Near-infrared (NIR) sensitized adhesives and sealant compositions

Abstract

The present invention comprises, based on the weight of the composition: a) Formula (I): TIFF2024509791000014.tif3777[In the formula, R 1 and R 2 is H, C1-C6 alkyl, C6-C 18 Aryl, or C7-C 18 It is aralkyl; Each R 3 are independent, C1-C 12 Alkylene group, C6-C 18 Arylene group, C2-C 12 alkenylene group, or poly(C1-C6 alkyleneoxy) group; and n is an integer from 1 to 3. at least one oxetane compound according to the present invention, 1 to 10% by weight; b) at least one epoxide compound, 5-20 wt.%, wherein component b) is characterized in that at least 50 wt.% of the total weight of the epoxide compounds is constituted by b1) at least one cycloaliphatic epoxide; c) at least one ionic photoacid generator, 0.1-5 wt.%; d) at least one free radical photoinitiator, 0-10 wt.%; e) at least one near infrared absorbing dye, 0.01 to 5% by weight; and f) Particulate filler, 50-90% by weight The present invention is directed to a light curable adhesive or sealant composition comprising:

Description

Technical Field

[0001] [Field of the Invention] The present invention relates to adhesive and sealant compositions that may have utility in optoelectronic and optomechanical devices. More particularly, the present invention relates to near-infrared (nIR) sensitized adhesive and sealant compositions based on oxetane and cycloaliphatic epoxide monomers.

Background Art

[0002] [Background of the Invention] Radiation curable materials have found utility as coating agents, adhesives, and sealants. Such applications have been driven in part by the generally low energy consumption of such materials during curing, and the rapid cure rate of the materials (even at low temperatures) by either a radical or cationic mechanism. Also, the materials are often formulated as solventless compositions, which may reduce the emission of volatile organic compounds during application. Due to these advantages, radiation curable materials are particularly suitable for the rapid adhesion and sealing (sealing) of electronic and optoelectronic devices that are temperature sensitive or cannot conveniently withstand long cure times. In particular, optoelectronic devices are often sensitive to heat and may require optical alignment and spatial immobilization by curing in a very short time.

[0003] Many optoelectronic devices are also sensitive to moisture or oxygen and need to be protected from exposure during their functional life. A common approach is to seal the device between an impermeable substrate and an impermeable glass or metal lid, and then use a radiation curable adhesive or sealant to seal or adhere the perimeter of the lid to the bottom substrate. An effective barrier sealant for this purpose exhibits low bulk moisture permeability, good adhesion, and strong interfacial adhesive-substrate interaction.

[0004] If the substrate-sealant interface is of poor quality, the interface can act as a weak boundary allowing moisture to penetrate the device, regardless of the sealant's bulk moisture permeability. If the interface is at least as continuous as the bulk sealant, moisture permeability is determined by the sealant's bulk moisture permeability itself. In practice, the curing matrix of adhesives or sealants for optoelectronic or optomechanical applications must have either high crosslinking density, microcrystalline properties, or dense packing of the molecular framework between the crosslinked portions of the matrix. The restricted molecular mobility of the matrix ensures low penetration mobility or diffusion rate.

[0005] It is customary in this art to focus on the glass transition temperature (Tg) of the cured material as a measure of its usefulness. Sealants and adhesives are formulated to produce Tg values ​​higher than necessary to ensure adequate tolerances. Indeed, meeting high Tg criteria may mean compromises, particularly with respect to tensile strength, lap shear strength, adhesive bond strength, and modulus of elasticity. However, apart from that, to meet such thermal criteria, it is important that curing is complete throughout the applied adhesive or sealant material, and in particular, that shadow curing effectively extends to areas of the applied material that are not illuminated by the incident starting light source. Insufficient curing in shadowed areas can expose components of optoelectronic devices to the risk of corrosion and can also have undesirable effects on the internal optical path. Therefore, to avoid the problem of insufficient shadow curing, adhesives or sealants are often formulated to exhibit thermosetting or moisture curing properties in addition to being radiation curable.

