阅读说明：本技术 (甲基)丙烯酸酯官能化的聚(甲基)丙烯酸酯-嵌段-聚酰亚胺-嵌段-聚(甲基)丙烯酸酯共聚物、其制备方法和用途 ((meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymers, method for the production thereof and use thereof ) 是由 施朱明 陆琤 欧阳江波 于 2017-04-21 设计创作，主要内容包括：本发明涉及(甲基)丙烯酸酯官能化的聚(甲基)丙烯酸酯-嵌段-聚酰亚胺-嵌段-聚(甲基)丙烯酸酯共聚物、其制备方法和用途。根据本发明的(甲基)丙烯酸酯官能化的聚(甲基)丙烯酸酯-嵌段-聚酰亚胺-嵌段-聚(甲基)丙烯酸酯共聚物表现出优异的热稳定性和优异的光学性能。(The present invention relates to (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymers, methods for their preparation and uses thereof. The (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer according to the present invention exhibits excellent thermal stability and excellent optical properties.)

A (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer represented by formula I:

in formula (I), m and n each independently represent an integer of from about 1 to about 50, provided that m and n are not simultaneously 1;

R1 and R14, equal to or different from each other, are independently hydrogen or methyl;

R2 is selected from C1-C12 alkyl;

r3 is-CH (CH3) -or-C (CH3) 2-;

R4 is selected from C1-C12 alkylene;

R5 represents a divalent linking unit selected from the group consisting of C6-C30 cycloaliphatic and C6-C30 arylene; and is

a represents a tetravalent linking unit selected from the group consisting of C4-C14 aliphatic groups, C4-C30 cycloaliphatic groups, C6-C30 aryl groups, ether groups, sulfone groups, sulfide groups, amide groups, and ester groups.

2. The copolymer of claim 1, wherein R2 is selected from C1-C6 alkyl.

3. The copolymer of claim 1 or 2, wherein R4 is selected from C1-C6 alkylene.

4. The copolymer of any preceding claim, wherein a is selected from the group consisting of:

Wherein R6 is a divalent linking unit, preferably, R6 is located at the 3,3'-, 3,4' -, 4,3 '-or 4,4' -position of the phenyl ring,

More preferably, R6 is selected from the group consisting of-O-, -S-, -C (O) -, -SO2-, -SO-, C1-C20 alkylene, halogenated C1-C20 alkylene (including C1-C20 perfluoroalkylene), and a group represented by-O-Z-O-, wherein Z is a divalent linking group selected from the group consisting of:

Wherein R7 is selected from the group consisting of-O-, -S-, -C (O) -, -SO2-, -SO-, C1-C20 alkylene, and halogenated C1-C20 alkylene (including C1-C20 perfluoroalkylene).

5. the copolymer of any one of the preceding claims, wherein R5 is selected from the group consisting of:

wherein R8 through R13 are each independently selected from C1-C20 alkylene groups and halogenated derivatives thereof, including C1-C20 perfluoroalkylene groups.

6. The copolymer of any one of the preceding claims, wherein the copolymer is represented by any one of formula II to formula IV:

Wherein R1 to R4, R6, R10, R11, R14, m and n are each as defined in any one of claims 1 to 5.

7. Copolymer according to any of the preceding claims, having a number average molecular weight Mn, measured by GPC, of 2,000-1,000,000 dalton, preferably 10,000-500,000 dalton, more preferably 15,000-300,000 dalton.

8. the copolymer of any of the preceding claims, wherein the number ratio of the polyimide blocks to the poly (meth) acrylate blocks, m:2n, is from 1:1 to 1: 100.

9. A method of making the (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer of any of claims 1-8, comprising:

-reacting a diamine, a dianhydride and a monoamine to form a polyamic acid according to scheme 1;

-dehydrating the polyimide acid to form a polyimide;

-reacting the polyimide with a (meth) acrylate to form a bromine terminated poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer represented by formula V:

And

-reacting the bromine-terminated poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer with (meth) acrylic acid to form a (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer represented by formula I,

Wherein R1 to R5, R14, A, m and n are each as defined in any one of claims 1 to 4.

10. Photocurable adhesive composition comprising a copolymer according to any of claims 1-8, wherein the adhesive composition is preferably a liquid optically clear adhesive.

11. The adhesive composition of claim 10, further comprising a (meth) acrylate monomer and/or a photoinitiator.

12. the adhesive composition of claim 11, wherein the (meth) acrylate monomer is monofunctional or difunctional.

