CN116529330A - Adhesive composition and adhesive sheet using same - Google Patents

Adhesive composition and adhesive sheet using same Download PDF

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Publication number
CN116529330A
CN116529330A CN202180082372.1A CN202180082372A CN116529330A CN 116529330 A CN116529330 A CN 116529330A CN 202180082372 A CN202180082372 A CN 202180082372A CN 116529330 A CN116529330 A CN 116529330A
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CN
China
Prior art keywords
meth
adhesive composition
acrylate
group
adhesive
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CN202180082372.1A
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Chinese (zh)
Inventor
郑景文
权惠琳
李晟澈
黄仁吾
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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Publication of CN116529330A publication Critical patent/CN116529330A/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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

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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 a urethane oligomer having a polyester skeleton and having a radically polymerizable functional group at least one terminal, a diluent monomer, and a photoinitiator. The adhesive composition of the present invention exhibits high adhesion to various substrates, and the adhesive layer after curing has a low storage modulus (G') at-20 ℃ and 1Hz and excellent folding properties.

Description

Adhesive composition and adhesive sheet using same
Technical Field
The present invention relates to an adhesive composition and an adhesive sheet using the same, and more particularly, to an adhesive composition which exhibits high adhesion to a substrate and is excellent in folding properties, and an adhesive sheet using the same.
Background
An optically clear adhesive (optically clear adhesive, OCA) having high transparency among adhesives is used for interlayer bonding for laminating components in an image display device. Such an optically clear adhesive is required to have high transmittance and low haze, and to satisfy physical properties such as adhesion to various substrates, heat resistance, and resistance to moist heat.
In recent years, a flexible (flexible) display device or a foldable (folder) display device capable of always maintaining display performance even if bent like paper is rapidly becoming a next-generation display device by using a material having flexibility such as plastic or Ultra Thin Glass (UTG) instead of a conventional inflexible glass substrate, and accordingly, development of an optical transparent adhesive excellent in adhesion and bending resistance is required to be suitable for these display devices. In addition, in order to ensure the quality of products in various environments, development of an optical transparent adhesive excellent in foldability even in extreme environments such as low temperatures has been demanded.
Korean registered patent No. 10-2084113 discloses an adhesive composition comprising a monomer mixture comprising an alkyl acrylate and a hydroxyl acrylate, and an initiator.
However, the adhesive composition has a problem that it is difficult to secure excellent foldability, particularly foldability at low temperature, when applied to a foldable display device.
Disclosure of Invention
Technical problem
An object of the present invention is to provide an adhesive composition which exhibits high adhesion to a plurality of substrates and is excellent in folding properties.
Another object of the present invention is to provide an adhesive sheet formed using the adhesive composition.
Means for solving the problems
In one aspect, the present invention provides an adhesive composition comprising a urethane oligomer having a polyester backbone and having a radically polymerizable functional group at least one terminal end, a diluent monomer, and a photoinitiator.
The adhesive composition of an embodiment of the present invention may have a storage modulus (G') at-20 ℃ and 1Hz after curing of 3 to 30kPa.
In one embodiment of the present invention, the radical polymerizable functional group may be a (meth) acryloyloxy group or a vinyl group.
In one embodiment of the present invention, the urethane oligomer may be a reactant of a polyester polyol, a polyisocyanate, and a radical polymerizable compound having a hydroxyl group.
In one embodiment of the present invention, the polyester polyol may be a compound represented by the following chemical formula 3.
[ chemical formula 3]
In the above-mentioned description of the invention,
r is an organic residue with the valence of 2,
n is an integer of 1 to 100,
m is an integer from 0 to 100.
In one embodiment of the present invention, the radically polymerizable compound having a hydroxyl group may include a (meth) acrylate having a hydroxyl group.
In one embodiment of the present invention, the diluent monomer may comprise a monomer having C 6 -C 30 (meth) acrylate of an alkyl group and a (meth) acrylic monomer having a polar functional group.