[0006] US 2008 / 272328 (Kong) discloses a cationic curable barrier composition for optoelectronic devices, the composition comprising essentially (a) an oxetane compound; (b) a cationic initiator; (c) optionally one or more fillers; and (d) optionally one or more adhesion promoters, or one or more epoxy resins. The amount of cationic initiator added does not determine the curing rate under chemical radiation. For the tested ratio of epoxy resin to oxetane in the disclosed composition, optimal curing conditions included temperatures above 130°C.

[0007] US2005061429 A1 (Hosaka) discloses a chemically radiation-curable adhesive comprising, based on the weight of the composition, 50–99 wt% of a bifunctional oxetane compound and / or a polyfunctional oxetane compound; 0–40 wt% of a monofunctional oxetane compound; 1–50 wt% of a cyclic epoxy compound; and a catalytic amount of a photopolymerization initiator. This cited document asserts only that the coated composition needs to be exposed to chemical radiation for complete curing. However, it should be noted that the gel point of the cured composition is at most 30 minutes at room temperature. This may be unsuitable for applications where the adhesive bond needs to cure more rapidly. In such cases, those skilled in the art will need to increase the curing temperature.

[0008] US2003062125 A1 (Takamatsu et al.) discloses a photocationically curable resin composition useful as a sealant for liquid crystal displays or electroluminescent displays, the composition comprising: (a) a cationic polymerizable compound; (b) a photocationic initiator; and (c) an aromatic ether compound or an aliphatic thioether compound. The exemplified composition is cured under irradiation with a high-intensity metal halide lamp, but complete conversion of the constituent monomers is not achieved.

[0009] DE102009012272A1 (Wellmann) discloses a double-curing adhesive for use in optomechanical and optoelectronic devices, the adhesive composition comprising: at least one monomer; a UV-curable adhesive component; at least one photopolymerization initiator; a component having a free isocyanate group or a component containing a free silane; and a primary, secondary, and / or tertiary amine. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] U.S. Patent Application Publication No. 2008 / 272328 [Patent Document 2] U.S. Patent Application Publication No. 2005061429 [Patent Document 3] U.S. Patent Application Publication No. 2003062125 [Patent Document 4] German Patent Application Publication No. 102009012272 Specification [Overview of the project] [Problems that the invention aims to solve]

[0011] The inventors believe there is a need in the art to provide a photocurable adhesive or sealant composition useful in optoelectronic devices, and that such a composition can be substantially cured without requiring a thermal curing step following irradiation with chemical rays. It would be desirable to develop a composition that does not exhibit a harmfully low glass transition temperature (Tg) when exposed to chemical ray irradiation alone. [Means for solving the problem]

[0012] [Detailed description of the invention] According to a first aspect of the present invention, based on the weight of the composition: a) The following equation (I): [ka] [In the formula, R 1 and R 2 H, C1-C6 alkyl, C6-C 18 Aryl, or C7-C 18 It is Aralquil; Each R 3 It is independently, C1-C 12 Alkylene group, C6-C 18 Arylene group, C2-C 12 It is an alkenylene group or a poly(C1-C6 alkylene oxy) group; and n is an integer between 1 and 3. At least one oxetane compound, 1-10% by weight; b) at least one epoxide compound, 5 to 20% by weight, wherein component b) is characterized in that at least 50% by weight of the total weight of the epoxide compound is composed of b1) at least one alicyclic epoxide; c) At least one ionic photoacid generator, 0.1-5% by weight; d) At least one free radical photoinitiator, 0-10% by weight; e) at least one near-infrared absorbing dye, 0.01 to 5% by weight; and f) Particulate filler, 50-90% by weight A photocurable adhesive or sealant composition containing the following is provided.

[0013] In one embodiment, the photocurable adhesive or sealant composition is, based on the weight of the composition, as follows: a) At least one oxetane compound according to formula (I), 5-10% by weight; b) At least one of the epoxide compounds, 5-15% by weight; c) At least one ionic photoacid generator (PAG), 0.1 to 5% by weight; d) At least one free radical photoinitiator, 0.1 to 10% by weight; e) At least one near-infrared absorbing dye, 0.01 to 1% by weight; and f) Particulate filler, 50-80% by weight Includes.

