CN111748302A - (meth) acrylate adhesive composition - Google Patents
(meth) acrylate adhesive composition Download PDFInfo
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- CN111748302A CN111748302A CN202010683779.7A CN202010683779A CN111748302A CN 111748302 A CN111748302 A CN 111748302A CN 202010683779 A CN202010683779 A CN 202010683779A CN 111748302 A CN111748302 A CN 111748302A
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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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a (meth) acrylic esterAn adhesive composition comprising a (meth) acrylate polymer, a crosslinking agent and a siloxane copolymer, wherein the siloxane copolymer comprises 70 to 95 parts by weight of a monomer having C1To C4An alkyl acrylic monomer and 5 to 30 parts by weight of a silane compound represented by the following formula (I): X-R1‑SiR2 3‑a(OR3)a(I) The siloxane copolymer has a weight average molecular weight of between 40,000 and 150,000. The siloxane copolymer in the adhesive composition provided by the invention can improve the initial adhesion, weather resistance and reworkability of the (methyl) acrylate adhesive composition, and has good bending recovery resistance and adhesion when used for a flexible optical film.
Description
Technical Field
The present invention relates to a (meth) acrylate adhesive composition useful for an optical film, and more particularly, to a (meth) acrylate adhesive composition having good adhesion and reworkability.
Background
In recent years, with the development of display technology, various optical films, such as polarizers, compensation films, brightness enhancement films, etc., have been applied to displays to achieve display effects and improve display quality.
The polarizer is one of the main optical components of liquid crystal displays and Organic Light Emitting Diode (OLED) displays, and after an adhesive layer is formed on the surface of the polarizer, the polarizer is adhered to a substrate of a display panel. Depending on the application field of the display, the adhesive layer for the polarizer should have proper adhesion, for example, the display used in the vehicle and outdoor environment needs to face a severe environment, so the adhesive layer used for the polarizer needs not only good adhesion but also good weather resistance. Moreover, when the polarizer is attached to the display panel, it is necessary to ensure that the optical axis of the polarizer is located at the correct position, so if a defect is found after the attachment, the polarizer must be easily removed from the display substrate and the damage to the substrate during the removal is avoided, and therefore, the adhesive layer is expected to have proper stripping property to meet the requirement of reworking.
In the prior art, various adhesive compositions containing silane compounds, for example, adhesive compositions using silane compounds containing epoxy groups, have been known, but the adhesive force thereof may be excessively increased under high temperature and high humidity conditions, and the adhesive remains on the substrate during peeling due to the excessive increase of the adhesive force during the rework process. Also, for example, an adhesive composition using a cyanoacetyl group-containing silane-based compound can have good reworkability without an excessive increase in adhesion under high temperature and high humidity conditions, but such an adhesive has relatively poor initial adhesion and weather resistance.
In the prior art, it has also been proposed to add an additive composition containing a polysiloxane compound, an organosilicon compound, a polyoxyalkylene and an acrylate to a (meth) acrylate adhesive composition to enhance the adhesion. However, after the polarizer and the substrate are bonded, the adhesion force of the acrylic adhesive increases with time, which is not favorable for reworking of the polarizer.
Furthermore, with the development of flexible display devices, in a composite structure containing multiple optical films in a flexible display device, adhesives are required to be used for laminating and assembling between heterogeneous optical films, but because the materials and the modulus of the films are different, the stress bearing degrees in the synchronous bending and folding process are also different, so that in addition to the problem that the materials of the films are required to overcome stress fracture, the adhesives between the films also need to have certain effects of slow release and stress absorption, and meanwhile, the materials of the films still need to have enough adhesion and filling performance so that the films are not peeled off after being stressed to cause damage and failure of the flexible display device. Therefore, adhesives for flexible display devices need to have good resistance to recovery from bending and adhesion, and to be free from the problem of creep.
Disclosure of Invention
In view of the problems in the prior art, the present invention is directed to a (meth) acrylate adhesive composition for bonding an optical film to a substrate, comprising a (meth) acrylate polymer, a crosslinking agent, and a siloxane copolymer, wherein the siloxane copolymer comprises an acrylic monomer and a silane compound. The siloxane copolymer of the (meth) acrylate adhesive composition of the present invention has an acrylic monomer which is polar-compatible with the acrylic component of the (meth) acrylate adhesive composition and a silane compound which can enhance the adhesion with the substrate, can improve the initial adhesion and weather resistance of the (meth) acrylate adhesive composition, and does not rapidly climb over time, and thus can have the rework properties required for the process. In addition, when used in an adhesive for flexible display devices, it can provide good flexibility without the problem of creep and has excellent adhesion.
In order to achieve the above object, the present invention provides a (meth) acrylate adhesive composition comprising:
(meth) acrylate polymers;
a crosslinking agent; and
a siloxane copolymer, wherein the siloxane copolymer comprises 70 to 95 parts by weight of a monomer having C1To C4An alkyl acrylic monomer, and 5 to 30 parts by weight of a silane compound represented by the following formula (I):
X-R1-SiR2 3-a(OR3)a(I)
in the formula (I), X is acryloyl or (meth) acryloyloxy, R1Is C1To C8Alkyl or alkoxy of, R2And R3Each is C1To C4A is an integer of 1 to 3, and the weight average molecular weight of the siloxane copolymer is between 40,000 and 150,000;
wherein the siloxane copolymer is used in an amount of 0.2 to 25 parts by weight per hundred parts by weight of the (meth) acrylate polymer.