In one embodiment of the present invention, the content of the (meth) acrylic monomer having a polar functional group may be 3 to 30% by weight relative to 100% by weight of the entire diluted monomer.
In an embodiment of the present invention, the mixing ratio of the urethane oligomer to the diluent monomer may be 1:9 to 5:5 on a weight basis.
In one embodiment of the present invention, the photoinitiator may be contained in an amount of 0.01 to 3 parts by weight with respect to 100 parts by weight of the total amount of the urethane oligomer and the diluent monomer.
In another aspect, the present invention provides an adhesive sheet formed using the adhesive composition described above.
The adhesive sheet according to an embodiment of the present invention may be used for a foldable display.
Effects of the invention
The adhesive composition of the present invention comprises a urethane oligomer having a polyester skeleton and having a radical polymerizable functional group at least one side terminal, thereby exhibiting high adhesion to various substrates, and after curing, the adhesive layer has a storage modulus (G') as low as 3 to 30kPa at-20 ℃ and 1Hz, and is excellent in folding at low temperatures.
Detailed Description
The present invention will be described in more detail below.
One embodiment of the present invention relates to an adhesive composition comprising a urethane oligomer having a polyester skeleton and having a radical polymerizable functional group at least one side end, a diluent monomer, and a photoinitiator.
The adhesive composition according to one embodiment of the present invention contains a urethane oligomer having a polyester skeleton and having a radically polymerizable functional group at least one terminal, and thus has a low storage modulus at low temperatures and excellent folding properties, and is excellent in adhesion to a wide variety of substrates.
The adhesive composition of an embodiment of the present invention may have a storage modulus (G') at-20℃and 1Hz after curing of 3 to 30kPa, and preferably may have a storage modulus of 3 to 20kPa. If the storage modulus (G') at-20 ℃ and 1Hz after the above-mentioned curing is less than 3kPa, it may be difficult to secure durability, and if it is more than 30kPa, it may be difficult to secure low-temperature foldability.
The storage modulus (G ') refers to energy stored without elastic loss, and the storage modulus (G ') at-20℃and 1Hz refers to the storage modulus (G ') measured at-20℃and 1 Hz.
The storage modulus (G') at-20℃and 1Hz is, for example, a value measured at-20℃at a frequency of 1Hz using a viscoelasticity measuring device (MCR-301, anton Paar Co.) for a sample having a 25 μm thick adhesive layer formed after curing.
In one embodiment of the present invention, the urethane oligomer has a urethane bond in a molecule, a polyester skeleton, and a radical polymerizable functional group at least at one terminal.
The radical polymerizable functional group may be a (meth) acryloyloxy group or a vinyl group, and particularly may be a (meth) acryloyloxy group.
For example, the urethane oligomer may have the structure of the following chemical formula 1.
[ chemical formula 1]
B 1 -L-A-L-B 2 In the above-mentioned description of the invention,
a is polyester, and the polyester is a polyester,
l is a urethane bond-containing linking group,
B 1 is acryloxy, methacryloxy or C 1 -C 10 Is a group consisting of an alkoxy group,
B 2 is acryloyloxy or methacryloyloxy.
C as used in the present specification 1 -C 10 The meaning of the alkoxy group of (a) is a straight-chain or branched alkoxy group having 1 to 10 carbon atoms, and includes methoxy, ethoxy, n-propoxy, butoxy and the like, but is not limited thereto.
Preferably, the above urethane oligomer may have the structure of the following chemical formula 2.
[ chemical formula 2]
In the above-mentioned description of the invention,
a is polyester, and the polyester is a polyester,
R 1 absent or C 1 -C 10 Is used for the preparation of an alkylene group,
R 2 is C 1 -C 10 Alkylene group, C 3 -C 10 Is a cycloalkylene group or an arylene group,
R 3 is C 1 -C 10 Alkylene or C of (2) 3 -C 10 Is a cyclic alkylene group of (a),
B 1 is acryloxy, methacryloxy or C 1 -C 10 Is a group consisting of an alkoxy group,
B 2 is acryloyloxy or methacryloyloxy.
