KR20170028732A - Pressure sensitive adhesive composition - Google Patents
Pressure sensitive adhesive composition Download PDFInfo
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- KR20170028732A KR20170028732A KR1020150125738A KR20150125738A KR20170028732A KR 20170028732 A KR20170028732 A KR 20170028732A KR 1020150125738 A KR1020150125738 A KR 1020150125738A KR 20150125738 A KR20150125738 A KR 20150125738A KR 20170028732 A KR20170028732 A KR 20170028732A
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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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
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- C09J7/0217—
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
Abstract
The present application relates to a pressure-sensitive adhesive composition, a protective film, an optical element and a display device. The pressure-sensitive adhesive composition of the present application exhibits excellent antistatic property, exhibits a suitable low-speed and high-speed peeling force after the crosslinked structure is formed, and has excellent balance of both. Accordingly, when the pressure-sensitive adhesive composition is applied to, for example, a protective film, it exhibits an excellent protective effect and is easily peeled off at high-speed peeling, is advantageous in terms of high-speed processing, and exhibits excellent antistatic properties in the process .
Description
The present application relates to a pressure-sensitive adhesive composition, an optical element protective film, an optical element and a display device.
A protective film may be used to prevent dust, dirt, or the like from adhering to the optical element such as a polarizing plate, other plastic products, household appliances, automobiles, or the like. The protective film is required to have an appropriate peeling force and antistatic property.
For example, when a protective film is peeled at a high speed for use of a product or for assembling another product, it is required that the peel force (hereinafter, referred to as "high peel force") be relatively low. On the other hand, the peeling force (hereinafter referred to as " low-speed peeling force ") at the time of peeling at a slow rate may be relatively high to exhibit an appropriate protective function.
In addition, foreign matter such as dust may be sucked due to static electricity generated mainly at the time of peeling off the protective film, and in the case of electronic products, electrostatic destruction or malfunction of the device may be caused. Particularly, in recent years, due to the spread of computers and the multifunctionality of liquid crystal TVs and mobile phones, components are integrated, and problems caused by static electricity are becoming more and more evident.
Accordingly, efforts have been made to impart an antistatic function to the pressure-sensitive adhesive contained in the protective film.
For example, in Patent Document 1, there is an attempt to suppress the generation of static electricity by blending an ethylene oxide-modified dioctyl phthalate plasticizer with a pressure-sensitive adhesive. In Patent Document 2, an organic salt is added to a pressure-sensitive adhesive, and in Patent Document 3, a metal salt and a chelating agent are mixed in a pressure-sensitive adhesive. However, according to the above methods, it is difficult to prevent the occurrence of contamination of the adhesive component by transfer to the protected product or to suppress the static electricity generated at the initial stage, and particularly, the low-speed peeling force which is important for the protective function is excessively low.
In particular, techniques for imparting hydrophobicity to the surface of an optical element such as a polarizing plate have recently been developed. It is becoming more difficult to maintain a balance between low speed and high speed peeling force while suppressing static electricity on such a hydrophobic surface.
The present application provides a pressure-sensitive adhesive composition, an optical element protective film, an optical element and a display device.
Exemplary pressure-sensitive adhesive compositions include pressure-sensitive adhesives, crosslinking agents, and reactive polyether-modified siloxane compounds. The pressure-sensitive adhesive composition of the present application can be used, for example, in a surface protective film for various applications. In particular, the pressure-sensitive adhesive composition can exhibit excellent static-electricity-blocking ability even when applied to the protection of hydrophobic surfaces, and can exhibit excellent balance between low-speed and high-speed peeling force. The term hydrophobic surface in the present application may refer to a surface having a contact angle to deionized water of at least about 90 degrees or less than or equal to 30 mN / m. In the above, the contact angle can be measured by a method using a drop shape analyzer (KRUSS DSA100) under the constant temperature and humidity conditions of 23 ° C and 60 RH% (relative humidity) by using a deionized water, Can be measured by the Owen-Wendt-Rabel-Kaelble method using the contact angle of deionized water and diiodo-methane measured by the contact angle measurement method.
As the adhesive polymer in the present application, those containing an alkyl (meth) acrylate, a monomer containing an alkylene oxide chain, a nitrogen-containing monomer and a hydroxyl group-containing monomer for the purpose of manifesting appropriate adhesive performance, antistatic property and peeling property Can be used. In the present specification, the polymer includes any compound or monomer, which may mean that the compound or monomer is polymerized in the polymer after polymerization.
As the alkyl (meth) acrylate, for example, an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms may be used in consideration of the cohesive force of the pressure-sensitive adhesive, the glass transition temperature, or the tackiness. The alkyl group may be, for example, a straight chain or branched alkyl group. Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, sec-butyl (Meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate and tetradecyl (meth) acrylate. Of these, one or more of the above- ≪ / RTI >
As the monomer having an alkylene oxide chain, for example, a compound represented by the following general formula (1) can be exemplified.
[Chemical Formula 1]
Q is hydrogen or an alkyl group, U is an alkylene group, Z is hydrogen, an alkyl group or an aryl group, and m is an arbitrary number, for example, a number within a range of 1 to 20. [
When two or more [-U-O-] units are present in the formula (1), the number of carbon atoms of the U in the unit may be the same or different.
In formula (1), m may be in the range of, for example, 1 to 16, 1 to 12, 1 to 9, or 2 to 9. Within this range, polymerization efficiency and crystallinity of the adhesive polymer can be maintained in an appropriate range during production of the adhesive polymer, and appropriate conductivity can be imparted to the adhesive.
As used herein, the term alkyl group may mean an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified. The alkyl group may be straight-chain, branched or cyclic. The alkyl group may be substituted by one or more substituents, or may be unsubstituted.
As used herein, unless otherwise specified, the term "alkylene group" or "alkylidene group" means an alkylene group or an alkylidene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, have. The alkylene group or alkylidene group may be linear, branched or cyclic. The alkylene or alkylidene group may be optionally substituted by one or more substituents.
In another embodiment, Q in formula (1) may be an alkyl group, for example, an alkyl group having 1 to 8 carbon atoms or 1 to 4 carbon atoms. When Q is an alkyl group, for example, it may be advantageous that the protective film is easily removed without residue or unevenness on the adherend when the pressure-sensitive adhesive composition is applied to a protective film or the like.
As used herein, the term aryl group, unless otherwise specified, includes a benzene ring, or two or more benzene rings may be connected, or two or more benzene rings may share one or more carbon atoms, May refer to a monovalent residue derived from a compound or a derivative thereof having a structure represented by the following formula: The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 22 carbon atoms, 6 to 16 carbon atoms, or 6 to 13 carbon atoms. Examples of the aryl group include a phenyl group, a phenylethyl group, a phenylpropyl group, a benzyl group, a tolyl group, a xylyl group and a naphthyl group.
Examples of the substituent which may be substituted in the specific functional group, for example, the alkyl group, the alkylidene group or the alkylene group in the present specification include an alkyl group, an alkoxy group, an alkenyl group, an epoxy group, a cyano group, a carboxyl group, An acryloyloxy group, a methacryloyloxy group or an aryl group, but the present invention is not limited thereto.
Examples of the compound represented by the formula (1) include alkoxy dialkylene glycol (meth) acrylic acid ester, alkoxy trialkylene glycol (meth) acrylic acid ester, alkoxy tetraalkylene glycol (meth) acrylic acid ester, aryloxy dialkylene glycol (Meth) acrylic acid esters, aryloxytetraalkylene glycol (meth) acrylic acid esters, and polyalkylene glycol monoalkyl ether (meth) acrylic acid esters. But is not limited to.
Examples of the alkoxy include alkoxy having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms and 1 to 4 carbon atoms, and specifically, a methoxy group or an ethoxy group can be exemplified .