As an alternative, the siloxane copolymer has a glass transition temperature of between-22 ℃ and-40 ℃.
As an alternative technical scheme, the silane compound shown in the formula (I) is 3-methacryloxypropyltrimethoxysilane.
As an optional technical solution, the acrylic monomer includes a butyl acrylate monomer and at least one acrylate monomer selected from the group consisting of a methyl acrylate monomer, an ethyl acrylate monomer, and a propyl acrylate monomer.
As an optional technical solution, the weight ratio of the butyl acrylate monomer and at least one acrylate monomer selected from the group consisting of methyl acrylate monomer, ethyl acrylate monomer and propyl acrylate monomer is between 1.5 and 0.6.
Alternatively, the siloxane copolymer has a weight average molecular weight of between 50,000 and 140,000.
As an alternative solution, the difference between the glass transition temperature of the (meth) acrylate polymer and the glass transition temperature of the siloxane copolymer is between 3 ℃ and 15 ℃.
As an alternative solution, the siloxane copolymer also comprises a chain transfer agent.
As an alternative solution, the (meth) acrylate polymer comprises a (meth) acrylate monomer and a crosslinkable monomer.
As an alternative solution, the (meth) acrylate monomer in the (meth) acrylate polymer accounts for 90 to 99.8 weight percent of the total weight of the (meth) acrylate monomer and the crosslinkable monomer, and the crosslinkable monomer in the (meth) acrylate polymer accounts for 0.2 to 10 weight percent of the total weight of the (meth) acrylate monomer and the crosslinkable monomer.
As an alternative solution, the (meth) acrylate monomer in the (meth) acrylate polymer accounts for 94 to 99.5 weight percent of the total weight of the (meth) acrylate monomer and the crosslinkable monomer, and the crosslinkable monomer in the (meth) acrylate polymer accounts for 0.5 to 6 weight percent of the total weight of the (meth) acrylate monomer and the crosslinkable monomer.
As an alternative solution, the (meth) acrylate polymer further comprises a free radical reactive monomer comprising 0.5 to 10 parts by weight, relative to the total weight of the (meth) acrylate monomer and the crosslinkable monomer per hundred parts by weight.
Compared with the prior art, the (methyl) acrylate adhesive composition has good initial adhesion and weather resistance, and the adhesion can not rapidly rise with time and has the reworkability required by the process. The (meth) acrylate adhesive composition of the present invention can also be used for a composite structure for attaching a flexible display device, which can provide effects of slow release and absorption of stress between film layers to achieve good flexibility without a creep problem and have excellent adhesion.
Detailed Description
In order to make the disclosure more complete and complete, the following description is given for illustrative purposes, with reference to embodiments and examples of the invention; it is not intended to be the only form in which the embodiments of the invention may be practiced or utilized. The various embodiments disclosed below may be combined with or substituted for one another where appropriate, and additional embodiments may be added to one embodiment without further recitation or description.
The advantages, features, and advantages of the present invention will be more readily understood by reference to the following detailed description of exemplary embodiments and the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein but, on the contrary, is provided for a person of ordinary skill in the art to so fully convey the scope of the present invention and that the present invention is defined only by the appended claims.
Unless otherwise defined, all terms (including technical and scientific terms) and terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and terms such as those defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an overly idealized or overly formal sense unless expressly so defined herein.
Furthermore, in this context, "(meth) acrylic acid" refers to methacrylic acid and acrylic acid, "(meth) acrylate" refers to methacrylate and acrylate, and "meth) acrylamide" refers to methacrylamide and acrylamide.
The present invention provides a (meth) acrylate adhesive composition comprising a (meth) acrylate polymer, a crosslinking agent and a siloxane copolymer, wherein the siloxane copolymer comprises 70 to 95 parts by weight of a monomer having C1To C4Alkyl acrylic monomers; and 5 to 30 parts by weight of a silane compound represented by the following formula (I):
X-R1-SiR2 3-a(OR3)a(I)
in the formula (I), X is acryloyl or (meth) acryloyloxy, R1Is C1To C8Alkyl or alkoxy of, R2And R3Each is C1To C4A is an integer of 1 to 3, and the weight average molecular weight of the siloxane copolymer is between 40,000 and 150,000. Wherein the siloxane copolymer is used in an amount of 0.2 to 25 parts by weight per hundred parts by weight of the (meth) acrylate polymer.