C as used in the present specification 1 -C 10 The alkylene group of (a) means a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and includes, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene and the like, but is not limited thereto.
C as used in the present specification 3 -C 10 The term "cycloalkylene group" as used herein means a monocyclic or condensed ring-shaped hydrocarbon group having 3 to 10 carbon atoms, and includes, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene and the like, but is not limited thereto.
Arylene as used in this specification includes aromatic groups, heteroaromatic groups, and partially reduced derivatives thereof. The above aromatic group means a 5-to 15-membered monocyclic or condensed cyclic aromatic group, and the heteroaromatic group means an aromatic group containing one or more oxygen, sulfur or nitrogen. Examples of the typical arylene group include, but are not limited to, a tolyl group, a phenylene group, and a naphthylene group.
The above C 3 -C 10 More than one hydrogen of the cycloalkylene and arylene groups of (2) may be replaced by C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy groups of (c) and halogen, etc.
The above urethane oligomer can be produced by a method well known in the art.
For example, the urethane oligomer can be produced by reacting a polyester polyol, a diisocyanate, and a radically polymerizable compound having a hydroxyl group. Removal ofIn addition to the above-mentioned radical polymerizable compound having a hydroxyl group, C may be further used 1 -C 10 An alcohol compound of (a).
The polyester polyol may be used as it is or may be produced by a method known in the art.
Examples of the polyester polyol include polycaprolactone polyols obtained by ring-opening polymerization of a low molecular weight polyol and epsilon-caprolactone.
The polyester polyol may be a compound represented by the following chemical formula 3.
[ chemical formula 3]
In the above-mentioned description of the invention,
r is an organic residue with the valence of 2,
n is an integer of 1 to 100,
m is an integer from 0 to 100.
In one embodiment of the present invention, R may be C 1 -C 20 Alkylene groups of (a).
C as used in the present specification 1 -C 20 The alkylene group of (a) means a linear or branched 2-valent hydrocarbon group having 1 to 20 carbon atoms, and includes, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and the like, but is not limited thereto.
In one embodiment of the present invention, R may be, for example, ethylene or butylene.
The number average molecular weight of the above polyester polyol may be 200 to 100,000. If the number average molecular weight of the above polyester polyol is less than 200, the low temperature elastic modulus is increased and it may be difficult to secure low temperature foldability, and if it is more than 100,000, the viscosity is too high and it may be difficult to synthesize urethane oligomer in a process.
As the diisocyanate compound, an aliphatic diisocyanate compound and/or an aromatic diisocyanate compound can be used.
Examples of the aliphatic diisocyanate compound include methyl diisocyanate, 1, 2-ethanediyl diisocyanate, 1, 3-propanediyl diisocyanate, 1, 4-butanediyl diisocyanate, 1, 6-hexanediyl diisocyanate, 3-methyl-octane-1, 8-diyl diisocyanate, 1, 2-cyclohexanediyl diisocyanate, 1, 3-cyclopentanediyl diisocyanate, 1, 4-cyclohexanediyl diisocyanate, 1, 3-cyclohexanediyl diisocyanate, dicyclohexylmethane 4,4' -diisocyanate, isophorone diisocyanate, cyclohexene 1, 4-diisocyanate, and 4-methyl-cyclohexane-1, 3-diyl diisocyanate.