Examples of the alkylene glycol include alkylene glycols having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms and 1 to 4 carbon atoms, for example, ethylene glycol or propylene glycol can be exemplified , Aryloxy is exemplified by aryloxy having 6 to 24 carbon atoms or 6 to 12 carbon atoms such as phenoxy.
The kind of the nitrogen-containing monomer which can be contained in the adhesive polymer is not particularly limited and, for example, an amide group-containing monomer, an amino group-containing monomer, an imide group-containing monomer or a cyano group-containing monomer can be used. Examples of the amide group-containing monomer include amides such as (meth) acrylamide or N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- (Meth) acrylamide, N, N'-methylenebis (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, , N, N-dimethylaminopropyl methacrylamide, N-vinylpyrrolidone, N-vinylcaprolactam or (meth) acryloylmorpholine. Examples of the amino group-containing monomer include aminoethyl (meth) Acrylate, N, N-dimethylaminoethyl (meth) acrylate or N, N-dimethylaminopropyl (meth) acrylate. Examples of the imide group-containing monomer include N-isopropyl maleimide, N - cyclohexylmaleimide or itaconimide etc. It can be exemplified, and a cyano group-containing monomer include, but as acrylonitrile or methacrylonitrile, etc. The nitrile can be exemplified, without being limited thereto. N-dialkyl (meth) acrylamide is particularly preferably used in combination with the above-mentioned nitrogen-containing monomer (s) in order to ensure excellent physical properties, for example, conductivity while ensuring excellent peeling properties, for example, balance of low- . In this case, the N, N-dialkyl (meth) acrylamide may include an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms.
The ratio of the weight of the monomer of the above formula (1) to the weight of the nitrogen-containing monomer in the pressure-sensitive adhesive polymer can be adjusted in order to secure the balance of the peeling properties, that is, the excellent low- have. For example, the ratio (A / B) of the weight (A) of the monomer of formula (1) to the weight (B) of the nitrogen containing monomer in the adhesive polymer may be within the range of about 1.5 to 20. It is possible to provide a pressure-sensitive adhesive which exhibits an appropriate antistatic property within such a ratio and exhibits a balance of appropriate high-speed and low-speed peeling force without leaving a contaminant at the time of peeling.
The adhesive polymer may further include a polymerization unit of a hydroxyl group-containing monomer. The monomer may provide a hydroxy group to the adhesive polymer.
As the hydroxy group-containing monomer, for example, a monomer represented by the following formula (2) can be mentioned.
(2)
In formula (2), Q is hydrogen or an alkyl group, A and B are each independently an alkylene group, and n is an arbitrary number, for example, a number of 0 to 10.
When two or more [-O-B-] units are present in the general formula (2), the number of carbon atoms of B in the unit may be the same or different
In formula (2), A and B may be, for example, each independently an alkylene group which is linear.
Examples of the compound of formula (2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (Meth) acrylate, 2-hydroxyethyleneglycol (meth) acrylate or 2-hydroxypropyleneglycol (meth) acrylate, but are not limited thereto.
In one example, as the hydroxy group-containing monomer, two types of monomers having different carbon numbers in the side chain may be used.
For example, the adhesive polymer may be represented by the formula (2), and the first monomer having the number of carbon atoms of the alkylene groups present in A and B in the formula (2) is present in the range of 1 to 3, 4 to 20, 4 to 16, 4 to 12, 4 to 8, or 4 to 6 carbon atoms of the alkylene group of the alkylene group.
When calculating the number of carbons in order to distinguish the first and second monomers, only the number of carbon atoms of the alkylene group formed in a straight chain form is considered. For example, when the substituents containing carbon are substituted for A and B The carbon number of the substituent is not taken into consideration. As described above, the pressure-sensitive adhesive excellent in the peeling force characteristic, that is, the balance between the high-speed and low-speed peeling force, can be provided through the polymerization unit of the two kinds of hydroxyl group monomers.
The ratio of the weight of the first and second monomers in the adhesive polymer can be adjusted in order to secure the balance of the peeling properties, that is, the excellent low-speed and high-speed peeling force, while securing various physical properties such as adhesion performance in an appropriate range. For example, the ratio (A / B) of the weight (A) of the first monomer to the weight (B) of the second monomer in the adhesive polymer may be 1 or more or more than 1. In another example, the ratio may be 25 or less, 20 or less, 15 or less, 10 or less, or about 8 or less. It is possible to provide a pressure-sensitive adhesive which exhibits an appropriate antistatic property within such a ratio and exhibits a balance of appropriate high-speed and low-speed peeling force without leaving a contaminant at the time of peeling.
The adhesive polymer comprises 40 to 94.8 parts by weight of alkyl (meth) acrylate, 0.1 to 15 parts by weight of the monomer of the formula (1), 0.1 to 5 parts by weight of the nitrogen-containing monomer, 5 to 20 parts by weight of the first monomer, 0.1 to 4 parts by weight of two monomers. Unless specifically stated otherwise in this specification, the unit weight portion may mean the ratio of the weight between each component. For example, the adhesive polymer may comprise 40 to 94.8 parts by weight of alkyl (meth) acrylate, 0.1 to 15 parts by weight of the monomer of the formula 1, 0.1 to 5 parts by weight of the nitrogen-containing monomer, (A) of the alkyl (meth) acrylate, the weight of the monomer of the formula (1), the weight of the nitrogen-containing monomer (C (A: B: C: D: E) of the weight of the first monomer and the weight of the second monomer is 40 to 94.8: 0.1 to 15: 0.1 to 5: 20: 0.1 to 4 ", respectively, from the mixture of the monomers containing the respective monomers. In another embodiment, the alkyl (meth) acrylate is used in an amount of 50 to 94.8 parts by weight, 55 to 94.8 parts by weight, 60 to 94.8 parts by weight, 60 to 90 parts by weight, 60 to 85 parts by weight, 65 to 85 parts by weight, To 85 parts by weight of the adhesive polymer.
In addition, the monomer of Formula 1 may be contained in an amount of about 3 to 15 parts by weight, about 5 to 15 parts by weight, or about 6 to 15 parts by weight. In addition, the nitrogen-containing monomer may also be included in about 0.5 to 5 parts by weight in another example.
The pressure-sensitive adhesive polymer may contain, if necessary, a known monomer used in the production of pressure-sensitive adhesive polymers such as (meth) acrylic acid, 2- (meth) acryloyloxyacetic acid, 3- Carboxylic group-containing monomers such as an acid, 4- (meth) acryloyloxybutyl acid, acrylic acid dimer, itaconic acid, maleic acid and maleic anhydride; A monomer having an isocyanate group, a monomer having a glycidyl group such as glycidyl (meth) acrylate, or a monomer having a nitrogen atom such as (meth) acrylamide, N-vinylpyrrolidone or N-vinylcaprolactam, And may further include a radically polymerizable monomer such as a monomer or styrene. These monomers may be polymerized and contained in the adhesive polymer, and may be included in the adhesive polymer in a proportion of, for example, about 20 parts by weight or less.
The pressure-sensitive adhesive polymer can be obtained by selecting the necessary monomers from among the monomers described above, and subjecting the mixture of the monomers having the desired proportions of the selected monomers to solution polymerization, photo polymerization, bulk polymerization, (suspension polymerization) or emulsion polymerization (polymerization).
The pressure-sensitive adhesive composition may further include a crosslinking agent, which can react with the crosslinking point of the pressure-sensitive adhesive polymer to realize a crosslinked structure. The crosslinking agent may also mediate the binding between the reactive polyether modified siloxane compound and the adhesive polymer described below.