In the (meth) acrylate adhesive composition of the present invention, the siloxane copolymer comprises at least one acrylic monomer which is polar compatible with the acrylate component of the (meth) acrylate adhesive and a silane compound which can enhance the adhesion, wherein the siloxane copolymer and the (meth) acrylate polymer are hydrogen bonds or weak bonds such as Vanderwal force, the initial adhesion is not affected in the adhesive, and due to the polarity difference between the siloxane copolymer and the acrylate polymer, when the (meth) acrylate adhesive is applied to a display panel to be adhered thereto, the siloxane copolymer of the (meth) acrylate adhesive slowly moves to the substrate surface of the display panel and reacts with the substrate surface to occupy the pores of the polarizer substrate, thereby reducing the adhesion. Therefore, the (meth) acrylate adhesive composition of the present invention has a better initial adhesion and can provide good reworkability required for the process, and the adhesion does not greatly climb over time to maintain stable adhesion and can meet the requirement of weather resistance.
On the other hand, since the glass transition temperature of the (meth) acrylate adhesive composition affects its applicability and process operability, the glass transition temperature of each component is considered to achieve the desired glass transition temperature of the adhesive when selecting the components of the (meth) acrylate adhesive composition. In the (meth) acrylate adhesive composition of the present invention, the difference between the glass transition temperature of the siloxane copolymer and the glass transition temperature of the (meth) acrylate polymer is between 3 ℃ and 15 ℃, and preferably between 3 ℃ and 12 ℃.
In the (meth) acrylate adhesive composition of the present invention, the glass transition temperature of the siloxane copolymer can be adjusted depending on the selected acrylic monomer. The acrylic monomer of the siloxane copolymer may comprise more than one acrylate monomer. In a preferred embodiment of the present invention, the acrylic monomer of the siloxane copolymer comprises butyl acrylate monomer and acrylate monomer selected from the group consisting of methyl acrylate monomer, ethyl acrylate monomer and propyl acrylate monomer, and the ratio of the butyl acrylate monomer to the at least one acrylate monomer selected from the group consisting of methyl acrylate monomer, ethyl acrylate monomer and propyl acrylate monomer is between 1.5 and 0.6. The (meth) acrylate adhesive composition of the present invention can be used in the lamination of functional optical films of optical displays, such as polarizers, so that the siloxane copolymer can be prepared by selecting an appropriate acrylic monomer so that the glass transition temperature is between-22 ℃ and-40 ℃, and preferably between-25 ℃ and-35 ℃.
In a preferred embodiment of the (meth) acrylate adhesive composition of the present invention, the weight average molecular weight of the siloxane copolymer is preferably between 50,000 and 140,000.
In a preferred embodiment of the (meth) acrylate adhesive composition of the present invention, the silicon atom and the at least one alkane in the siloxane copolymer represented by formula (I)Oxy (-OR)3) Bonded, in particular with 1 to 3C1To C4The alkoxy group of (3) is preferably bonded. In a preferred embodiment of the siloxane copolymers of the invention, 3-methacryloxypropyltrimethoxysilane is particularly suitable as silane compound.
The preparation method of the siloxane copolymer of the (methyl) acrylate adhesive composition comprises the steps of dissolving an acrylic monomer and a silane compound shown as a formula (I) in a solvent under an inert gas environment, and then adding an initiator to initiate polymerization reaction to obtain the siloxane copolymer of the (methyl) acrylate adhesive composition.
Suitable initiators for the preparation of the siloxane copolymers are those customary in the art, such as azo-based initiators, which may be, for example and without limitation, 2' -azobis (2-methylbutyronitrile), 2' -azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), dimethyl-2, 2' -azobis (2-methylpropionic acid), etc., preferably 2,2' -azobisisobutyronitrile; for example, the diacyl peroxide initiator may be, but is not limited to, benzoyl peroxide, lauroyl peroxide, and decanoyl peroxide.
Suitable solvents for preparing the siloxane copolymers are those customary in the art, such as ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene or xylene.
In still another preferred embodiment of the (meth) acrylate adhesive composition of the present invention, the siloxane copolymer may further comprise a chain transfer agent to control the molecular weight of the siloxane copolymer. Chain transfer agents used in the siloxane copolymers of the present invention may be those known in the art, such as aliphatic thiols, for example n-dodecyl mercaptan; such as, but not limited to, xanthogen disulfides, for example diisopropyl xanthogen disulfide.
The (meth) acrylate adhesive composition of the present invention may comprise a (meth) acrylate polymer, a crosslinking agent, a siloxane copolymer, and optionally suitable additives.
The (meth) acrylate polymer of the (meth) acrylate adhesive composition of the present invention may include a (meth) acrylate monomer and a crosslinkable monomer.
The (meth) acrylate monomer suitable for the (meth) acrylate polymer of the present invention may be C having a linear, branched, or cyclic structure1-C12Alkyl or alkoxy, or aryloxy (meth) acrylate monomers, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl acrylate, phenoxypropyl (meth) acrylate, and mixtures thereof, Phenoxybutyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, tolyl (meth) acrylate, polystyrene-based (meth) acrylate, or the like, and the above monomers may be used alone or in combination. The (meth) acrylate monomer in the (meth) acrylate polymer is 90 to 99.8 weight percent, preferably 94 to 99.5 weight percent, based on the total weight of the (meth) acrylate monomer and the crosslinkable monomer.