As the above-mentioned aromatic diisocyanate compound, examples thereof include 1, 2-phenylene diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 3-chloro-1, 2-phenylene diisocyanate, 4-chloro-1, 2-phenylene diisocyanate, 5-chloro-1, 2-phenylene diisocyanate, 2-chloro-1, 3-phenylene diisocyanate, 4-chloro-1, 3-phenylene diisocyanate, 5-chloro-1, 3-phenylene diisocyanate, 2-chloro-1, 4-phenylene diisocyanate, 3-methyl-1, 2-phenylene diisocyanate, 4-methyl-1, 2-phenylene diisocyanate, 5-methyl-1, 2-phenylene diisocyanate 2-methyl-1, 3-benzenediisocyanate, 4-methyl-1, 3-benzenediisocyanate, 5-methyl-1, 3-benzenediisocyanate, 2-methyl-1, 4-benzenediisocyanate, 3-methoxy-1, 2-benzenediisocyanate, 4-methoxy-1, 2-benzenediisocyanate, 5-methoxy-1, 2-benzenediisocyanate, 2-methoxy-1, 3-benzenediisocyanate, 4-methoxy-1, 3-benzenediisocyanate, 5-methoxy-1, 3-benzenediisocyanate, 2-methoxy-1, 4-benzenediisocyanate, 3-methoxy-1, 4-benzenediisocyanate, 3, 4-dimethyl-1, 2-benzenediisocyanate, 4, 5-dimethyl-1, 3-benzenediisocyanate, 2, 3-dimethyl-1, 4-benzenediisocyanate, 3-chloro-4-methyl-1, 2-benzenediisocyanate, 3-methyl-4-chloro-1, 2-benzenediisocyanate, 3-methyl-5-chloro-1, 2-benzenediisocyanate, 2-chloro-4-methyl-1, 3-benzenediisocyanate, 4-chloro-5-methoxy-1, 3-benzenediisocyanate, 5-chloro-2-fluoro-1, 3-benzenediisocyanate, 2-chloro-3-bromo-1, 4-benzenediisocyanate, 3-chloro-5-isopropoxy-1, 4-benzenediisocyanate 4,4 '-methylenebis (phenylisocyanate), 2-diphenylpropane-4, 4' -diisocyanate, 4 '-diphenyldiisocyanate, azobenzene-4, 4' -diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, xylylene diisocyanate, 1, 4-naphthylene diisocyanate, 1, 5-naphthylene diisocyanate, m-or p-tetramethylxylene diisocyanate, 2, 3-diisocyanato pyridine, 2, 4-diisocyanato pyridine, 2, 5-diisocyanato pyridine, 2, 6-diisocyanato pyridine, 2, 5-diisocyanate-3-methylpyridine, 2, 5-diisocyanate-4-methylpyridine, 2, 5-diisocyanate-6-methylpyridine, and the like.
As the radical polymerizable compound having a hydroxyl group, a hydroxyl group-containing (meth) acrylate compound can be used. Examples of the hydroxyl group-containing (meth) acrylate compound include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxy-n-propyl (meth) acrylate, 2-hydroxy-isopropyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 5-hydroxy-n-pentyl (meth) acrylate, 2-hydroxy-n-pentyl (meth) acrylate, 3-hydroxy-n-pentyl (meth) acrylate, 4-hydroxy-n-pentyl (meth) acrylate, 2-hydroxy-cyclopropyl (meth) acrylate, 3-hydroxy-cyclopentyl (meth) acrylate, and 4-hydroxy-cyclohexyl (meth) acrylate.
As the above C 1 -C 10 Examples of the alcohol compound(s) include methanol, ethanol, n-propanol, and butanol.
The weight average molecular weight (in terms of polystyrene) of the urethane oligomer measured by gel permeation chromatography (Gel permeation chromatography, GPC) may be 1000 or more and less than 20 ten thousand, and preferably may be 10,000 to 100,000. When the weight average molecular weight of the urethane oligomer is out of the above range, it may be difficult to ensure the workability or the reliability to be lowered.
In one embodiment of the present invention, the diluent monomer is a component that acts as a dispersion medium for the urethane oligomer and is capable of polymerizing by the action of a photoinitiator. In addition, the above-mentioned diluent monomer can facilitate coating by adjusting the viscosity by diluting the adhesive composition.
The diluent monomer may contain a (meth) acrylic monomer.
Here, (meth) acrylic acid means acrylic acid and/or methacrylic acid.
Preferably, the above-mentioned diluent monomer may contain a monomer having C 6 -C 30 (meth) acrylate of an alkyl group and a (meth) acrylic monomer having a polar functional group.