[0014] The presence of near-infrared absorbing dyes accelerates the curing of the present invention upon exposure to near-infrared (nIR) radiation. While such nIR radiation may be used alone for curing, irradiation of the composition with other chemical beams may also be applied before, simultaneously with, or after nIR irradiation. Under these curing conditions, the cured adhesive or sealant of the present invention should have minimal residual enthalpy and exhibit a high monomer conversion rate, e.g., over 85%. Furthermore, in tests, the composition demonstrated a favorable curing depth without requiring a thermal curing step.

[0015] According to a second aspect of the present invention, an adhesive structure is provided comprising a first material layer and a second material layer, wherein a cured adhesive composition as defined herein and in the appended claims is positioned between the first and second material layers and in contact with the first and second material layers.

[0016] The present invention also provides the use of adhesive or sealant compositions, as defined herein and in the appended claims, in optoelectronic devices or optomechanical devices. [Modes for carrying out the invention]

[0017] [Definition] As used herein, the singular forms "a," "an," and "the" include multiple references unless the context clearly indicates otherwise.

[0018] As used herein, the terms “comprising,” “comprises,” and “comprised of” are synonymous with “including,” “includes,” “containing,” or “contains,” and are comprehensive or open-ended, not excluding additional, unquoted members, elements, or process steps.

[0019] As used herein, the term “consisting of” excludes any unspecified elements, components, members, or process steps.

[0020] When quantities, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper limits, lower limits, or preferred upper and lower limits, any range obtained by any combination of any upper or preferred value and any lower or preferred value should be understood to be specifically disclosed, regardless of whether the obtained range is explicitly mentioned in the context.

[0021] Furthermore, according to standard understanding, the weight range expressed as "0 to x" specifically includes 0% by weight. The components defined by the range may not be present in the composition, or they may be present in the composition in amounts up to x% by weight.

[0022] The words “preferred,” “preferably,” “desirably,” and “particularly” are frequently used herein to refer to embodiments of the disclosure that may offer particular advantages under specific circumstances. However, the use of one or more “preferable,” “preferred,” “desirable,” or “desirable” descriptions of particular embodiments does not imply that other embodiments are not useful, nor is it intended to exclude those other embodiments from the scope of the disclosure.

[0023] When used throughout this application, the word "may" is used in an allowable sense (i.e., possible) rather than an obligatory sense.

[0024] As used herein, room temperature is 23°C plus or minus 2°C. As used herein, “ambient conditions” means the temperature and pressure of the surrounding environment in which the composition is placed, or in which the coating layer or the substrate of the coating layer is placed.

[0025] The molecular weights referred to herein can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards, as performed in accordance with ASTM 3536 (to describe the polymer, oligomer, and polymer components of curable compositions).

[0026] The viscosity of the coating compositions described herein is measured using a viscometer under standard conditions of 20°C and 50% relative humidity (RH), unless otherwise specified. The calibration method for the viscometer is selected according to the manufacturer's instructions, depending on the composition being measured.

[0027] In this specification, "average particle size (D50)" refers to the particle diameter corresponding to 50% of the particles in a distribution curve where particles are accumulated in order of particle diameter from the smallest particle to the largest particle, and the total number of accumulated particles is 100%.

[0028] In this specification, the glass transition temperature ("Tg") of a polymer or copolymer may be calculated using Fox's formula (TGFox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, page 123 (1956)). The glass transition temperatures of specific homopolymers are described in published literature.

[0029] The actual glass transition temperature (Tg) of a polymer can be determined by dynamic mechanical thermal analysis (DMTA). The glass transition temperature (Tg) specifically measured in this patent application is measured by DMTA according to the methodologies of the International Organization for Standardization (ISO) standards ISO 6721-1 and ISO 6721-11.

[0030] As used herein, "near-infrared (nIR) radiation" refers to electromagnetic radiation having a wavelength of 700 to 1500 nm (such as emitted by a laser or a light-emitting diode (LED)). Non-limiting examples of such near-infrared radiation are the light emitted by diode lasers equipped with plate setters and available from Creo-Kodak, Dinippon Screen, Heidelberg, and Presstek International. Further exemplary nIR radiation sources are the FireJet® and FireEdge® LED lamps available from Phoseon Technology Inc. With respect to the compositions of the present invention, it may be mentioned that irradiation with nIR radiation having a wavelength of 780 to 980 nm is preferred.