As the crosslinking agent, for example, an aliphatic isocyanate crosslinking agent can be used. When such a cross-linking agent has a cross-linking structure with the above-mentioned pressure-sensitive adhesive polymer, that is, the pressure-sensitive adhesive polymer containing two or more kinds of hydroxy group-containing monomers, a pressure-sensitive adhesive having antistatic properties necessary together with appropriate low- and high- For example, as the crosslinking agent, a crosslinking agent comprising an aliphatic cyclic isocyanate compound and / or an aliphatic acyclic isocyanate compound can be used. The term aliphatic cyclic isocyanate compound as used herein means an isocyanate compound containing a cyclic structure and having a cyclic structure in which the structure does not correspond to an aromatic ring. The aliphatic acyclic isocyanate compound may be, for example, an aliphatic linear or branched May mean a branched isocyanate compound. Examples of the aliphatic cyclic isocyanate compound include isocyanate compounds such as isophorone diisocyanate or methylene dicyclohexyl diisocyanate or cyclohexane diisocyanate, A derivative such as a dimer or a trimer or a reaction product of any of the above with a polyol (ex. Trimethylol propane) can be exemplified. As the aliphatic acyclic isocyanate compound, there may be mentioned a compound having a carbon number of 1, such as hexamethylene diisocyanate An alkylene diisocyanate compound having from 1 to 20 carbon atoms, from 1 to 12 carbon atoms, or from 1 to 8 carbon atoms, a derivative thereof such as a dimer or a trimer thereof, or any one of the above and a polyol (e.g., trimethylol Propane) And the like, but the present invention is not limited thereto.
When the aliphatic cyclic isocyanate compound and the aliphatic acyclic isocyanate compound are used together, the ratio is not particularly limited and may be appropriately selected as needed. Generally, from 1 part by weight to 500 parts by weight or from 20 parts by weight to 300 parts by weight of an aliphatic acyclic isocyanate compound may be included in the crosslinking agent, relative to 100 parts by weight of the aliphatic cyclic isocyanate compound. As such a crosslinking agent, that is, a crosslinking agent containing an aliphatic cyclic isocyanate compound and an aliphatic acyclic isocyanate compound may be used, and examples thereof include MHG-80B and Duranate P manufactured by Asahi, or NZ-1 manufactured by BAYER .
As the crosslinking agent, ethylene glycol diglycidyl ether, triglycidyl ether, trimethylol propane triglycidyl ether, N, N, N ', N'-tetraglycidyl ethylenediamine or glycerin Epoxy cross-linking agents such as diglycidyl ether and the like; Bis (1-aziridine carboxamide), N, N'-diphenylmethane-4,4'-bis (1-aziridine carboxamide), triethylene melamine Iron, zinc, tin, titanium, antimony, magnesium, and / or vanadium, such as bis (isoproparyl) -1- (2-methyl aziridine), or tri-1-aziridinyl phosphine oxide, Can be used together with a known crosslinking agent such as a metal chelate crosslinking agent, which is a compound coordinated to acetyl acetone, acetyl acetate or the like.
The pressure-sensitive adhesive composition is used in an amount of 1 to 15 parts by weight, 2 to 15 parts by weight, 3 to 15 parts by weight, 4 to 15 parts by weight, 5 to 15 parts by weight, 5 to 14 parts by weight, 5 to 13 parts by weight, 5 to 12 parts by weight, 5 to 11 parts by weight, 5 to 10 parts by weight or 5 to 9 parts by weight of a crosslinking agent. In such a range, an appropriate crosslinking structure is realized, and the low speed and high speed peeling force of the pressure sensitive adhesive can be adjusted to a desired range.
The pressure-sensitive adhesive composition of the present application may further comprise a reactive polyether-modified siloxane compound. In the present application, the polyether-modified siloxane compound is reactive, which means that the polyether-modified siloxane compound contains a reactive functional group, and the reactive functional group is, for example, a functional group of the aforementioned adhesive polymer, A hydroxyl group, a carboxyl group, or the like, or may be a functional group capable of binding with the functional group of the adhesive polymer via another compound. The polyether-modified siloxane compound can serve to impart antistatic properties to the pressure-sensitive adhesive, and in particular, by containing the above-mentioned reactive functional groups, the polyether-modified siloxane compound maintains excellent compatibility with the pressure-sensitive adhesive polymer, It is possible to prevent elution to the outside of the layer or contamination of the adherend.
The kind of the reactive functional group contained in the reactive polyether-modified siloxane compound is not particularly limited, but needs to be selected in consideration of the possibility of bonding to the adhesive polymer. For example, the reactive polyether-modified siloxane compound may include a hydroxyl group, an epoxy group or an amine group as a reactive functional group. The reactive functional group is preferably present at the terminal of the polyether-modified siloxane compound. When the reactive functional group is a hydroxy group and the adhesive polymer is a hydroxy group, the polyether modified siloxane compound may be connected to the adhesive polymer by a compound having at least two isocyanates, for example, the aliphatic isocyanate crosslinking agent described above. That is, in such a case, one isocyanate group of the crosslinking agent reacts with the hydroxyl group of the polyether-modified siloxane compound to form a urethane bond, and the other isocyanate group of the crosslinking agent reacts with the hydroxyl group of the adhesive polymer to form a urethane bond, The polyether-modified siloxane compound can be bonded to the adhesive polymer. Even when the reactive functional group of the polyether-modified siloxane compound is another functional group such as an epoxy group or an amine group, a functional group capable of reacting with the functional group is introduced into the adhesive polymer, or a functional group capable of reacting with the functional group and a functional group The introduction of the reactive polyether-modified siloxane compound may be possible by using a compound capable of reacting with the functional group.
Therefore, as one example, the reactive polyether-modified siloxane compound has a hydroxyl group as a reactive functional group, and the hydroxyl group of the polyether-modified siloxane compound is bonded to the hydroxyl group of the first or second monomer of the adhesive polymer via an aliphatic isocyanate compound They may be coupled and connected.
As the reactive polyether-modified siloxane compound, for example, a compound represented by the following formula (A) or (B) or a mixture of the compounds may be used.
[Chemical Formula 1]
[Chemical Formula B]
Formula A or B in the R 1 to R 15 are each independently a hydrogen atom, an alkyl group or alkenyl group, Z is - (CH 2) p - ( O-CH 2 -CH 2) q - (O-CH 2 -CH 2 -CH 2 ) r -U where U is a hydroxyl group, an amine group or an epoxy group, p is a number in the range of 1 to 4, q + r is a number in the range of 1 or more, x is a number in the range of 1 to 10 , and y is a number in the range of 1 to 10.
R 1 to R 15 in the formula (A) or (B) may be independently an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms.
Further, in the formula (A) or (B), q may be about 1 to 30 in another example, and r may be about 1 to 30.
The reactive polyether modified siloxane compound may have a weight average molecular weight of about 500 to 30,000. In the case of the present application, the reactive polyether modified siloxane compound can be incorporated into the pressure-sensitive adhesive layer in a form bonded to the pressure-sensitive adhesive polymer, so that it can exhibit excellent miscibility even in the molecular weight within the above range.
The pressure-sensitive adhesive composition is used in an amount of 0.01 to 5 parts by weight, 0.05 to 5 parts by weight, 0.1 to 5 parts by weight, 0.5 to 5 parts by weight, 0.5 to 4 parts by weight, 0.5 to 3 parts by weight, or 0.5 to 2.5 parts by weight And the reactive polyether-modified siloxane compound. Within this range, appropriate antistatic properties can be ensured, and the low speed and high-speed peeling force of the pressure-sensitive adhesive can be adjusted to a desired range.
The pressure-sensitive adhesive composition may further include a light stabilizer, for example, a light stabilizer such as a hindered amine compound. Such a light stabilizer is not agglomerated even when the pressure-sensitive adhesive is left under high temperature conditions, for example, without causing the phenomenon that the concentration of an antistatic agent to be described later increases in the agglomerated clusters, and the alkylene oxide It is possible to prevent the problem that the ether bonding site of the chain is decomposed by heat to generate radicals or that the hydroxyl group containing monomer causes a condensation reaction and the storage stability of the pressure sensitive adhesive composition can be greatly improved.