The above-mentioned having C 6 -C 30 The alkyl (meth) acrylate of (a) has a low glass transition temperature (Tg), and thus can reduce the storage modulus after curing of the adhesive composition and can improve the foldability.
As the above having C 6 -C 30 Examples of the alkyl (meth) acrylate include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate, and among these, 2-ethylhexyl (meth) acrylate is preferable. They may be used singly or in combination of two or more.
The polar functional group-containing (meth) acrylic monomer can form a hydrogen bond or an ionic bond with the polar group of the lower substrate, and thus can improve the adhesion of the adhesive composition.
The polar functional group-containing (meth) acrylic monomer may be one or more of a hydroxyl group-containing (meth) acrylate and a nitrogen atom-containing (meth) acrylamide.
Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethanediol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, and hydroxyalkylene glycol (meth) acrylate having an alkylene group with a carbon number of 2 to 4, and among these, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and the like are preferable.
Examples of the (meth) acrylamide having a nitrogen atom include (meth) acrylamide, dimethyl (meth) acrylamide, acryloylmorpholine, dimethylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, diethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, and diacetone (meth) acrylamide.
The content of the (meth) acrylic monomer having a polar functional group may be 3 to 30% by weight relative to 100% by weight of the whole of the diluted monomer. If the content of the above-mentioned (meth) acrylic monomer having a polar functional group is less than 3% by weight, the adhesion may be lowered, and if it is more than 30% by weight, the low-temperature elastic modulus may be increased.
In an embodiment of the present invention, the mixing ratio of the urethane oligomer to the diluent monomer may be 1:9 to 5:5, preferably may be 2:8 to 6:4 on a weight basis. In the case where the mixing ratio of the urethane oligomer to the diluent monomer is less than the above range, the thickness variation in the step of producing the sheet may be increased, and if it exceeds the above range, the adhesion may be decreased, and the reliability may be lowered.
The diluent monomer may further contain a polymerizable monomer other than the monomer.
Specific examples of the other polymerizable monomer include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, and isobornyl (meth) acrylate, and among them, isobornyl (meth) acrylate is preferable. They may be used singly or in combination of two or more.
The content of the other polymerizable monomer may be 10% by weight or less based on 100% by weight of the whole of the diluent monomer. In the case where the content of the other polymerizable monomer is more than 10% by weight, the low-temperature elastic modulus may be increased.
In one embodiment of the present invention, the photoinitiator is an initiator that absorbs active energy rays to generate radicals.
As the above-mentioned photoinitiator, there is used, examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone 4,4' -bis (diethylamino) benzophenone (EAB-F), dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-Diethylthioxanthone (DETX), 4-Isopropylthioxanthone (ITX), benzil dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo [ 2-hydroxy-2-methyl-1 [4- (1-methylvinyl) phenyl ] propane ], 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, 2- (3, 4-methylenedioxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbiimidazole (HABI-101), 2' -bis (2-methoxyphenyl) -4,4', 5' -tetraphenylbiimidazole (HABI-107), 2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4',5' -diphenylbiimidazole (TCDM), and the like. They may be used singly or in combination of two or more.
The content of the photoinitiator may be 0.01 to 3 parts by weight relative to 100 parts by weight of the total amount of the urethane oligomer and the diluent monomer. In the case of less than 0.01 parts by weight, the photo-curing may not be sufficiently performed, it may be difficult to achieve mechanical properties or adhesive force of the finally obtained adhesive sheet, and in the case of more than 3 parts by weight, discoloration or durability may occur due to the remaining initiator.
The adhesive composition according to an embodiment of the present invention may further contain additives such as plasticizers, silane coupling agents, tackifying resins, antioxidants, anticorrosive agents, leveling agents, surface lubricants, dyes, pigments, antifoaming agents, fillers, light stabilizers, antistatic agents, and the like in addition to the above-described components to adjust the required adhesion, cohesion, tackiness, elastic modulus, glass transition temperature, antistatic properties, and the like according to the purpose.