[0031] As used herein, "near-infrared (nIR) absorbing dye" is a compound, complex, or molecule having substantial absorbance in the wavelength range of 700 nm to 1500 nm.

[0032] As used herein, the term "monomer" means a substance that can undergo a polymerization reaction to contribute a structural unit to the chemical structure of a polymer. As used herein, the term "monofunctional" means having one polymerizable site. The term "polyfunctional" as used herein means having two or more polymerizable sites.

[0033] As used herein, the term "equivalent (eq.)" relates to the relative number of reactive groups present during a reaction, as is normal in chemical notation. The term "milliequivalent (meq)" is one thousandth (10 -3 ) of a chemical equivalent.

[0034] As used herein, the term "equivalent" refers to the molecular weight divided by the number of functional groups. Therefore, "epoxy equivalent" (EEW) means the gram weight of a resin containing one equivalent of epoxy. This parameter can be measured by Shell Analytical Method HC427D-89 using perchloric acid titration.

[0035] In this specification, oxetane compounds and epoxide compounds undergo "ring-opening polymerization," which means polymerization in which a cyclic compound (monomer) opens its ring in the presence of a suitable catalyst to form a linear polymer. The reaction system tends to move toward equilibrium between the desired target polymer compound, a mixture of cyclic compounds, and / or linear oligomers, and the achievement of this equilibrium depends largely on the properties and amount of the cyclic monomer, the catalyst used, and the reaction temperature. The use of solvents and emulsions in polymerization is not recommended because their removal after the reaction is complete becomes complicated.

[0036] As used herein, the term “epoxide” refers to a compound characterized by the presence of at least one cyclic ether group, i.e., a group in which an ether oxygen atom is bonded to two adjacent carbon atoms, thereby forming a cyclic structure. This term is intended to encompass monoepoxide compounds, polyepoxide compounds (having two or more epoxy groups), and epoxide-terminated prepolymers. The term “monoepoxide compound” means an epoxide compound having one epoxy group. The term “polyepoxide compound” means an epoxide compound having at least two epoxy groups. The term “diepoxide compound” means an epoxide compound having two epoxy groups.

[0037] The epoxide may be unsubstituted or inertly substituted. Exemplary inert substituents include chlorine, bromine, fluorine, and phenyl.

[0038] As used herein, the term “photoinitiator” refers to a compound that can be activated by an activation beam having energy, for example, irradiation (e.g., electromagnetic radiation). This term is intended to encompass both free radical photoinitiators, as well as photoacid generators and photobase generators. Specifically, the term “photoacid generator” refers to a compound or polymer that generates acids for catalysts in acid-curable resin systems by chemical beam irradiation. The term “photobase generator” means any material that generates one or more bases when exposed to appropriate radiation.

[0039] As used herein, the term "Lewis acid" refers to a molecule or ion (often called an electrophile) that can bond to another molecule or ion by forming a covalent bond with two electrons from a second molecule or ion. Therefore, Lewis acids are electron acceptors.

[0040] When used herein, "C 1- C n An alkyl group is a monovalent group containing 1 to n carbon atoms, is an alkane group, and includes both linear and branched organic groups. 1- C 18 An alkyl group is a monovalent group containing 1 to 18 carbon atoms, which is an alkane group and includes linear and branched organic groups. Examples of alkyl groups, but not limited to these, include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and 2-ethylhexyl. In the present invention, such alkyl groups may be unsubstituted or substituted with one or more halogens. Where applicable to a given site (R), the permissible range of one or more non-halogen substituents within the alkyl group is described herein.

[0041] As used herein, the term "C1-C6 hydroxyalkyl" refers to an HO-(alkyl) group having 1 to 6 carbon atoms, where the substituent bond is via an oxygen atom, and the alkyl group is as defined above.