As the light stabilizer, for example, a compound represented by the following formula (3) can be exemplified.
(3)
In Formula 3 M 1 to M 5 are each independently R 1 -N, (R 2) (R 3) -C or (R 4) (R 5) -C , and, in said R 1 is a hydrogen atom, an alkyl group or alkoxy group, R 2 and R 3 are each and independently selected from an alkyl group, R 4 and R 5 are each independently a hydrogen atom or an alkyl group, L is an alkylene group or an alkylidene group, P is an alkyl group or a substituent of the formula (4) to be. In the above formula (3) at least one of M 2 to M 4 is wherein R 1 -N, R 1 -N of M 2, M 3 or M 1, present immediately adjacent to M 4 M 2, M 3, M 4 or M 5 may be in the (R 2) (R 3) -C.
[Chemical Formula 4]
In formula (4), M 6 to M 10 are each independently R 1 -N, (R 2 ) (R 3 ) -C or (R 4 ) (R 5 ) -C, wherein R 1 is a hydrogen atom, R 2 and R 3 are each independently an alkyl group, and R 4 and R 5 are each independently a hydrogen atom or an alkyl group. In the above formula (4) at least one of M 7 to M 9 is the R 1 -N, M 7, M 8 or M M 6, M 7, M 8, M 9 or M 10 immediately adjacent to the existing 9 is the (R 2 ) (R 3 ) -C.
In the formulas (3) and 4 M 1 to M 10 is R 1 -N, (R 2) (R 3) -C or (R 4) (R 5) -C called it, the nitrogen of said M 1 to M 10 position May mean a form in which an atom (N) or a carbon atom (C) is present and a substituent such as R 1 to R 5 is bonded to the nitrogen atom or the carbon atom.
In the formula (4)
L, which is an alkylene group or an alkylidene group in the general formula (3), may be substituted or unsubstituted, if necessary. For example, L may be substituted by an aryl group, and examples of the aryl group include 3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl group and the like, It is not.
In formula (3), R 1 may be, for example, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or 1 to 4 carbon atoms, an alkoxy group having 4 to 16 carbon atoms or 4 to 12 carbon atoms. The alkyl or alkoxy group may be linear or branched and may be substituted by one or more substituents.
In formula (3), R 2 , R 3 and P may each independently be an alkyl group having 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear or branched and may be substituted by one or more substituents.
In the formula (3), R 4 and R 5 may be a hydrogen atom.
In Formula 3, L may be, for example, an alkylene group having 4 to 12 carbon atoms or 6 to 10 carbon atoms, or an alkylidene group having 2 to 10 carbon atoms or 4 to 8 carbon atoms. The alkylene or alkylidene group may be linear or branched and may be substituted by one or more substituents.
Examples of the compound of Formula 3 include bis (1,2,2,6,6-pentamethyl-4 (2,2,2,6,6-pentamethyl-4-piperidyl) -piperidyl sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, propanedioic acid, Methyl] -2-butyl-1,3-bis (1,2,2,6,6-pentamethyl-pyrimidin- Propanedioic acid, 2 - [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -2-butyl-1,3-bis , 6,6-pentamethyl-4-piperidinyl) ester, bis (2,2,6,6-tetramethyl-4- piperidyl sebacate) or bis (1-octyloxy-2,2,6,6-tetramethyl-4 -piperidinyl sebacate, and the like, but are not limited thereto.
The compound of Formula 3 may be used in an amount of, for example, 0.01 to 10 parts by weight, 0.05 to 10 parts by weight, 0.05 to 8 parts by weight, 0.05 to 6 parts by weight, or 0.05 By weight to 5 parts by weight of the pressure-sensitive adhesive composition. It is possible to provide a pressure-sensitive adhesive composition which effectively prevents generation of radicals due to decomposition of the alkylene oxide chain and condensation of a hydroxyl group-containing monomer under such a ratio, and is excellent in storage stability.
The pressure-sensitive adhesive composition may further comprise an antistatic agent. As the antistatic agent, for example, an ionic compound may be used.
As the ionic compound, for example, a metal salt may be used. The metal salt may include, for example, an alkali metal cation or an alkaline earth metal cation. Examples of the cation include lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), rubidium ion (Rb + ), cesium ion (Cs + ), beryllium ion (Be 2+ ) Mg 2 +), calcium ions (Ca 2 +), strontium ion (Sr 2 +) and barium ion (Ba 2 +) there is iljong or two kinds or more of the like can be illustrated, for example, a lithium ion, a sodium ion, Potassium ion, magnesium ion, calcium ion and barium ion, or ion stability and mobility.
As the anion contained in the ionic compound is PF 6 -, AsF -, NO 2 -, fluoride (F -), chloride (Cl -), bromide (Br -), iodide (I -), perchlorate (ClO 4 -), hydroxide (OH -), carbonate (CO 3 2-), nitrate (NO 3 -), trifluoromethane sulfonate (CF 3 SO 3 -), sulfonate (SO 4 -), hexafluorophosphate (PF 6 -), methyl benzene sulfonate (CH 3 (C 6 H 4 ) SO 3 -), p- toluenesulfonate (CH 3 C 6 H 4 SO 3 -), tetraborate (B 4 O 7 2-), carboxymethyl sulfonate (COOH (C 6 H 4) SO 3 -), sulfonate as a triple (CF 3 SO 2 -), benzo carbonate (C 6 H 5 COO -) , acetate ( a), a triple acetate - CH 3 COO (CF 3 COO -), tetrafluoroborate (BF 4 -), tetra-benzyl borate (B (C 6 H 5) 4 -) or tris pentafluoroethyl trifluoromethyl Phosphate (P (C 2 F 5 ) 3 F 3 - ), and the like.
In another example, the anion may be an anion or bifluorosulfonylimide represented by the following formula (5), or the like.
[Chemical Formula 5]
[X (YO m R f ) n ] -
X is a nitrogen atom or a carbon atom, Y is a carbon atom or a sulfur atom, R f is a perfluoroalkyl group, m is 1 or 2, and n is 2 or 3.
In formula (5), when Y is carbon, m is 1, and when Y is sulfur, m is 2, n is 2 when X is nitrogen, and n is 3 when X is carbon.
The anion or bis (fluorosulfonyl) imide of formula (5) exhibits high electronegativity due to the perfluoroalkyl group (R f ) or the fluorine group and also forms a weak bond with the cation, including a unique resonance structure And at the same time has hydrophobicity. Therefore, the ionic compound exhibits excellent compatibility with other components of a composition such as an adhesive polymer, and can give a high antistatic property even in a small amount.
R f in formula (5) may be a perfluoroalkyl group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, wherein the perfluoroalkyl group may be a straight chain, Type structure. The anion of formula (5) may be a sulfonylimide-based, sulfonylimide-based, carbonylimide-based or carbonylimide-based anion, and specifically includes tris trifluoromethanesulfonylmethide, bistrifluoromethanesulfonyl A perfluorobutanesulfonylimide, bispentafluoroethanesulfonylimide, tris trifluoromethanecarbonylmide, bis perfluorobutanecarbonylimide or bispentafluoroethanecarbonyl, bispentafluoroethanesulfonylimide, bis Imide, etc., or a mixture of two or more species.
Examples of the ionic compound include N, N-dimethyl N-propylammonium, N, N, N-trimethyl-N-propylammonium, N-methyl- N, N, N-trihexylammonium, N-methyl-N, N, N-trihexylammonium, N-ethyl- Quaternary ammonium such as N, N, N-trioctylammonium or N-ethyl-N, N, N-trioctylammonium, phosphonium, pyridinium, imidazolium, An organic salt containing pyrolidinium or piperidinium together with the anion component may be used and, if necessary, the metal salt and the organic salt may be used in combination.
The content of the ionic compound in the pressure-sensitive adhesive composition is not particularly limited and may be, for example, 0.01 to 5 parts by weight relative to 100 parts by weight of the pressure-sensitive adhesive polymer. The ratio of the ionic compound can be changed in consideration of the desired antistatic property and compatibility between the components.