An embodiment of the present invention relates to an adhesive sheet formed by using the adhesive composition.
The adhesive sheet may be a sheet obtained by forming an adhesive layer from the adhesive composition of the present invention on a base film, or may be a sheet in which an adhesive layer formed from the adhesive composition of the present invention is sandwiched between 2 base films.
Examples of the substrate film include polyolefin films, polyester films, acrylic films, styrene films, amide films, polyvinyl chloride films, polyvinylidene chloride films, and polycarbonate films, and these substrate films may be subjected to an appropriate mold release treatment such as a silicon-based film, a fluorine-based film, and a silica powder.
The thickness of the base film is preferably 30 to 80. Mu.m. In the case of less than 30 μm, a puncture (sticking) failure tends to occur in the base film, and in the case of more than 80 μm, the handleability may be degraded.
The adhesive layer may be formed by a method of coating an adhesive composition on 1 sheet of substrate film. The coating method is not particularly limited, and methods known in the art may be used, for example, bar coating, air knife, gravure, reverse roll, lip die roll, spray, doctor blade, die coating, casting, spin coating, and the like. Specifically, the adhesive composition may be coated on 1 sheet of substrate film and at a rate of about 100 to 2000mJ/cm 2 Preferably 200 to 1500mJ/cm 2 Is formed by irradiating with ultraviolet irradiation amount to be photo-cured.
The thickness of the adhesive layer may be 10 to 2,000 μm, and preferably may be 25 to 1,500 μm. If the thickness of the adhesive layer is less than 10 μm, it may be difficult to alleviate the impact generated from the outside, and if it is more than 2,000 μm, the transmission may be degraded and the optical performance may be degraded.
The adhesive sheet according to one embodiment of the present invention may have an adhesive layer surface treated before joining to improve adhesion.
The surface treatment method is not particularly limited, and for example, the surface of the adhesive layer may be activated by a method such as corona discharge treatment, plasma treatment, ultraviolet irradiation, electron beam irradiation, or anchor (anchor) coating.
The adhesive sheet according to an embodiment of the present invention can be applied not only to a general flat panel display and a flexible display but also to a foldable display. In particular, the adhesive sheet according to one embodiment of the present invention is excellent in folding property because the storage modulus at low temperature is controlled in the range of 3 to 30kPa, and therefore can be effectively used for interlayer adhesion in which components are laminated in a foldable display device. Specifically, the adhesive sheet can be applied to the bonding of various display materials such as antennas, display panels, polarizers, touch sensors, exterior windows, frames, polymer films, and FPCBs.
Hereinafter, the present invention will be described more specifically with reference to examples, comparative examples and experimental examples. It is obvious to those skilled in the art that these examples, comparative examples and experimental examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
Production example 1: production of urethane oligomers
500ppm of dibutyltin dilaurate catalyst (DBTDL) and 10 parts by weight of isophorone diisocyanate were reacted with a polycaprolactone diol having a number average molecular weight of 1230 (trade name: placce 212]81 parts by weight was reacted at 80℃and then the obtained isocyanate polymer was reacted with 9 parts by weight of 2-hydroxyethyl acrylate to produce a urethane oligomer having a weight average molecular weight of 60,000.
Production example 2: production of urethane oligomers
500ppm of dibutyltin dilaurate catalyst (DBTDL) and 10 parts by weight of isophorone diisocyanate were reacted with a polycaprolactone diol having a number average molecular weight of 2000 [ trade name of Dai Jiu Chemie Co., ltd.: placce 220]81 parts by weight was reacted at 80℃and then the obtained isocyanate polymer was reacted with 9 parts by weight of 2-hydroxyethyl acrylate to produce a urethane oligomer having a weight average molecular weight of 80,000.
Production example 3: production of urethane oligomers
500ppm of dibutyltin dilaurate catalyst (DBTDL) and 10 parts by weight of 1, 6-hexamethylene diisocyanate were mixed with a polycaprolactone diol having a number average molecular weight of 1230 (trade name: placce 212]81 parts by weight was reacted at 80℃and then the obtained isocyanate polymer was reacted with 9 parts by weight of 2-hydroxyethyl acrylate to produce a urethane oligomer having a weight average molecular weight of 70,000.