13. The adhesive composition of claim 11 or 12, wherein the photoinitiator is selected from the group consisting of benzoin ether photoinitiators, benzil ketal photoinitiators, acetophenone photoinitiators, anthraquinone photoinitiators, thioxanthone photoinitiators, benzophenone photoinitiators, acylphosphine oxide photoinitiators, and benzoate photoinitiators, and any combination thereof.

14. Use of the adhesive composition according to any one of claims 10-13 for bonding substrates, wherein the substrate is preferably glass or transparent plastic.

Technical Field

The present invention relates to (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymers, methods for their preparation and uses thereof. The (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer according to the present invention exhibits excellent thermal stability and excellent optical properties.

background

polyimides are known to have good thermal stability, chemical resistance, mechanical properties, and the like. However, the use of polyimides in adhesives is limited due to their low solubility, poor compatibility with the usual components of the adhesive, high melting point and extreme difficulties in processing.

Many studies have been conducted to change the thermal and mechanical properties of polyimides. For example, Fu-Ming Wang et al synthesized poly (acrylate-co-imide) -based gel polymer electrolytes. See "The network gel polymer based on poly (acrylate-co-imide) and bits transport properties in lithium ion batteries", J Solid State Electrochem (2009)13: 1425-. Those gel polymers based on poly (acrylate-co-imide) are graft polymers. These graft polymers are insoluble in most organic solvents. In addition, the bond between the imide moiety and the acrylate moiety is weak, which may impair the thermal stability of the graft polymer.

Despite the prior art, there is still a need to develop new adhesive materials that exhibit both good thermal stability and good optical properties.

disclosure of Invention

As a result of intensive research, the present inventors have developed a novel (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer represented by formula I:

In formula (I), m and n each independently represent an integer of 1 to about 50, provided that m and n are not simultaneously 1;

R1 and R14, equal to or different from each other, are independently hydrogen or methyl;

R2 is selected from C1-C12 alkyl;

R3 is-CH (CH3) -or-C (CH3) 2-;

R4 is selected from C1-C12 alkylene;

R5 represents a divalent linking unit selected from the group consisting of C6-C30 cycloaliphatic and C6-C30 arylene; and is

A represents a tetravalent linking unit selected from the group consisting of C4-C14 aliphatic groups, C4-C30 cycloaliphatic groups, C6-C30 aryl groups, ether groups, sulfone groups, sulfide groups, amide groups, and ester groups.

The invention also relates to a process for preparing the copolymers according to the invention.

The invention also relates to a photocurable adhesive composition comprising a copolymer according to the invention.

the invention also relates to the use of the adhesive composition according to the invention for bonding substrates.

Drawings

additional features and advantages of the present disclosure will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the technical features; and, wherein:

FIG. 1 compares the UV-VIS transmission-wavelength plots for copolymers prepared according to examples of the present invention and comparative examples.

FIG. 2 compares the thermogravimetric analysis (TGA) curves of copolymers prepared according to examples of the present invention and comparative examples.

figures 3 through 5 each show a thermogravimetric analysis (TGA) profile of a copolymer prepared according to an example of the present invention.

FIG. 6 shows a thermogravimetric analysis (TGA) curve of a copolymer prepared according to the comparative example.

Reference will now be made to some illustrative examples, and specific language will be used herein to describe the same. It will nevertheless be understood that no limitation of the scope of the disclosure is thereby intended.

Detailed Description

In the following paragraphs, the present disclosure is described in more detail. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.

In the context of the present disclosure, the terms used should be construed according to the following definitions, unless the context indicates otherwise.

as used herein, the singular forms "a", "an" and "the" include both singular and plural referents unless the context clearly dictates otherwise.

as used herein, the terms "comprising," "comprises," and "comprising" are synonymous with "including," or "containing," and are inclusive or open-ended and do not exclude additional, unrecited elements, components, or method steps.

in the specification, the term "(meth) acrylate" means both or one of acrylate and methacrylate, the term "(meth) acrylic acid" means both or one of acrylic acid and methacrylic acid, and the term "poly (meth) acrylate" means both or one of polyacrylate and polymethacrylate.

The recitation of numerical endpoints includes all numbers and fractions subsumed within the corresponding range, as well as the recited endpoints.

All references cited in this specification are incorporated herein by reference in their entirety.

Unless otherwise defined, all terms, including technical and scientific terms, used in the present disclosure have the meaning commonly understood by one of ordinary skill in the art to which this disclosure belongs. By way of further guidance, definitions of terms are included herein to better understand the teachings of the present disclosure.

all materials and reagents used in the present disclosure are commercially available unless otherwise indicated.

(meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymers

In one aspect, the present invention provides a (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer represented by formula I:

In formula (I), m and n each independently represent an integer of from about 1 to about 50, provided that m and n are not simultaneously 1;

R1 and R14, equal to or different from each other, are independently hydrogen or methyl;

R2 is selected from C1-C12 alkyl, preferably, R2 is selected from C1-C6 alkyl;

R3 is-CH (CH3) -or-C (CH3) 2-;

R4 is selected from C1-C12 alkylene, preferably, R4 is selected from C1-C6 alkylene;

R5 represents a divalent linking unit selected from the group consisting of C6-C30 cycloaliphatic and C6-C30 arylene; and is

A represents a tetravalent linking unit selected from the group consisting of C4-C14 aliphatic groups, C4-C30 cycloaliphatic groups, C6-C30 aryl groups, ether groups, sulfone groups, sulfide groups, amide groups, and ester groups.

it was surprisingly found that the (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymers according to the present invention exhibit excellent thermal stability and excellent optical properties. In addition, the block copolymer is soluble in various solvents and monomers, easy to process, and compatible with common components of adhesives such as (meth) acrylic resins.

Without being bound by any theory, it is believed that the polyimide block of the block copolymer according to the present invention imparts excellent thermal stability to the (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer. The (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer further exhibits excellent optical properties by modifying the polyimide block and end groups with a (meth) acrylate. The (meth) acrylate block also imparts good flexibility to the copolymer, which in turn significantly improves the solubility, compatibility, and processability of the copolymer.

The term "aliphatic radical" as used herein refers to a linear or branched, substituted or unsubstituted hydrocarbon chain that is fully saturated or contains one or more units of unsaturation, but is not aromatic. Suitable aliphatic groups include, but are not limited to, linear or branched, substituted or unsubstituted alkyl, alkenyl, and alkynyl groups. In some embodiments, aliphatic groups contain 1 to 20 carbon atoms. The aliphatic group may be optionally substituted with, for example, halogen, alkyl, alkenyl, cycloalkyl, nitro, hydroxyl, amino, alkylamino, alkoxy, alkylthio, or acyl.

The term "alkyl" refers to a saturated linear or branched, substituted or unsubstituted monovalent hydrocarbon group, wherein the alkyl group may be optionally substituted with, for example, halogen, alkyl, alkenyl, cycloalkyl, nitro, hydroxy, amino, alkylamino, alkoxy, alkylthio, or acyl. In some embodiments, the alkyl group has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. Some non-limiting examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like.

The term "alkylene" refers to a saturated divalent hydrocarbon radical derived from a linear or branched saturated hydrocarbon by removal of two hydrogen atoms, wherein the alkylene radical may be optionally substituted with, for example, halogen, alkyl, alkenyl, cycloalkyl, nitro, hydroxy, amino, alkylamino, alkoxy, alkylthio, or acyl. In some embodiments, the alkylene group has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. Some non-limiting examples of alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, and the like.

the term "alkenyl" refers to a linear or branched monovalent hydrocarbon radical having at least one carbon-carbon unsaturated double bond site, wherein the alkenyl radical may be optionally substituted. In some embodiments, alkenyl groups have 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms. Non-limiting examples of suitable alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, and the like.

the term "alkynyl" refers to a linear or branched monovalent hydrocarbon radical having at least one carbon-carbon triple bond site of unsaturation, wherein the alkynyl radical may be optionally substituted. In some embodiments, alkynyl groups have 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms. Non-limiting examples of suitable alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecylynyl, dodecynyl, and the like.

The term "alicyclic" refers to a monovalent or polyvalent non-aromatic, saturated or partially unsaturated ring in the form of a monocyclic or polycyclic (e.g., bicyclic and tricyclic) ring system. Suitable alicyclic groups include, but are not limited to, cycloalkyl, cycloalkenyl, and cycloalkynyl. The cycloaliphatic group may be optionally substituted with, for example, halogen, alkyl, alkenyl, cycloalkyl, nitro, hydroxy, amino, alkylamino, alkoxy, alkylthio, or acyl.

The term "cycloalkyl" refers to an optionally substituted saturated ring system having from 3 to 30 ring carbon atoms, more preferably from 4 to 30 ring carbon atoms. Exemplary monocyclic cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

The term "cycloalkenyl" as used herein refers to cyclic aliphatic hydrocarbon groups having one or more carbon-carbon unsaturated double bonds. In one embodiment cycloalkenyl groups have from 3 to 30 carbon atoms, more preferably from 4 to 30 ring carbon atoms in the ring system.