The crosslinkable monomer suitable for the (meth) acrylate polymer of the present invention may be a carboxylic acid group-containing or hydroxyl group-containing monomer, and may be, for example, without limitation, acrylic acid, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, chloro-2-hydroxypropyl (meth) acrylate, etc., which may be used alone or in combination, preferably 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate. The crosslinkable monomer in the (meth) acrylate polymer is present in an amount of 0.2 to 10 wt%, preferably 0.5 to 6 wt%, based on the total weight of the (meth) acrylate monomer and the crosslinkable monomer.
In an embodiment of the present invention, the (meth) acrylate polymer may be obtained by dissolving a (meth) acrylate monomer and a crosslinkable monomer in a solvent under an inert gas environment, and then adding an initiator to initiate a polymerization reaction, wherein the initiator used may be azobisisobutyronitrile, 2 '-azobis (2, 4-dimethylvaleronitrile), azobisisoheptonitrile, dimethyl-2, 2' -azobis (2-methylpropionic acid), benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, or the like. Suitable solvents may be organic solvents such as ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene or xylene.
The (meth) acrylate polymer of the present invention may optionally contain a radical reactive monomer such as a vinyl-based monomer, for example, vinyl acetate, styrene or the like, but not limited thereto, in addition to the (meth) acrylate monomer and the crosslinkable monomer. The free radical reactive monomer may comprise 0.5 to 10 parts by weight, and preferably 0.5 to 5 parts by weight, per hundred parts by weight of the total weight of the (meth) acrylate monomer and the crosslinkable monomer.
The (meth) acrylate polymer of the present invention may have a weight average molecular weight of 500,000 to 1,800,000, preferably 800,000 to 1,500,000, and a glass transition temperature of-60 ℃ to 0 ℃, preferably-50 ℃ to-20 ℃.
In one embodiment of the present invention, the (meth) acrylate polymer and the siloxane copolymer are polymerized in a solvent in the presence of a crosslinking agent. The crosslinking agent suitable for the polymerization reaction may be one or more of an isocyanate compound, an amine compound, an epoxy compound or a metal chelate compound. Suitable isocyanate-based compound crosslinking agents include, for example, tolylene diisocyanate and its trimer, hydrogenated tolylene diisocyanate, tolylene diisocyanate adduct of trimethylolpropane, xylylene diisocyanate adduct of trimethylolpropane, triphenylmethane triisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 4' -diisocyanate dihexyl methane, etc.; suitable amine-based compound crosslinking agents may be, for example, hexamethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, amino resins or melamine resins; suitable epoxy-based compound crosslinking agents may be, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diglycidyl amine, N '-tetracyclooxypropyl-m-xylenediamine, bisphenol F diglycidyl ether, or 1, 3-bis (N, N' -diepoxylaminomethyl) cyclohexane; suitable metal chelate crosslinking agents may be, for example, polyvalent metal chelates of acetylacetone with aluminum, iron, copper, zinc, tin, titanium, zirconium, magnesium, or the like, but are not limited thereto.
In one embodiment of the present invention, the crosslinking agent may be between 0.1 and 25 parts by weight, and preferably between 0.5 and 20 parts by weight per hundred parts by weight of the (meth) acrylate polymer.
Suitable solvents for the polymerization reaction may include, but are not limited to, organic solvents such as methyl ethyl ketone, acetone, acetylacetone, ethyl acetate, tetrahydrofuran, cyclohexanone, n-hexane, toluene, xylene, etc., which may be used alone or in combination.
The adhesive composition of the present invention may further comprise a silane coupling agent for adjusting adhesion, for example, a silicon compound having an epoxy group structure, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, or 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, may be used.
The adhesive composition of the present invention may further optionally contain additives commonly used in the art, such as antistatic agents, UV absorbers, antioxidants, plasticizers, fillers, colorants or pigments, and the like.
The (meth) acrylate adhesive composition of the present invention may be applied to a substrate to a predetermined thickness by, for example, roll coating, doctor blade coating, dip coating, roll coating, slit coating, drying, and curing to form an adhesive layer having adhesive properties. The adhesive layer provides improved initial adhesion, good weatherability and reworkability when used to adhere a polarizer and a display panel.
The following examples are intended to further illustrate the invention, the subject of which is not intended to be limiting.
Examples
Preparation example 1: preparation of siloxane copolymers I
90 parts by weight of n-butyl acrylate, 90 parts by weight of methyl acrylate, 20 parts by weight of 3-methacryloxypropyltrimethoxysilane (KBM-503, available from Kyowa chemical industry, Japan), 1 part by weight of n-dodecylmercaptan, 216 parts by weight of ethyl acetate and 59 parts by weight of butyl acetate were mixed, and then nitrogen gas was introduced to remove oxygen to form a solution A. 1.6 parts by weight of Azobisisoheptonitrile (ADVN), 24 parts by weight of ethyl acetate and 1 part by weight of butyl acetate are mixed and heated to 90 ℃ to be added into the solution A, after the reaction is completed, the solid content of the reaction product is 40 percent, and the siloxane copolymer I with the weight average molecular weight of 64,000 and the glass transition temperature of-36.19 ℃ is prepared.