The pressure-sensitive adhesive composition may further include a silane coupling agent. Examples of the coupling agent include gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropyltriethoxysilane , 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-aminopropyltri But are not limited to, methoxy silane, gamma-aminopropyl triethoxy silane, 3-isocyanatopropyl triethoxy silane, gamma-acetoacetate propyl trimethoxysilane, gamma-acetoacetate propyl triethoxy silane, Trimethoxysilane, beta-cyanoacetyltriethoxysilane, acetoxyacetotrimethoxysilane, and mixtures of one or more of the above can be used. . For example, as the silane coupling agent, it may be appropriate to use a silane coupling agent having an acetoacetate group or a beta-cyanoacetyl group. The silane coupling agent may be included in the adhesive composition in an amount of 0.01 to 5 parts by weight, or 0.01 to 1 part by weight based on 100 parts by weight of the adhesive polymer. An appropriate adhesive force increasing effect and endurance reliability can be ensured within the above range.
The pressure-sensitive adhesive composition may further include a tackifier in view of control of the tack performance. Examples of the tackifier include a hydrocarbon resin or a hydrogenated product thereof, a rosin resin or a hydrogenated product thereof, a rosin ester resin or a hydrogenated product thereof, a terpene resin or a hydrogenated product thereof, a terpene phenol resin or a hydrogenated product thereof, Ester resins and the like, or mixtures of two or more thereof. The tackifier may be included in the composition in an amount of 1 part by weight to 100 parts by weight based on 100 parts by weight of the cohesive polymer. It is possible to secure a suitable addition effect and a commercial and cohesive force improving effect in the above content range.
The pressure-sensitive adhesive composition may also contain a coordinating compound capable of forming a coordination bond with the antistatic agent, a photoinitiator, a multifunctional acrylate, an epoxy resin, a crosslinking agent, a UV stabilizer, an antioxidant, A colorant, a reinforcing agent, a filler, a defoaming agent, a surfactant, and a plasticizer.
The pressure-sensitive adhesive composition has a low peel strength of about 1 gf / 25 mm to about 10 gf / 25 mm for an adherend having a surface energy of 30 mN / m or less in a state where a crosslinked structure is implemented, a high peel strength of 40 gf / And may be about 200 gf / 25 mm, 40 gf / 25 mm to 150 gf / 25 mm, or 40 gf / 25 mm to 100 gf / 25 mm.
The term low-speed peeling force is, for example, the peeling force measured at a peeling angle of 180 degrees and a peeling speed of 0.3 m / min. The high-speed peeling force was measured at a peeling angle of 180 degrees and a peeling speed of 30 m / min It can be peeling force.
Specifically, each of the peel strengths was measured by attaching a pressure-sensitive adhesive composition having a crosslinked structure to an adherend having a surface energy of 30 mN / m or less, holding the layer at 23 ° C and 65% relative humidity for 24 hours, And may be one measured at each peeling angle and peeling speed. A specific method of measuring each of the peeling forces is described in the following examples. The surface energy of the adherend may be, for example, about 10 m / N / m to 30 mN / m.
The pressure-sensitive adhesive composition may further have a ratio H / L of the high-speed peeling force H to the low-speed peeling force L of about 1 to 30, 1 to 25, 5 to 25, 10 to 25, or 13 to 20 have.
The pressure-sensitive adhesive composition is also excellent in peeling electrification voltage, which is generated when the adherend, i.e., an adherend having a surface energy of 30 mN / m or less is peeled off at a peeling angle of 180 degrees and a peeling speed of 40 m / Can be 0.7 kV or less. The method of measuring the peeling electrification voltage is described in the following examples.
If the low-speed peeling force, the high-speed peeling force and / or the peeling electrification voltage are secured as described above, it can be easily peeled off at a high speed while minimizing the occurrence of static electricity while exhibiting an appropriate protection function for the adherend.
The present application is also directed to a pressure sensitive adhesive sheet. The adhesive sheet may be, for example, a protective film, specifically a protective film for an optical element.
For example, the pressure-sensitive adhesive sheet can be used as a protective film for an optical element such as a polarizing plate, a polarizer, a polarizer protective film, a retardation film, a viewing angle compensation film, and a brightness enhancement film. As used herein, the term polarizer and polarizer refers to objects that are distinguished from each other. That is, the polarizer refers to a film, sheet or device itself exhibiting a polarization function, and the polarizer refers to an optical element including other elements together with the polarizer. Other elements that can be included in the optical element together with the polarizer include, but are not limited to, a polarizer protective film or a retardation layer.
The pressure sensitive adhesive sheet may include, for example, a surface protecting base film and a pressure sensitive adhesive layer present on one side of the base film. The pressure-sensitive adhesive layer may include, for example, a pressure-sensitive adhesive composition that is crosslinked, that is, a pressure-sensitive adhesive composition having a crosslinked structure, as the pressure-sensitive adhesive composition.
The pressure-sensitive adhesive composition exhibits relatively high low-speed peeling force and relatively low high-speed peeling force after the crosslinked structure is implemented, and excellent balance between the peel strength and excellent durability reliability, workability, transparency and antistatic property. Thus, the protective film is used for protecting the surface of an optical element such as a polarizing plate, a retardation plate, an optical compensation film, a reflection sheet and a brightness enhancement film used for various optical devices or parts, display devices or parts such as LCD , But the use of the protective film is not limited to the use of the protective film.
As the surface protective base film, a general film or sheet known in this field can be used. For example, a polyester film such as polyethylene terephthalate or polybutylene terephthalate, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a poly (vinyl chloride) film or a polyimide film And the like. Such a film may be composed of a single layer, or two or more layers may be laminated, and in some cases, a functional layer such as an antifouling layer or an antistatic layer may further be included. From the viewpoint of improving the adhesion of the substrate, a surface treatment such as a primer treatment may be performed on one surface or both surfaces of the substrate.
The thickness of the base film may be suitably selected depending on the application and is not particularly limited, and may be generally formed to a thickness of 5 to 500 탆 or 10 to 100 탆.
The thickness of the pressure-sensitive adhesive layer included in the pressure-sensitive adhesive sheet is not particularly limited, and may be, for example, 2 m to 100 m or 5 m to 50 m.
The method for forming the pressure-sensitive adhesive layer is not particularly limited, and for example, a pressure-sensitive adhesive composition or a coating solution prepared therefrom may be coated on a base film or the like by a conventional means such as a bar coater and cured, A method of coating on the surface of the base material and curing the base material, and transferring the base material film onto the base material film.
The process of forming the pressure-sensitive adhesive layer is preferably performed after sufficiently removing the bubble-inducing component such as the volatile component or the reaction residue in the pressure-sensitive adhesive composition or the coating liquid. Accordingly, the crosslinking density or the molecular weight of the pressure-sensitive adhesive is too low to lower the elastic modulus, and bubbles existing between the glass plate and the pressure-sensitive adhesive layer at high temperature are increased to form scattering bodies therein.
Also, a method of curing the pressure-sensitive adhesive composition in the above process is not particularly limited. For example, the pressure-sensitive adhesive composition may be subjected to an appropriate aging process so that the adhesive polymer and the crosslinking agent contained in the composition may react with each other, For example, ultraviolet irradiation, or the like.
The pressure-sensitive adhesive layer may have, for example, a gel content of about 80% to about 99%. The gel content can be calculated, for example, by the following equation (1).
[Equation 1]
Gel content = B / A x 100
In the formula 1, A represents the mass of the pressure-sensitive adhesive, and B represents the dry mass of the insoluble fractions recovered after immersing the pressure-sensitive adhesive in ethyl acetate at room temperature for 48 hours.