The term "cycloalkynyl" as used herein refers to a cyclic aliphatic hydrocarbon group having one or more carbon-carbon triple unsaturated bonds. In one embodiment, cycloalkynyl has from 3 to 30 carbon atoms, more preferably from 4 to 30 ring carbon atoms, in the ring system.

the term "aryl" refers to an optionally substituted C6-C30 arene moiety containing 1-3 aromatic rings. Specific examples of such groups include, but are not limited to, phenyl, tolyl, xylyl, and naphthyl, particularly phenyl or naphthyl. Aryl groups may be optionally substituted with, for example, halogen, alkyl, alkenyl, cycloalkyl, nitro, hydroxy, amino, alkylamino, alkoxy, alkylthio, or acyl.

the term "arylene" as used herein denotes an aryl system as described herein, but having two points of attachment to the rest of the molecule.

in some embodiments, a is selected from the following groups:

Wherein R6 is a divalent linking unit, preferably, R6 is located at the 3,3'-, 3,4' -, 4,3 '-or 4,4' -position of the phenyl ring,

More preferably, R6 is selected from the group consisting of-O-, -S-, -C (O) -, -SO2-, -SO-, C1-C20 alkylene, halogenated C1-C20 alkylene (including C1-C20 perfluoroalkylene), and a group represented by-O-Z-O-, wherein Z is a divalent linking group selected from the group consisting of:

Wherein R7 is selected from the group consisting of-O-, -S-, -C (O) -, -SO2-, -SO-, C1-C20 alkylene, and halogenated C1-C20 alkylene (including C1-C20 perfluoroalkylene);

Even more preferably, R6 is selected from C1-C12 alkylene and halo C1-C12 alkylene, e.g., C1-C12 perfluoroalkylene.

The term "halo" as used herein refers to fluoro, chloro, bromo, iodo or any combination thereof.

In some embodiments, R5 is selected from the following groups:

Wherein R8 through R13 are each independently selected from C1-C20 alkylene groups and halogenated derivatives thereof, including C1-C20 perfluoroalkylene groups; C1-C12 alkylene and its halogenated derivatives, e.g. C1-C12 perfluoroalkylene, are preferred.

In some examples, the block copolymer according to the present invention is represented by any one of formula II to formula IV:

Wherein R1 to R4, R6, R10, R11, R14, m and n are each as defined above for formula I.

in some embodiments, R4 is C1-C12 alkylene, preferably C1-C6 alkylene, more preferably n-hexylene (- (CH2) 6-). In some embodiments, R6 and R11 are each independently C1-C20 perfluoroalkylene, preferably C1-C12 perfluoroalkylene, and more preferably hexafluoroisopropylidene (-C (CF3) 2-). In some embodiments, R10 is C1-C12 alkylene, preferably C1-C6 alkylene, more preferably methylene (-CH 2-).

In some embodiments, the block copolymers according to the present invention have a number average molecular weight (Mn) as measured by GPC of from about 2,000 to about 1,000,000 daltons, preferably from about 10,000 to about 500,000 daltons, more preferably from about 15,000 to about 300,000 daltons.

In some embodiments, the block copolymers according to the present invention have a polydispersity index (PDI) of about 1.1 to about 2.0, preferably about 1.2 to about 1.6.

In some embodiments, the block copolymer according to the present invention is in the form of a solid powder or a bulk solid (bulk solid). In some embodiments, the copolymer is white.

In some embodiments, the functionality of the block copolymer is from about 1.0 to about 2.0. The functionality of the copolymer refers to the number of unsaturated double bonds in the backbone of the block copolymer.

Process for preparing (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymers

In another aspect, the present invention provides a method of making a (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer according to the present invention, comprising:

-reacting a diamine, a dianhydride and a monoamine to form a polyamic acid (polyaminoacid) according to scheme 1;

-dehydrating the polyimide acid (polyimic acid) to form a polyimide;

-reacting the polyimide with a (meth) acrylate to form a bromine terminated poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer represented by formula V:

And

-reacting the bromine-terminated poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer with (meth) acrylic acid to form a (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer represented by formula I,

Wherein R1 to R5, R14, A, m and n each have the same definitions and preferred ranges as described for formula I.

in some embodiments, the (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer is synthesized by single electron transfer-living radical polymerization (SET-LRP reaction). By adjusting the feed ratio of the dianhydride monomer to the (meth) acrylate monomer, the number ratio of the polyimide block to the poly (meth) acrylate block and the chain length of the entire copolymer can be controlled. Further, the PDI of the poly (meth) acrylate moiety in the (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer can be precisely controlled to about 1.01 to about 1.2, preferably about 1.05 to about 1.1, by the SET-LRP reaction.