Preparation example 2: preparation of siloxane copolymers II
After 50 parts by weight of n-butyl acrylate, 50 parts by weight of ethyl acrylate, 30 parts by weight of 3-methacryloxypropyltrimethoxysilane (KBM-503) and 90 parts by weight of methyl ethyl ketone were mixed, nitrogen gas was introduced to remove oxygen to form a solution B. 0.3 part by weight of Azobisisobutyronitrile (AIBN) and 20 parts by weight of butanone are mixed and heated to 85 ℃, then the solution B is added, after the reaction is completed, the reaction product is diluted by ethyl acetate to form a solid content of 50 percent, and the siloxane copolymer II with the weight average molecular weight of 133,600 and the glass transition temperature of-32.48 ℃ is obtained.
Preparation example 3: preparation of siloxane copolymer III
Siloxane copolymer III was prepared as in preparation 2, but using 20 parts by weight of 3-methacryloxypropyltrimethoxysilane and 78 parts by weight of methyl ethyl ketone to give siloxane copolymer III having a weight average molecular weight of 118,600 and a glass transition temperature of-30.41 ℃.
Preparation example 4: preparation of siloxane copolymer IV
Silicone copolymer IV was prepared as in preparation 2, but using 10 parts by weight of 3-methacryloxypropyltrimethoxysilane and 70 parts by weight of methyl ethyl ketone produced a silicone copolymer IV having a weight average molecular weight of 117,000 and a glass transition temperature of-30.71 ℃.
Example 1: preparation of adhesive composition
72 parts by weight of n-butyl acrylate, 30 parts by weight of methyl acrylate, 5 parts by weight of vinyl acetate, 1 part by weight of acrylic acid, 0.5 part by weight of 2-hydroxyethyl methacrylate (2-HEMA) and ethyl acetate were mixed. After the mixed solution was deaerated by introducing nitrogen gas for 0.5 hour, 0.5 part by weight of Azobisisobutyronitrile (AIBN) was added to react. After the reaction was completed, the reaction mixture was diluted with Ethyl Acetate (EAC) to obtain a (meth) acrylate resin having a solid content of 30%, a weight-average molecular weight of 954,000 and a glass transition temperature of-24.59 ℃.
To 100 parts by weight of the obtained acrylic resin solution were added 7 parts by weight of an isocyanate crosslinking agent (D-262, available from Mitsui chemical Co., Ltd., Japan), 2 parts by weight of aluminum acetylacetonate (CA190T, available from Xinxing, Taiwan, China), 1.5 parts by weight of bisphenol F diglycidyl ether (EPALLOY 8820, available from CVC Thermoset Specialties, USA), 0.05 parts by weight of a silane coupling agent (KR516, shiner chemical, Japan) and 0.23 parts by weight of the siloxane copolymer I prepared in preparation example 1, and the mixture was uniformly mixed to obtain a (meth) acrylate adhesive composition.
The prepared (methyl) acrylate adhesive composition is coated on a release film and is put into a 95 ℃ oven for drying, and an adhesive layer with the thickness of 20 micrometers (mum) is obtained. The adhesive layer was attached to one surface of the polarizer, and after aging for 5 days in a room temperature environment, adhesion and weather resistance tests were performed according to the following test methods, and the test results are shown in table 1.
Measuring the adhesive force: and cutting the polarizer into the size of 25mm x 200mm, removing the release film, and attaching the polarizer to the glass substrate. The test specimens were respectively subjected to adhesion, standing at room temperature for 7 days, standing at 60 ℃ for 4 hours, and standing at 60 ℃ and 90% Relative Humidity (RH) for 24 hours, and then the adhesion was measured at an angle of 180 ℃ with a 2Kg roller at a tensile rate of 300mm/min in accordance with JIS Z0237 test method. In addition, the adhesion test after the test sample is left to stand at room temperature for 7 days can be regarded as a rework property measurement.
Weather resistance judgment: the polaroid is cut into the size of 312.4mm x 176.95mm, and the glass substrate is attached after the release film is removed. The test sample was left to stand at 60 ℃/90% RH for 500 hours, and then it was observed whether or not the adhered polarizer was peeled from the glass substrate, and if no defective appearance such as foaming, peeling, or cracking was observed, the sample was rated as o, and if no defective appearance such as foaming, peeling, or cracking was observed, the sample was rated as X.
Table 1: test results of adhesive composition of example 1
As is apparent from Table 1, the (meth) acrylate adhesive composition of example 1 had an appropriate initial adhesion and the adhesion was stably maintained after 7 days, meeting the rework requirement. Further, the (meth) acrylate adhesive composition of example 1 has good adhesion even after passing through a high temperature and high humidity environment, and has high temperature and high humidity resistance without defects after being stored for 500 hours under a high temperature and high humidity environment.
Example 2: preparation of (meth) acrylate adhesive composition
Mixing 65 parts by weight of n-butyl acrylate, 15 parts by weight of methyl acrylate, 20 parts by weight of 2-phenoxyethyl acrylate (2-PHEA), 2 parts by weight of acrylic acid, 1 part by weight of 2-hydroxyethyl methacrylate (2-HEMA) and 150 parts by weight of Ethyl Acetate (EAC), introducing nitrogen to remove oxygen, heating to 65 ℃, and adding 0.6 part by weight of 2,2' -Azobisisobutyronitrile (AIBN) for reaction. After completion of the reaction, the reaction mixture was diluted with ethyl acetate to a solid content of 20% to obtain an acrylic polymer having a weight average molecular weight of 1,450,000 and a glass transition temperature of-22 ℃.