The present application is also directed to optical elements. An exemplary optical element may include an optical element and the adhesive sheet attached to the surface of the optical element. For example, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is attached to the surface of the optical element, so that the optical element can be protected by the surface-protecting base film.
As the optical element included in the optical element, for example, a polarizer, a polarizing plate, a polarizer protective film, a retardation layer or a viewing angle compensation layer can be exemplified.
As the polarizer, for example, general types known in the art such as polyvinyl alcohol polarizers and the like can be employed without limitation.
A polarizer is a functional film or sheet capable of extracting only light vibrating in one direction from incident light while vibrating in various directions. Such a polarizer may be, for example, a form in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film. The polyvinyl alcohol-based resin constituting the polarizer can be obtained by, for example, gelling a polyvinyl acetate-based resin. In this case, the polyvinyl acetate-based resin that can be used may include not only a single adhesive polymer of vinyl acetate but also a co-adhesion polymer of vinyl acetate and other monomers copolymerizable therewith. Examples of the monomer copolymerizable with vinyl acetate include monomers such as unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group, or a mixture of two or more thereof. no. The degree of gelation of the polyvinyl alcohol-based resin may be generally from 85 mol% to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be further modified. For example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol-based resin may be about 1,000 to 10,000, preferably about 1,500 to 5,000.
A polyvinyl alcohol-based resin may be formed and used as the original film of the polarizer. The method of forming the polyvinyl alcohol-based resin is not particularly limited, and a general method known in this field can be used. The thickness of the original film formed of a polyvinyl alcohol-based resin is not particularly limited, and can be suitably controlled within a range of, for example, 1 m to 150 m. The thickness of the original film can be controlled to 10 mu m or more in consideration of easiness of drawing and the like. The polarizer is formed by a process of stretching a polyvinyl alcohol-based resin film as described above (e.g., uniaxial stretching), dyeing a polyvinyl alcohol-based resin film with a dichroic dye and adsorbing the dichroic dye, A process of treating a polyvinyl alcohol resin film with a boric acid aqueous solution and a process of washing with a boric acid aqueous solution after washing. As the dichroic dye, iodine or dichroic organic dyes may be used.
The polarizer may include, for example, the polarizer; And other optical films attached to one side or both sides of the polarizer. Examples of the other optical films include the above-described polarizer protective film, retardation layer, viewing angle compensation layer, antiglare layer, and the like.
The polarizer protective film is a protective film for a polarizer in a concept distinct from a protective film containing the pressure-sensitive adhesive layer. As the polarizer protective film, for example, a cellulose-based film such as triacetylcellulose; Acrylic film; Polyester-based films such as polycarbonate film or polyethylene terephthalate film; Polyethersulfone-based films; And a protective film composed of a polyethylene film, a polypropylene film, or a polyolefin film such as a polyolefin film having a cyclo system or a norbornene structure or an ethylene propylene co-adhesion polymer, or the like. The thickness of the protective film is also not particularly limited, and can be formed in a usual thickness.
In the optical element, a surface treatment layer may be present on the surface of the optical element protected by the protective film. The surface treatment layer may have a surface energy of 30 mN / m or less, for example. That is, a surface treatment layer having a surface energy of 30 mN / m or less is formed on a surface of an optical element protected by the protective film in the optical element, and the pressure sensitive adhesive layer of the protective film is attached to the surface treatment layer .
The surface treatment layer may be a low reflection layer such as an anti-glare layer or an anti-reflection (AR) layer or a low reflection (LR) layer such as a hard layer, an anti-glare layer or a semi- Can be illustrated.
The high hardness layer may be a layer having a pencil hardness of at least 1H or 2H or more under a load of 500 g. Pencil hardness can be measured, for example, according to ASTM D 3363 specification using the pencil lead specified in KS G2603.
The high hardness layer may be, for example, a resin layer having a high hardness. The resin layer may include, for example, a room temperature curing type, a moisture curing type, a thermosetting type, or an active energy ray curing type resin composition in a cured state. In one example, the resin layer may include a thermosetting or active energy ray-curable resin composition, or an active energy ray-curable resin composition in a cured state. The term " cured state " in the description of the hardened layer means a case where the components contained in each of the resin compositions are converted into a hard state through a cross-linking reaction or a polymerization reaction. The above-mentioned room temperature curing type, moisture curing type, thermosetting type or active energy ray curable type resin composition can be prepared by heating the cured state at room temperature or by heating in the presence of appropriate humidity or irradiation of active energy rays ≪ / RTI > composition.
In this field, various resin compositions are known which can satisfy the pencil hardness in the above-mentioned range in a cured state, and an average person can easily select a suitable resin composition.
In one example, the resin composition may include an acrylic compound, an epoxy compound, a urethane compound, a phenol compound or a polyester compound as a main component. In the above, the "compound" may be a monomeric, oligomeric or adhesive polymeric compound.
In one example, an acrylic resin composition excellent in optical properties such as transparency and excellent in resistance to yellowing, for example, an active energy ray-curable acrylic resin composition can be used as the resin composition.
The active energy ray-curable acrylic composition may include, for example, an active energy ray-polymerizable adhesive polymer component and a reactive diluting monomer.
Examples of the adhesive polymer component include a component known as an active energy pre-polymerizable oligomer such as urethane acrylate, epoxy acrylate, ether acrylate or ester acrylate, or a monomer such as a (meth) acrylic acid ester monomer or the like Can be exemplified. Examples of the (meth) acrylic acid ester monomer include alkyl (meth) acrylate, (meth) acrylate having an aromatic group, heterocyclic (meth) acrylate or alkoxy (meth) acrylate. Various adhesive polymer components are known in the art for preparing active energy ray-curable compositions, and such compounds can be selected as needed.
Examples of the reactive diluting monomer which can be contained in the active energy ray-curable acrylic composition include monomers having one or more active energy ray-curable functional groups such as an acryloyl group or a methacryloyl group . As the reactive diluting monomer, for example, the above (meth) acrylic acid ester monomers, multifunctional acrylates, and the like can be used.
The selection of the above-mentioned components for forming the active energy ray-curable acrylic composition, the blending ratio of the selected components and the like are not particularly limited and can be adjusted in consideration of the hardness and other physical properties of the desired resin layer.
As the anti-glare layer such as the AG layer or the SG layer, for example, a resin layer in which an uneven surface is formed or a resin layer containing particles, wherein the resin is a particle layer having a refractive index different from that of the resin layer .
As the resin layer, for example, a resin layer used for forming the high hardness layer may be used. In the case of forming the anti-glare layer, it is not necessary to adjust the components of the resin composition so that the resin layer necessarily exhibits high hardness, but a resin layer may be formed so as to exhibit high hardness.
The method of forming the uneven surface on the resin layer is not particularly limited. For example, the resin composition may be cured in a state in which a coating layer of the resin composition is brought into contact with a metal mold having a desired concavo-convex structure, or particles having a particle diameter appropriate for the resin composition may be blended, have.
The anti-glare layer may also be formed using particles having different refractive indices from the resin layer.
In one example, the difference in refractive index between the particles and the resin layer may be 0.03 or less or 0.02 to 0.2, for example. If the difference in refractive index is too small, it is difficult to cause haze. On the contrary, if the refractive index difference is excessively large, scattering in the resin layer occurs a lot and haze increases, but deterioration of light transmittance or contrast characteristics may be induced. And appropriate particles can be selected.
The shape of the particles contained in the resin layer is not particularly limited and may be, for example, spherical, elliptical, polyhedral, amorphous or other shapes. The particles may have an average diameter of 50 nm to 5,000 nm. In one example, as the particles, particles having irregularities on the surface can be used. Such particles may have a mean surface roughness (Rz) of, for example, 10 nm to 50 nm or 20 nm to 40 nm, and / or a maximum height of irregularities formed on the surface of about 100 nm to 500 nm or 200 nm to 400 nm, and the width between the irregularities may be 400 nm to 1,200 nm or 600 nm to 1,000 nm. Such particles are excellent in compatibility with the resin layer and in dispersibility therein.