Photocurable adhesive composition

In another aspect, the present invention provides a photocurable adhesive composition comprising a copolymer according to the invention, wherein the adhesive composition is preferably a liquid optically clear adhesive composition.

In addition to the (meth) acrylate-functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer, the adhesive composition also includes a (meth) acrylate monomer and/or a photoinitiator.

in some embodiments, the (meth) acrylate monomer is monofunctional or difunctional.

in some embodiments, the (meth) acrylate ester monomers include, but are not limited to, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and mixtures thereof, Carboxymethyl diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoro (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-methoxy polyethylene glycol (meth) acrylate, 2, 2-trifluoroethyl (meth) acrylate, 2, 2-2, Dicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, 1, 4-butanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, di (meth), Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene oxide addition bisphenol a di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, cyclopentadiene distearate (meth) acrylate, 1, 3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified isocyanuric acid di (meth) acrylate, carbonate glycol di (meth) acrylate, and the like. Examples of commercially available (meth) acrylate monomers include, for example, EB230, EB264, EB265, EB284, EB280, EB1290, EB270, EB4833, EB8210, EB8402, EB8808 (aliphatic urethane acrylates), EB220, EB4827, EB4849 (aromatic urethane acrylates), EB657, EB885, EB600, EB3200, EB3700, EB3702, EB3703, EB3720(Daicel Cytec co., Ltd.); CN8000NS, CN8001NS, CN8003, CN9001NS, CN9002, CN9014NS, CN991NS (urethane acrylate), CN146, CN2203NS, CN2254NS, CN2261, CN2302, CN293, CN3108, CN704, CN8200 (polyester acrylate), CN104NS, CN120NS, CN131NS, CN2003NS, CN159 (epoxy acrylate, available from Sartomer), and the like.

In some embodiments, the photoinitiator is selected from the group consisting of benzoin ether photoinitiators, benzil ketal photoinitiators, acetophenone photoinitiators, anthraquinone photoinitiators, thioxanthone photoinitiators, benzophenone photoinitiators, acyl phosphine oxide photoinitiators, benzoate photoinitiators, and any combination thereof.

In some embodiments, the adhesive composition further comprises optional additives. There is no particular limitation on other optional additives that may be included in the composition, and additives commonly used in adhesives may be used. In some embodiments, other optional additives may include, but are not limited to, thermoplastic polymers, organic or inorganic fillers, thixotropic agents, silane coupling agents, diluents, modifiers, colorants such as pigments and dyes, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents, and the like. In particular, the adhesive composition preferably comprises an organic or inorganic filler and/or a thixotropic agent.

Fillers include, but are not limited to, inorganic fillers such as silica, diatomaceous earth, alumina, zinc oxide, iron oxides, magnesium oxide, tin oxides, titanium oxides, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite-activated clay, bentonite, aluminum nitride, silicon nitride, and the like; and organic fillers such as polymethyl methacrylate, polyethyl methacrylate, polypropylene methacrylate, polybutyl methacrylate, butyl acrylate-methacrylic acid-methyl methacrylate copolymer, polyacrylonitrile, polystyrene, polybutadiene, polypentadiene, polyisoprene, polyisopropylene, and the like. These fillers may be used alone or in combination.

thixotropic agents include, but are not limited to talc, fumed silica, ultra-fine surface treated calcium carbonate, fine particle alumina, platy alumina; layered compounds, such as montmorillonite; acicular compounds such as aluminum borate whiskers and the like. Among them, talc, fumed silica and fine-particle alumina are preferable.

in a further aspect, the present invention provides the use of an adhesive composition according to the invention for bonding substrates, wherein the substrate is preferably glass or transparent plastic.

in some embodiments, a method of bonding substrates comprises:

-applying the adhesive composition of the invention to the surface of a substrate;

-contacting the substrate having the adhesive composition applied thereon with a further substrate; and

-exposing the bonded substrate to actinic radiation.

The adhesive composition may be cured after exposure to actinic radiation, such as ultraviolet, visible, or black light radiation. In a preferred embodiment, the composition is cured using ultraviolet radiation having a wavelength of from about 200nm to about 450nm, preferably from about 300nm to about 450 nm. In another preferred embodiment, the ultraviolet radiation applied to the composition has a radiant energy of from about 100mJ/cm2 to about 10,000mJ/cm2, preferably from about 500mJ/cm2 to about 5,000mJ/cm 2. Preferably, the radiation source is substantially perpendicular to the substrate during curing.