To 100 parts by weight of the acrylic polymer thus obtained, 0.20 part by weight of tolylene diisocyanate-trimethylolpropane (TDI-TMP) (AD75, available from SAPICI SpA, Italy), 0.3 part by weight of an epoxy-based crosslinking agent (Tetrad-C, available from Mitsubishi gas corporation, Japan) and 0.09 part by weight of the silicone copolymer III prepared in preparation example 3 were added, and mixed and reacted to obtain a (meth) acrylate adhesive composition.
The prepared (meth) acrylate adhesive composition was coated on a release film, and dried in an oven at 95 ℃ to obtain an adhesive layer having a thickness of 25 micrometers (μm). The adhesive layer was attached to one surface of the polarizer, and after aging at room temperature for 5 days, adhesion and weather resistance were measured according to the test method of example 1, and the test results are shown in Table 2. But the test samples increased adhesion testing at room temperature for 14 days, 21 days, 28 days, and were instead tested after 16 hours of standing at 60 ℃/90% RH. The test results are shown in Table 2.
Example 3: preparation of (meth) acrylate adhesive composition
A (meth) acrylate adhesive composition was prepared as in example 2, but using 0.36 parts by weight of the siloxane copolymer II instead. The prepared (meth) acrylate adhesive composition was subjected to the test sample according to example 2, and the adhesion and weather resistance test according to the test method of example 2, and the test results are shown in table 2.
Example 4: preparation of (meth) acrylate adhesive composition
A (meth) acrylate adhesive composition was prepared as in example 2, except that 0.36 parts by weight of the silicone copolymer III was used. The prepared (meth) acrylate adhesive composition was subjected to the test sample according to example 2, and the adhesion and weather resistance test according to the test method of example 2, and the test results are shown in table 2.
Example 5: preparation of (meth) acrylate adhesive composition
A (meth) acrylate adhesive composition was prepared as in example 2, except that 0.36 parts by weight of the silicone copolymer IV was used instead. The prepared (meth) acrylate adhesive composition was subjected to the test sample according to example 2, and the adhesion and weather resistance test according to the test method of example 2, and the test results are shown in table 2.
Comparative example 1
An acrylic resin was prepared in the same manner as in example 2, and 100 parts by weight of the obtained acrylic resin, 0.20 parts by weight of tolylene diisocyanate-trimethylolpropane (TDI-TMP) (AD75), 0.3 parts by weight of an epoxy-based crosslinking agent (Tetrad-C), 0.1 parts by weight of a silane additive (KBM-403, available from shin-Etsu chemical Co., Ltd., Japan) and 0.05 parts by weight of a silane additive (KBM-503) were uniformly mixed to obtain a (meth) acrylate adhesive composition.
The prepared (meth) acrylate adhesive composition was subjected to the test sample according to example 2, and the adhesion and weather resistance test according to the test method of example 2, and the test results are shown in table 2.
Table 2: results of adhesion test of examples 2 to 5 and comparative example 1
As is apparent from Table 2, the (meth) acrylate adhesive compositions of examples 2 to 5 are superior to comparative example 1 in initial adhesion, and show that the adhesion tends to be stable over time from 7 days to 28 days, which is advantageous in improving reworkability. The (meth) acrylate adhesive compositions of examples 2 to 5 maintained stable adhesion even after passing through a high temperature and high humidity environment, and had high temperature and high humidity resistance without defects after passing through a high temperature and high humidity environment for 500 hours. The initial adhesion of comparative example 1 was low, but the adhesion rapidly increased with time, increasing the difficulty of reworking.
Example 6: preparation of (meth) acrylate adhesive composition
50 parts by weight of n-butyl acrylate, 50 parts by weight of 2-isobutyl acrylate, 10 parts by weight of methyl acrylate, 5 parts by weight of acrylic acid, 1 part by weight of 2-hydroxyethyl methacrylate (2-HEMA) and 66.7 parts by weight of Ethyl Acetate (EAC) are mixed, nitrogen is introduced to remove oxygen, the temperature is raised to 85 ℃, and 0.1 part by weight of Azobisisobutyronitrile (AIBN) is added for reaction. After completion of the reaction, the reaction mixture was diluted with ethyl acetate to a solid content of 30% to obtain a (meth) acrylate polymer having a weight average molecular weight of 878,000 and a glass transition temperature of-35.85 ℃.
To 100 parts by weight of the (meth) acrylate polymer obtained above were added 0.3 part by weight of tolylene diisocyanate-trimethylolpropane (TDI-TMP) (AD75), 0.2 part by weight of zirconium metal chelate complex (K-KAT4205, available from King industries, USA) and 3 parts by weight of siloxane copolymer II of preparation example 2, and mixed and reacted to obtain a (meth) acrylate adhesive composition.