[0042] An "alkoxy group" refers to a monovalent group represented by -OA where A is an alkyl group, and non-limiting examples include the methoxy group, ethoxy group, and isopropyloxy group. The term "C" as used herein refers to a monovalent group represented by -OA where A is an alkyl group. 1- C 18 "Alkoxyalkyl" refers to an alkyl group having an alkoxy substituent as defined above, where the alkyl-O-alkyl portion contains a total of 1 to 18 carbon atoms. Examples of such groups include methoxymethyl (-CH2OCH3), 2-methoxyethyl (-CH2CH2OCH3), and 2-ethoxyethyl.

[0043] The term "C1-C" as used herein 12 An alkylene is defined as a saturated divalent hydrocarbon group having 1 to 12 carbon atoms. By extension, the term "C1-C6 alkylene oxy" refers to the divalent group -RO-, where R is C1-C6 alkylene.

[0044] The term “C 3- C 18 "Cycloalkyl" is understood to mean a saturated monocyclic or polycyclic hydrocarbon group having 3 to 18 carbon atoms. In the present invention, such cycloalkyl groups may be unsubstituted or substituted with one or more halogens. Where applicable to a given site (R), the permissible range of one or more non-halogen substituents in the cycloalkyl group is described herein. Examples of cycloalkyl groups include cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornane.

[0045] When used herein, "C6-C" is used alone or as part of a larger part. 18The "aryl" group refers to monocyclic, bicyclic, and tricyclic ring systems, where monocyclic ring systems are aromatic, or bicyclic or at least one ring in a bicyclic system is aromatic. Bicyclic and tricyclic ring systems include benzo-condensed 2-3 membered carbon rings. In the present invention, such aryl groups may be unsubstituted or substituted with one or more halogens. Where applicable to a given site (R), the permissible range of one or more non-halogen substituents in the aryl group is described herein. Examples of aryl groups include phenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; and tetrahydroanthracenyl.

[0046] The term "C6-C" used in this specification 18 An "arylene group" refers to a divalent radical having 6 to 18 carbon atoms, derived from monocyclic, bicyclic, and tricyclic ring systems, where the monocyclic ring system is aromatic, or at least one ring in the bicyclic or tricyclic ring system is aromatic. The arylene group may be substituted with at least one halogen substituent, but the aromatic portion of the arylene group contains only carbon atoms. An example is "C6-C 18 The "arylene" group includes phenylene and naphthalene-1,8-diyl.

[0047] As used herein, the term "aryloxy" means an O-aryl group, where aryl is as defined above. In the present invention, such an aryloxy group may be unsubstituted or substituted with one or more halogens.

[0048] The term "aralkyl group" refers to a group in which at least one hydrogen atom of the alkyl group defined above is substituted with the aryl group defined above. For completeness, such an aralkyl group may be unsubstituted or substituted with one or more halogens.

[0049] As used herein, the term "aralkylene" refers to a divalent group in which at least one hydrogen atom of the alkylene group as defined above is substituted with an aryl group. The aralkylene group may be substituted with at least one halogen substituent.

[0050] As used herein, "alkylaryl" refers to an alkyl-substituted aryl group. Furthermore, the term "alkarylene" refers to a divalent radical that is an alkyl-substituted aryl radical in which one hydrogen at any position on the alkyl carbon backbone is substituted by an additional bonding site. Examples of alkarylene groups include methylphenylene and ethylphenylene.

[0051] As used herein, the “aralkoxy” group is an aralkyl group that is bonded to a compound via an oxygen substituent on the alkyl moiety of the aralkyl group. Examples of arylalkoxy groups include phenylmethoxy and phenylethoxy.

