hydrophilic functional group-containing monomer, moisture absorption of not less than 5% and moisture permeability of 110 g / m 2 · 24hr or less were not obtained. Peeling force before absorption and peeling force after water absorption were measured similarly. Desorption of the pressure-sensitive adhesive composition that does not have a difference in peeling force due to water absorption is still difficult, and even if peeling, foreign substances and impurities still exist, so it is difficult to rework the LCD.
그러므로, 점착제 조성물에 있어서 친수성 관능기 함유 단량체를 일정함량 포함함으로써 수분흡수력 및 투습도를 확보할 수 있고, 이로인해 수분흡수 전후의 박리력을 조절하고, 흡수된 수분의 응축 및 부피팽창 등의 과정을 통해 광학부재와의 탈착이 가능하게 되어 결과적으로 피착제에 재사용(rework)기능을 부여할 수 있다. Therefore, by containing a certain amount of the hydrophilic functional group-containing monomer in the pressure-sensitive adhesive composition to ensure moisture absorption and moisture permeability, thereby controlling the peeling force before and after the absorption of water, through the process of condensation and volume expansion of the absorbed moisture Desorption with the optical member becomes possible, and as a result, it is possible to give a rework function to the adherend.
이상에서는 본 발명의 실시예를 중심으로 설명하였으나, 이는 예시적인 것에 불과하며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 기술자라면 이로부터 다양한 변형 및 균등한 타 실시예가 가능하다는 점을 이해할 것이다. 따라서, 본 발명의 진정한 기술적 보호범위는 이하에 기재되는 특허청구범위에 의해서 판단되어야 할 것이다.Although the above description has been made with reference to the embodiments of the present invention, this is only an example, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. . Therefore, the true technical protection scope of the present invention should be judged by the claims described below.

Claims (9)

  1. (메타) 아크릴산 에스테르계 단량체 100중량부에 대하여, 친수성 관능기 함유 단량체를 25중량부 이상 포함하는 것을 특징으로 하는 점착제 조성물.The adhesive composition characterized by including 25 weight part or more of hydrophilic functional group containing monomers with respect to 100 weight part of (meth) acrylic acid ester monomers.
  2. 제 1항에 있어서,The method of claim 1,
    상기 친수성 관능기 함유 단량체가 수산기 함유 단량체, 아미노기 함유 단량체, 카르복실기 함유 단량체, 설폰기 함유 단량체, 모르폴린기 함유 단량체, 글리시딜기 함유 단량체로 이루어진 군으로부터 선택된 하나 이상인 것을 특징으로 하는 점착제 조성물.The pressure-sensitive adhesive composition, characterized in that the hydrophilic functional group-containing monomer is at least one selected from the group consisting of a hydroxyl group-containing monomer, an amino group-containing monomer, a carboxyl group-containing monomer, a sulfone group-containing monomer, a morpholine group-containing monomer, a glycidyl group-containing monomer.
  3. 제 1항에 있어서,The method of claim 1,
    상기 (메타) 아크릴산 에스테르계 단량체 및 상기 친수성 관능기 함유 단량체의 중합체 분자량이 100만~120만인 것을 특징으로 하는 점착제 조성물. The adhesive composition of the said (meth) acrylic-ester type monomer and the said hydrophilic functional group containing monomer has a polymer molecular weight of 1 million-1,20 million.
  4. 제 1항에 있어서,The method of claim 1,
    상기 (메타) 아크릴산 에스테르계 단량체가 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, n-프로필 (메타)아크릴레이트, 이소프로필 (메타)아크릴레이트, n-부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, sec-부틸 (메타)아크릴레이트, 펜틸 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, 2-에틸부틸 (메타)아크릴레이트, n-옥틸 (메타)아크릴레이트, 이소옥틸 (메타)아크릴레이트, 이소노닐 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트 및 테트라데실 (메타)아크릴레이트로 이루어진 군으로부터 선택된 하나 이상인 것을 특징으로 하는 점착제 조성물.The (meth) acrylic acid ester monomer is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t -Butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) Pressure-sensitive adhesive composition, characterized in that at least one selected from the group consisting of acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate and tetradecyl (meth) acrylate.
  5. 제 1항에 있어서,The method of claim 1,
    상기 (메타) 아크릴산 에스테르계 단량체 100중량부에 대하여, 광중합 개시제 0.5~1.0중량부를 추가로 포함하는 것을 특징으로 하는 점착제 조성물. The adhesive composition, further comprising 0.5 to 1.0 parts by weight of the photopolymerization initiator with respect to 100 parts by weight of the (meth) acrylic acid ester monomer.
  6. 제 1항에 있어서,The method of claim 1,
    상기 점착제 조성물은 온도 25℃, 습도 50%의 환경에서 48시간 동안 수분을 흡수하고, 온도 100℃에서 1시간 동안 건조한 결과 상기 점착제 조성물 중량과 대비하여 5.0중량%이상의 수분을 흡수하는 것을 특징으로 하는 점착제 조성물. The pressure-sensitive adhesive composition absorbs moisture for 48 hours in an environment of temperature 25 ℃, humidity 50%, and dried for 1 hour at a temperature of 100 ℃, absorbing more than 5.0% by weight of water relative to the weight of the pressure-sensitive adhesive composition Pressure-sensitive adhesive composition.
  7. 제 1항에 있어서,The method of claim 1,
    상기 점착제 조성물의 투습도가 온도 40℃, 상대 습도 70%의 조건에서 110g/m2·24hr이하인 것을 특징으로 하는 점착제 조성물. The water vapor transmission rate of the said pressure-sensitive adhesive composition is an adhesive composition, characterized in that 110g / m 2 · 24hr or less under the conditions of temperature 40 ℃, relative humidity 70%.
  8. 제 1항에 있어서,The method of claim 1,
    상기 점착제 조성물은 수분흡수 후 박리력이 수분흡수 전 박리력보다 더 작은 것을 특징으로 하는 점착제 조성물. The pressure-sensitive adhesive composition is a pressure-sensitive adhesive composition, characterized in that the peel force after water absorption is smaller than the peel force before water absorption.
  9. 제 1항에 있어서,The method of claim 1,
    상기 점착제 조성물은 수분흡수 전 박리력은 1,500~2,000g/in, 수분흡수 후 박리력은 800~1,100g/in인 것을 특징으로 하는 점착제 조성물. The pressure-sensitive adhesive composition is a pressure-sensitive adhesive composition, characterized in that the peeling force before water absorption 1,500 ~ 2,000g / in, the peeling force after water absorption is 800 ~ 1,100g / in.
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