The (meth) acrylate adhesive composition prepared as described above is used to prepare an optical laminate film for a flexible display. The optical laminate film was a 33 μm polarizing film, a 2 μm first optical compensation film and a 2 μm second optical compensation film in this order, and they were laminated with the 5 μm (meth) acrylate adhesive composition prepared above. The optical laminate was further laminated to a 38 micrometer (μm) thick polyester film (replacing the electro-optic portion of the display) and subjected to static bending and dynamic bending tests as described below.
Storage modulus (G '), loss modulus (G') and loss factor (tan) measurements
The protective cover sheet laminate film prepared in the preceding example was cut into a size of 10mm x 8mm as a measurement sample. At a frequency of 0.1/1Hz and a temperature range of
The dynamic viscoelasticity test of the test sample was measured using a Rheogel-E4000 manufactured by UBM corporation at a temperature rise rate of 3 deg.C/minute, and the storage modulus (G ') and loss modulus (G') and loss factor (tan) at 30 deg.C and 80 deg.C were read based on the test results.
Static bending test
The bonded test specimen was cut into a rectangular specimen of 10mm × 120mm, the short sides of the specimen were fixed with tapes, and the specimen was mounted on a tensionless U-fold testing machine (under the instrument name DLDMLH-FS, manufactured by Yuasa System corporation) with a minimum interval of 2 sides of the durability testing machine set to 4mm, an outer diameter (Φ) of the machine-bending portion set to 4mm, and a radius (R) set to 2 mm. The samples were subjected to static inner and outer bending tests, i.e., the samples were subjected to an inner bending test with the facing of the polarizing film and an outer bending test with the facing of the polyester film. The test conditions were standing at room temperature for 7 days, and after 7 days, the rebound angle of the sample after spreading with the plane was measured, very good: below 30 degrees; o: 30 degrees to 39 degrees; and (delta): 40 degrees to 49 degrees; x: above 50 deg. The results are reported in table 3.
Dynamic internal bending test
The bonded test sample was cut into a rectangular sample of 10mm × 120mm, the short sides of the sample were fixed with tapes, the sample was mounted on a tensionless U-fold tester (under the instrument name DLDMLH-FS, Yuasa System), the outer diameter (Φ) of the bend of the tester was set to 4mm, the radius (R) was set to 2mm, the sample was subjected to a dynamic bending test of 180 ° for 20 ten thousand folds with the polarizing film facing each other, and the test was evaluated as o if the bend had not been broken or cracked and as x if the bend had been broken or cracked.
Dynamic overbending test
The bonded test sample was cut into a rectangular sample of 10mm × 120mm, the short sides of the sample were fixed with tapes, the sample was mounted on a tensionless U-fold tester (equipment name DLDMLH-FS, manufactured by Yuasa systems), the outer diameter (Φ) of the bend of the tester was set to 6mm, the radius (R) was set to 4mm, the sample was subjected to a dynamic bending test of 180 ° for 20 ten thousand folds with the polyester film facing each other, and it was examined whether or not a crack or a crack occurred in the bend, and if no crack or a crack occurred in the bend, the test sample was evaluated as (good), and if a crack or a crack occurred in the bend, the test sample was evaluated as (x).
Example 7: preparation of (meth) acrylate adhesive composition (OCA-2B TEST EXAMPLE 4)
A (meth) acrylate polymer was prepared in the same manner as in example 6, and to 100 parts by weight of the prepared (meth) acrylate polymer were added 0.3 part by weight of the amount of tolylene diisocyanate-trimethylolpropane (AD75), 0.2 part by weight of zirconium metal chelate complex (K-KAT4205, available from King Industries, USA), and 6 parts by weight of the silicone copolymer II of preparation example 2, followed by mixing and reaction to obtain a (meth) acrylate adhesive composition.
The (meth) acrylate adhesive composition prepared as described above was subjected to the property test as in example 6, and the results are shown in Table 3.
Table 3: results of Property testing of examples 6 and 7
The results in table 3 show that the acrylate adhesive composition of the present invention shows good adhesion in both static bending and dynamic bending tests, and can recover to a low spring back angle after the static bending test, and shows stable recovery, so that it can be applied to electronic products requiring bending function.
In summary, the present invention discloses a (meth) acrylate adhesive composition for bonding an optical film to a substrate, comprising a (meth) acrylate polymer, a crosslinking agent, and a siloxane copolymer, wherein the siloxane copolymer comprises an acrylic monomer and a silane compound. The siloxane copolymer of the (meth) acrylate adhesive composition of the present invention has an acrylic monomer which is polar-compatible with the acrylic component of the (meth) acrylate adhesive composition and a silane compound which can enhance the adhesion with the substrate, can improve the initial adhesion and weather resistance of the (meth) acrylate adhesive composition, and does not rapidly climb over time, and thus can have the rework properties required for the process. In addition, when used in an adhesive for flexible display devices, it can provide good flexibility without the problem of creep and has excellent adhesion.
The present invention has been described in relation to the above embodiments, which are only exemplary of the implementation of the present invention. It should be noted that the disclosed embodiments do not limit the scope of the invention. Rather, it is intended that all such modifications and variations be included within the spirit and scope of this invention.