Production example 4: production of urethane oligomers
500ppm of dibutyltin dilaurate catalyst (DBTDL) and 10 parts by weight of isophorone diisocyanate were reacted with 81 parts by weight of polypropylene glycol (Han Nong to PPG 1000) having a number average molecular weight of 1000 at 80℃and then the obtained isocyanate polymer was reacted with 9 parts by weight of 2-hydroxyethyl acrylate to produce a urethane oligomer having a weight average molecular weight of 60,000.
Examples 1 to 5 and comparative examples 1 to 2: adhesive composition and production of adhesive sheet
Adhesive compositions (parts by weight) were prepared by mixing the compositions shown in table 1 below.
TABLE 1
2-EHA: 2-ethylhexyl acrylate
4-HBA: acrylic acid 4-hydroxybutyl ester
2-HEA: acrylic acid 2-hydroxy ethyl ester
ACMO: acryloylmorpholines
I-184: irgacure 184 (Basf) Inc
The adhesive compositions of examples 1 to 5 and comparative examples 1 to 2 manufactured above were coated on a polyethylene terephthalate film (thickness: 75 μm) subjected to a mold release treatment using a bar coater. Thereafter, the UV lamp was used at 2.0J/cm 2 The adhesive sheet was produced by irradiating the adhesive composition with ultraviolet rays for 10 minutes to cure the adhesive composition so that the thickness of the adhesive composition became 50 μm after curing.
Experimental example 1:
physical properties of the adhesive sheets manufactured in examples and comparative examples were measured by the following methods, and the results are shown in table 2 below.
(1) Bonding force
The adhesion force of the adhesive sheets manufactured in examples and comparative examples to various substrates was measured.
The release film on one side of the adhesive sheet was peeled off, and the adhesive sheet was subjected to corona treatment and then joined to a 38 μm PET film, followed by cutting into pieces having a width of 25mm and a length of 100mm, to thereby produce test pieces. Then, the release film on the remaining surface was peeled off, and the adhesive sheet was attached to the alkali glass using a 2kg roller according to JIS Z0237. The pressure-bonding treatment was performed for about 20 minutes in an autoclave (50 ℃ C., 5 atm), and the pressure-bonding sheet was peeled off from the alkali glass at a peeling rate of 300mm/min and a peeling angle of 180 degrees by using a TA instrument (Texture Analyzer, manufactured by UK Stable Microsystems) after storage under constant temperature and humidity conditions (23 ℃ C., 50% relative humidity) for 1 hour.
The adhesion force of polyethylene terephthalate (polyethylene terephthalate, PET) was measured by the same method except that an object obtained by adhering a PET film to an alkali glass with a double-sided tape was used as an adherend.
(2) Storage modulus (G')
The storage modulus at-20℃was measured for the adhesive sheets produced in examples and comparative examples using a viscoelasticity measuring apparatus (MCR-301, anton Paar Co.). More specifically, the adhesive sheet was cut to a length of 30mm×width of 30mm, the release film attached to one surface of the cut adhesive sheet was removed, and the adhesive sheet was bonded to a glass substrate, and then measured at a temperature range of-30 to 100 ℃ in a state of being bonded to a measuring head (tip) under conditions of a frequency of 1.0Hz, a strain of 2%, and a heating rate of 5 ℃/min, and at this time, a measured value of-20 ℃ was read.
(3) Folding property
The adhesive sheets produced in examples and comparative examples were joined to 50 μm PET film, and cut into 20mm X100 mm pieces to be used as test pieces. The test piece was fixed to a bending property evaluation device (COVOTECH Co., CFT-720C) for evaluating the bending property, and the bending property was evaluated at-20℃under the conditions of folding (folding) with a radius of curvature of 2mm and holding for 0.2 seconds after folding 25 times per minute and 1 time per minute. In the folding property evaluation, 1 folding was performed to 1 cycle, and the minimum number of cycles in which streaks and the like occur at the folding portion or breakage, warpage, peeling and the like of the adhesive sheet occur was evaluated, and if streaks and the like occur at the folding portion or breakage, warpage, peeling and the like of the adhesive sheet occur, it was judged as failed (NG), and if not, it was judged as failed (OK).