As the particles, various inorganic or organic particles can be exemplified. Examples of the inorganic particles include silica, amorphous titania, amorphous zirconia, indium oxide, alumina, amorphous zinc oxide, amorphous cerium oxide, barium oxide, calcium carbonate, amorphous barium titanate, barium sulfate, Examples of the organic particles include crosslinked or non-crosslinked particles of an organic material such as an acrylic resin, a styrene resin, a urethane resin, a melamine resin, a benzoguanamine resin, an epoxy resin or a silicone resin, It is not.
The concavo-convex structure or the content of the particles formed on the resin layer is not particularly limited. The shape of the concave-convex structure or the content of the particles may be controlled such that the haze of the AG layer is about 5% to 15%, 7% to 13%, or about 10% And in the case of the SG layer, the haze can be adjusted to be about 1% to 3%. The haze can be measured according to the manufacturer's manual using a hazemeter such as HR-100 or HM-150 of Sephiroth Co.,
A low reflection layer such as an AR layer or an LR layer can be formed by coating a low refractive material. A low refractive index material capable of forming a low reflection layer is variously known and can be suitably selected and used for the optical element. The low reflection layer can be formed to have a reflectance of about 1% or less through coating of a low refractive material.
The formation of the surface treatment layer may be carried out in the manner described in Korean Patent Publication Nos. 2007-0101001, 2011-0095464, 2011-0095004, 2011-0095820, 2000-0019116, 2000-0009647, 2000 -0018983, 2003-0068335, 2002-0066505, 2002-0008267, 2001-0111362, 2004-0083916, 2004-0085484, 2008-0005722, 2008-0063107 A material known in JP-A-2008-0101801 or JP-A-2009-0049557 can also be used.
The surface treatment layer may be formed singly, or two or more of them may be formed in combination. As an example of the combination, a case where a high hardness layer is first formed on the surface of the base layer and a low reflection layer is formed again on the surface of the base layer is exemplified.
The present application also relates to a display device, for example, a liquid crystal display (LCD). An exemplary display device may include a liquid crystal panel, and the optical element may be attached to one or both sides of the liquid crystal panel. The film may be attached to the liquid crystal panel using, for example, an adhesive or a pressure-sensitive adhesive. In the above, the adhesive or pressure-sensitive adhesive is an adhesive or a pressure-sensitive adhesive other than the pressure-sensitive adhesive present in the protective film described above.
The type of the liquid crystal panel included in the liquid crystal display device is not particularly limited. For example, the present invention is not limited to the type, but various passive matrix methods including TN (Twisted Neumatic) type, STN (Super Twisted Neumatic) type, F (ferroelectric) type and PD (polymer dispersed LCD) type; Various active matrix systems including two-terminal and three-terminal; Any known liquid crystal panel including a horizontal mode (IPS mode) panel and a vertical mode (VA mode) panel can be applied. The types of other structures included in the liquid crystal display device and the manufacturing method thereof are also not particularly limited, and general structures in this field can be employed without any limitations.
The pressure-sensitive adhesive composition of the present application exhibits excellent antistatic property, exhibits a suitable low-speed and high-speed peeling force after the crosslinked structure is formed, and has excellent balance of both. Accordingly, when the pressure-sensitive adhesive composition is applied to, for example, a protective film, it exhibits an excellent protective effect and is easily peeled off at high-speed peeling, is advantageous in terms of high-speed processing, and exhibits excellent antistatic properties in the process .
Hereinafter, the pressure-sensitive adhesive composition will be described in more detail with reference to Examples and Comparative Examples, but the scope of the pressure-sensitive adhesive composition is not limited to the following examples.
1. Measurement of surface resistance
The pressure-sensitive adhesive sheet of the example or the comparative example was cut so as to be 150 mm in width and 50 mm in length, and the releasable PET film was peeled off at a constant speed. Thereafter, the releasable pressure- Three surface areas were arbitrarily designated on the surface to measure the surface resistance, and the average value was obtained. The surface resistance was measured according to the manufacturer's manual using an MCP-HT 450 instrument (Mitsubishi hemical).
2. Measurement of low speed peeling force
The pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were evaluated according to JIS Z 0237 to a high-definition anti-glare film (trade name: ALR1, LG Chemical Co., Ltd., surface contact angle with respect to deionized water: 110 °, surface energy: 20 mN / m) And attached with a roller of 2 Kg. Thereafter, the above-mentioned film with the adhesive sheet was cut and stored at a temperature of 23 캜 and a relative humidity of 65% for 24 hours. The cut was 25 mm long and 100 mm long. Thereafter, the specimen was fixed on a glass substrate, and the pressure-sensitive adhesive sheet was stretched in the longitudinal direction at a stripping angle of 180 degrees and a stripping rate of 0.3 m / min using a tensile tester (Texture Analyzer, Stable Micro System Co., Ltd.) The peeling force was measured while peeling from the anti-glare film. The peeling force was measured for two identical specimens and the average value was adopted.
3. Measurement of high-speed peeling force
The pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were affixed to a high-definition anti-glare film (trade name: ALR1, manufactured by LG Chemical Co., Ltd.) in accordance with JIS Z 0237 with a roller of 2 Kg. Thereafter, the above-mentioned film with the adhesive sheet was cut and stored at a temperature of 23 캜 and a relative humidity of 65% for 24 hours. The cuts were 25 mm long and 250 mm long. Thereafter, the specimen was fixed on a glass substrate, and the pressure-sensitive adhesive sheet was stretched in the longitudinal direction at a peeling angle of 180 degrees and a peeling speed of 30 m / min using a tensile tester (Texture Analyzer, Stable Microsystems, Ltd.) The peeling force was measured while peeling from the anti-glare film. The peeling force was measured for two identical specimens and the average value was adopted.
4. Measurement of stripping voltage (ESD)
The pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were cut to have a length of 220 mm and a length of 250 mm. The cut adhesive sheet thus cut was attached to a high-definition anti-glare film (trade name: ALR1, manufactured by LG Chemical Co., Ltd.) in accordance with JIS Z 0237 with a roller of 2 Kg. Thereafter, the adhesive sheet was peeled from the anti-glare film at a peeling angle of 180 degrees and a speed of 40 m / min at a temperature of 23 ° C and a relative humidity of 65%. The peeling was performed using a tensile tester (Texture Analyzer, Stable Microsystems, Inc.). The peeling electrification voltage was measured at a distance of 40 mm from the surface of the anti-glare film in the normal direction using the measuring equipment (electrostatic potential meter, KSD-200) immediately after the peeling. The peeling electrification voltage was measured twice for the same specimen, and the average value was obtained. The characteristics were evaluated according to the following criteria.
<Characteristic evaluation criteria>
A: When the peeling electrification voltage is 1.0 kV or less
B: When the peeling electrification voltage exceeds 1.0 kV
5. Pollution assessment
The pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were cut to a length of 150 mm and a length of 250 mm. The cut adhesive sheet thus cut was attached to a high-definition anti-glare film (trade name: ALR1, manufactured by LG Chemical Co., Ltd.) in accordance with JIS Z 0237 with a roller of 2 Kg. Thereafter, a black adhesive film was adhered to the surface of the anti-glare film on which the adhesive sheet was not adhered, and was stored at room temperature for 24 hours. Then, the adhesive sheet was peeled off and the anti-glare film was allowed to stand at a temperature of 60 ° C and a relative humidity of 90% for 1 hour. Thereafter, it was judged whether or not contaminants were present in the anti-glare film in the light of a Xenon HID lamp (Polarion) And the characteristics were evaluated according to the following criteria.