Claims (12)
1. A (meth) acrylate adhesive composition comprising:
(meth) acrylate polymers;
a crosslinking agent; and
a siloxane copolymer, wherein the siloxane copolymer comprises 70 to 95 parts by weight of a monomer having C1To C4An alkyl acrylic monomer, and 5 to 30 parts by weight of a silane compound represented by the following formula (I):
X-R1-SiR2 3-a(OR3)a(I)
in the formula (I), X is acryloyl or (meth) acryloyloxy, R1Is C1To C8Alkyl or alkoxy of, R2And R3Each is C1To C4A is an integer of 1 to 3, and the weight average molecular weight of the siloxane copolymer is between 40,000 and 150,000;
wherein the siloxane copolymer is used in an amount of 0.2 to 25 parts by weight per hundred parts by weight of the (meth) acrylate polymer.
2. The (meth) acrylate adhesive composition according to claim 1 wherein the siloxane copolymer has a glass transition temperature between-22 ℃ and-40 ℃.
3. The (meth) acrylate adhesive composition according to claim 1, wherein the silane compound of formula (I) is 3-methacryloxypropyltrimethoxysilane.
4. The (meth) acrylate adhesive composition of claim 1 wherein the acrylic monomer comprises butyl acrylate monomer and at least one acrylate monomer selected from the group consisting of methyl acrylate monomer, ethyl acrylate monomer and propyl acrylate monomer.
5. The (meth) acrylate adhesive composition according to claim 4, wherein the butyl acrylate monomer and at least one acrylate monomer selected from the group consisting of methyl acrylate monomer, ethyl acrylate monomer and propyl acrylate monomer are used in a weight ratio of 1.5 to 0.6.
6. The (meth) acrylate adhesive composition according to claim 1 wherein the siloxane copolymer has a weight average molecular weight of between 50,000 and 140,000.
7. The (meth) acrylate adhesive composition according to claim 1 wherein the difference between the glass transition temperature of the (meth) acrylate polymer and the glass transition temperature of the siloxane copolymer is between 3 ℃ and 15 ℃.
8. The (meth) acrylate adhesive composition of claim 1 wherein the siloxane copolymer further comprises a chain transfer agent.
9. The (meth) acrylate adhesive composition of claim 1 wherein the (meth) acrylate polymer comprises a (meth) acrylate monomer and a crosslinkable monomer.
10. The (meth) acrylate adhesive composition according to claim 9, wherein the (meth) acrylate monomer in the (meth) acrylate polymer is 90 to 99.8 weight percent of the total weight of the (meth) acrylate monomer and the crosslinkable monomer, and the crosslinkable monomer in the (meth) acrylate polymer is 0.2 to 10 weight percent of the total weight of the (meth) acrylate monomer and the crosslinkable monomer.
11. The (meth) acrylate adhesive composition according to claim 10, wherein the (meth) acrylate monomer in the (meth) acrylate polymer is 94 to 99.5 weight percent of the total weight of the (meth) acrylate monomer and the cross-linkable monomer, and the cross-linkable monomer in the (meth) acrylate polymer is 0.5 to 6 weight percent of the total weight of the (meth) acrylate monomer and the cross-linkable monomer.
12. The (meth) acrylate adhesive composition according to claim 9 wherein the (meth) acrylate polymer further comprises a free radical reactive monomer in an amount of 0.5 to 10 parts by weight, relative to the total weight of the (meth) acrylate monomer and the crosslinkable monomer.
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| WO2021111995A1 (en) * | 2019-12-06 | 2021-06-10 | 大塚化学株式会社 | Adhesive material, adhesive sheet, and flexible laminate member |
| CN115353590A (en) * | 2022-08-30 | 2022-11-18 | 上海高邦印刷材料有限公司 | Preparation method of heat-resistant emulsion for water-based ink |
| TWI855956B (en) | 2024-01-15 | 2024-09-11 | 碁達科技股份有限公司 | (Meth)acrylate polymer having silyl groups |
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| JPS63291969A (en) * | 1987-05-23 | 1988-11-29 | Nitto Electric Ind Co Ltd | Repeelable tackifying agent |
| JPH02123182A (en) * | 1988-11-01 | 1990-05-10 | Nitto Denko Corp | Re-releasing-type tack agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021111995A1 (en) * | 2019-12-06 | 2021-06-10 | 大塚化学株式会社 | Adhesive material, adhesive sheet, and flexible laminate member |
| JP6888181B1 (en) * | 2019-12-06 | 2021-06-16 | 大塚化学株式会社 | Adhesive material, adhesive sheet and flexible laminated member |
| CN115353590A (en) * | 2022-08-30 | 2022-11-18 | 上海高邦印刷材料有限公司 | Preparation method of heat-resistant emulsion for water-based ink |
| CN115353590B (en) * | 2022-08-30 | 2024-04-26 | 上海高邦印刷材料有限公司 | Preparation method of heat-resistant emulsion for water-based ink |
| TWI855956B (en) | 2024-01-15 | 2024-09-11 | 碁達科技股份有限公司 | (Meth)acrylate polymer having silyl groups |
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