(4) High temperature reliability
The adhesive sheets produced in examples and comparative examples were placed between a polarizing plate and a PET film to produce a plywood, and then stored at a high temperature and high humidity (85 ℃ C., 85% relative humidity) for 10 days, and then observed with the naked eye to confirm whether or not air bubbles or peeling occurred.
< evaluation criterion >
OK: no air bubbles and peeling
NG: with bubbles and/or peeling
TABLE 2
As shown in table 2 above, the adhesive compositions of examples 1 to 5 according to the present invention, which contained a urethane oligomer having a polyester skeleton and having a radical polymerizable functional group at least one terminal, a diluent monomer, and a photoinitiator, were excellent in adhesion to various substrates, and the storage modulus (G') of the adhesive layer after curing at-20 ℃ and 1Hz was as low as 3 to 30kPa level, and thus it was confirmed that the foldability was excellent.
On the other hand, the adhesive compositions of comparative examples 1 to 2, in which the urethane oligomer having a polyether skeleton was used instead of the urethane oligomer having a polyester skeleton and having a radical polymerizable functional group at least one side end, exhibited poor foldability when the adhesive layer had a storage modulus (G') of more than 30kPa at-20 ℃ and 1Hz after curing.
While specific parts of the present invention have been described in detail hereinabove, it will be apparent to those skilled in the art that such details are merely preferred embodiments, and the scope of the invention is not limited thereto. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above description.
Therefore, it is intended that the actual scope of the invention be defined by the scope of the appended claims and their equivalents.

Claims (12)

1. An adhesive composition comprising a urethane oligomer having a polyester backbone and having a free radically polymerizable functional group at least one terminal end, a diluent monomer, and a photoinitiator.
2. The adhesive composition of claim 1 having a storage modulus G' at-20 ℃ and 1Hz of 3 to 30kPa after curing.
3. The adhesive composition of claim 1, the free radically polymerizable functional group being a (meth) acryloxy group or a vinyl group.
4. The adhesive composition of claim 1, the urethane oligomer being a reactant of a polyester polyol, a polyisocyanate, and a radically polymerizable compound having a hydroxyl group.
5. The adhesive composition according to claim 4, wherein the polyester polyol is a compound represented by the following chemical formula 3:
[ chemical formula 3]
In the above-mentioned formula, the catalyst,
r is an organic residue with the valence of 2,
n is an integer of 1 to 100,
m is an integer from 0 to 100.
6. The adhesive composition according to claim 4, wherein the radically polymerizable compound having a hydroxyl group comprises a (meth) acrylate having a hydroxyl group.
7. The adhesive composition of claim 1, the diluent monomer comprising a monomer having C 6 -C 30 (meth) acrylate of an alkyl group and a (meth) acrylic monomer having a polar functional group.
8. The adhesive composition according to claim 7, wherein the content of the (meth) acrylic monomer having a polar functional group is 3 to 30% by weight relative to 100% by weight of the whole of the diluted monomer.
9. The adhesive composition of claim 1, the mixing ratio of the urethane oligomer to the diluent monomer being 1:9 to 5:5 on a weight basis.
10. The adhesive composition according to claim 1, wherein the photoinitiator is contained in an amount of 0.01 to 3 parts by weight relative to 100 parts by weight of the total amount of the urethane oligomer and the diluent monomer.
11. An adhesive sheet formed using the adhesive composition according to any one of claims 1 to 10.
12. The adhesive sheet of claim 11 for use in a foldable display.
CN202180082372.1A 2020-12-08 2021-12-01 Adhesive composition and adhesive sheet using same Pending CN116529330A (en)

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