<Characteristic evaluation criteria>
A: If there is no contamination
B: In case of contamination
Production Example 1. Preparation of acrylic adhesive polymer (A)
86 parts by weight of 2-ethylhexyl acrylate (2-EHA) and 3 parts by weight of 2-hydroxybutyl acrylate (2-HBA) were added to a 3 L reactor equipped with a cooling device so that nitrogen gas was refluxed and temperature- , 3 parts by weight of 2-hydroxyethyl acrylate (2-HEA), 1 part by weight of N, N-dimethylacrylamide (DMAA) and 1 part by weight of polyethylene glycol monomethyl ether methacrylate (FM- : 9 mol) was added (weight ratio (2-EHA: 4-HBA: 2-HEA: DMAA: FM-401) = 86: 3: 3: 1: 11), 100 parts by weight of ethyl acetate Respectively. Nitrogen gas was then purged for 1 hour to remove oxygen and the temperature was maintained at 60 占 폚. Thereafter, an appropriate amount of a reaction initiator (AIBN: azobisisobutyronitrile) and a molecular weight regulator (n-dodecyl mercaptan) was added and reacted for about 8 hours. The reaction product was diluted with ethyl acetate to prepare an adhesive polymer (A) Concentration: 44% by weight, weight average molecular weight: 35,000).
Production Examples 2 to 11. Preparation of Adhesive Polymers (B) to (K)
An adhesive polymer was prepared in the same manner as in Production Example 1, except that the ratio of the monomers in the production of the adhesive polymer was changed as shown in Tables 1 and 2.
Solids Unit: wt%
Viscosity unit: cP
2-
EHA
: 2-
Ethylhexyl
Acrylate
4-
HBA
: 4-
Hydroxybutyl
Acrylate
2-
HEA
: 2-
Hydroxyethyl
Acrylate
DMAA
:
Dimethylacrylamide
EOEOEA
: 2-2-
Ethoxyethoxyethyl
Acrylate
FM-401:
Polyethylene glycol
Monomethyl ether
Methacrylate
(Number of moles of ethylene oxide units added: 9 moles)
AIBN
(Unit: ppm):
Azobisisobutyronitrile
n-
DDM
(Unit: ppm): n-
Dodecyl
Mercaptan
Solids Unit: wt%
Viscosity unit: cP
2-
EHA
: 2-
Ethylhexyl
Acrylate
4-
HBA
: 4-
Hydroxybutyl
Acrylate
2-
HEA
: 2-
Hydroxyethyl
Acrylate
DMAA
:
Dimethylacrylamide
EOEOEA
: 2-2-
Ethoxyethoxyethyl
Acrylate
FM-401:
Polyethylene glycol
Monomethyl ether
Methacrylate
(Number of moles of ethylene oxide units added: 9 moles)
AIBN
(Unit: ppm):
Azobisisobutyronitrile
n-
DDM
(Unit: ppm): n-
Dodecyl
Mercaptan
Example One.
Preparation of pressure-sensitive adhesive composition
, 6 parts by weight of a mixture of an isoboron diisocyanate crosslinking agent and a hexamethylene diisocyanate crosslinking agent (MHG-80B, manufactured by Asahi) as a crosslinking agent, and 6 parts by weight of LiTFSi (lithium bis ( 1 part by weight of OFX-0193 (Dow Corning) and 3 parts by weight of acetylacetone as a reactive polyether-modified siloxane compound were further uniformly blended to obtain an appropriate concentration To prepare a pressure-sensitive adhesive composition.
Production of pressure-sensitive adhesive sheet
The pressure-sensitive adhesive composition thus prepared was coated on one side of a PET (poly (ethylene terephthalate)) film (thickness: 38 占 퐉) and dried to form a uniform coating layer having a thickness of about 20 占 퐉. Subsequently, a poly (ethylene terephthalate) film was laminated on the coating layer and aged at about 50 캜 for about 3 days to prepare a pressure-sensitive adhesive sheet (protective film).
Example 2 to 7 and Comparative Example 1 to 9
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the composition of the pressure-sensitive adhesive composition was changed as shown in Tables 3 and 4.
Polymer
compound
Cross-linking agent
Kinds:
Isoboron
Diisocyanate series
Cross-linking agent
And
Hexamethylene
Diisocyanate series
Cross-linking
mixture(
MHG
-80B, manufactured by Asahi)
Compound A:
OFX
-0193 (Dow Corning)
Compound B:
OFX
-3667 (Dow Corning)
Li
Salt type: LiTFSi (lithium bis (
trifluoromethanesulfonyl
)
imide
)
Polymer
compound
Cross-linking agent
Kinds:
Isoboron
Diisocyanate series
Cross-linking agent
And
Hexamethylene
Diisocyanate series
Cross-linking
mixture(
MHG
-80B, manufactured by Asahi)
Compound A:
OFX
-0193 (Dow Corning)
Compound C:
silwet
L 77 (
Momentive
)
Li
Salt type: LiTFSi (lithium bis (
trifluoromethanesulfonyl
)
imide
)
The results of evaluating the physical properties of the pressure-sensitive adhesive compositions of the examples and comparative examples prepared above are summarized in Tables 5 and 6 below.
H-peel: High-speed peel force (unit:
gf
/ 25mm)
H / L: High speed
Peel force (H) and
sleaze
The peeling force (L)
ratio
Surface Resistance Unit: × 10
10
Ω / □
H-peel: High-speed peel force (unit:
gf
/ 25mm)
H / L: High speed
Peel force (H) and
sleaze
The peeling force (L)
ratio
Surface Resistance Unit: × 10
10
Ω / □
Claims (16)
[Chemical Formula 1]
(2)
Wherein Q is hydrogen or an alkyl group, U is an alkylene group, Z is hydrogen, an alkyl group or an aryl group, m is a number within a range of 1 to 20, A and B are each independently an alkylene group, and n is a number in the range of 0 to 10.
(A)
[Chemical Formula B]
Formula A or B in the R 1 to R 15 are each independently a hydrogen atom, an alkyl group or alkenyl group, Z is - (CH 2) p - ( O-CH 2 -CH 2) q - (O-CH 2 -CH 2 -CH 2 ) r -U where U is a hydroxyl group, an amine group or an epoxy group, p is a number in the range of 1 to 4, q + r is a number in the range of 1 or more, x is a number in the range of 1 to 10 , and y is a number in the range of 1 to 10.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140519A (en) | 1991-11-19 | 1993-06-08 | Nitto Denko Corp | Surface-protected tacky tape or sheet reduced in occurrence of static electricity |
| KR20040030919A (en) | 2001-08-02 | 2004-04-09 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Optically clear and antistatic pressure sensitive adhesives |
| KR20060128659A (en) | 2005-06-08 | 2006-12-14 | 주식회사 엘지화학 | Acrylic pressure sensitive adhesive compositions |
| KR20140013916A (en) * | 2012-07-27 | 2014-02-05 | 후지모리 고교 가부시키가이샤 | Adhesive composition and surface-protective adhesive film |
| KR20140147764A (en) * | 2013-06-19 | 2014-12-30 | 주식회사 엘지화학 | Pressure sensitive adhesive composition |
-
2015
- 2015-09-04 KR KR1020150125738A patent/KR102024260B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140519A (en) | 1991-11-19 | 1993-06-08 | Nitto Denko Corp | Surface-protected tacky tape or sheet reduced in occurrence of static electricity |
| KR20040030919A (en) | 2001-08-02 | 2004-04-09 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Optically clear and antistatic pressure sensitive adhesives |
| KR20060128659A (en) | 2005-06-08 | 2006-12-14 | 주식회사 엘지화학 | Acrylic pressure sensitive adhesive compositions |
| KR20140013916A (en) * | 2012-07-27 | 2014-02-05 | 후지모리 고교 가부시키가이샤 | Adhesive composition and surface-protective adhesive film |
| KR20140147764A (en) * | 2013-06-19 | 2014-12-30 | 주식회사 엘지화학 | Pressure sensitive adhesive composition |
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|---|---|
| KR102024260B1 (en) | 2019-09-23 |
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