[0052] As used herein, "C 2- C 24 "Alkenyl" refers to a hydrocarbyl group having 2 to 24 carbon atoms and at least one unit of ethylenically unsaturated carbon. Alkenyl groups can be linear, branched, or cyclic and may be substituted with one or more halogens. Where applicable to a given site (R), the permissible range of one or more non-halogen substituents in an alkenyl group is described herein. The term "alkenyl" also encompasses groups having "cis" and "trans" configurations, or alternatively, "E" and "Z" configurations, as understood by those skilled in the art. However, generally, 2 to 10 (C) 2-10 ) or 2-8(C 2-8 The selection of an unsubstituted alkenyl group containing the carbon atom of the C should be taken into consideration. 2- C 12Examples of alkenyl groups are not limited to these, but include: -CH=CH2; -CH=CHCH3; -CH2CH=CH2; -C(=CH2)(CH3); -CH=CHCH2CH3; -CH2CH=CHCH3; -CH2CH2CH=CH2; -CH=C(CH3)2; -CH2C(=CH2)(CH3); -C(=CH2)CH2CH3; -C(CH3)=CHCH3; -C(CH3)CH=CH2; -CH=CHCH2CH2CH3; -CH2CH=CHCH2CH3; -CH2CH2CH=CHCH3; -CH2CH2CH2CH=CH2; -C(=CH2)CH2CH2CH3; -C(CH3)=CHCH2CH3; -CH(CH3)CH=CHCH; -CH(CH3)CH2CH=CH2; -CH2CH=C(CH3)2; Examples include 1-cyclopent-1-enyl; 1-cyclopent-2-enyl; 1-cyclopent-3-enyl; 1-cyclohex-1-enyl; 1-cyclohex-2-enyl; and 1-cyclohexyl-3-enyl.

[0053] As used herein, "C2-C 12 "Alkenylene" refers to a di-radical group having 2 to 24 carbon atoms and at least one unit of ethylenically unsaturated atoms. Alkenylene radicals can be linear, branched, or cyclic and may be substituted with one or more halogens. Where applicable to a given site (R), the permissible range of one or more non-halogen substituents in an alkenylene radical is described herein. As will be understood by those skilled in the art, the term "alkenylene" also includes radicals having "cis" and "trans" configurations, or alternatively, "E" and "Z" configurations. The C2-C 12 Examples of alkenyl groups include, but are not limited to, the following: Ethenylene; ethene-1,1-diyl; propenylene; propene-1,1-diyl; prop-2-en-1,1-diyl; 1-methyl-ethenylene; but-1-enylene; but-2-enylene; but-1,3-dienylene; butene-1,1-diyl; but-1,3-diene-1,1-diyl; but-2-en-1,1-diyl; but-3-en-1,1-diyl; 1-methyl-prop-2-en-1,1-diyl; 2-methyl-prop-2-en-1,1-diyl; 1-ethyl-ethenylene; 1,2-dimethyl-ethenylene; 1-methyl-propenylene; 2-methyl-propenylene; 3-methyl-propenylene; 2-methyl-propene-1,1-diyl; and 2,2-dimethyl-ethene-1,1-diyl.

[0054] As used herein, the term "hetero" refers to a group or moiety containing one or more heteroatoms such as N, O, Si, and S. Thus, for example, "heterocyclic ring" refers to a cyclic group having, for example, N, O, Si, or S as part of the ring structure. "Heteroalkyl", "heterocycloalkyl", and "heteroaryl" moieties are, respectively, alkyl groups, cycloalkyl groups, and aryl groups as defined herein that contain N, O, Si, or S as part of their structures.

[0055] The compositions of the present invention may be defined herein as "substantially free" of certain compounds, elements, ions, or other similar components. The term "substantially free" is intended to mean that the compound, element, ion, or other similar component is not intentionally added to the composition and is present at only trace amounts that do not affect (adversely) the desired properties of the coating. Exemplary trace amounts are less than 1000 ppm by weight of the composition. The term "substantially free" encompasses embodiments in which the particular compound, element, ion, or other similar component is not present at all in the composition or is not present in any measurable amount by techniques generally used in the art.

[0056] [Detailed Description of the Invention] <a) Oxetane compounds> The composition of the present invention is based on the weight of the composition and contains 1 to 10% by weight of the following formula (I): [ka] [In the formula, R 1 and R 2 H, C1-C6 alkyl, C6-C 18 Aryl, or C7-C 18 It is Aralquil; Each R 3 It is independently, C1-C 12 Alkylene group, C2-C 12 It is an alkenylene group or a poly(C1-C6 alkylene oxy) group; n is an integer between 1 and 3. It contains at least one oxetane compound.

[0057] The composition may, for example, contain 5 to 10% by weight of at least one oxetane compound according to formula (I) based on the weight of the composition.

[0058] In one embodiment, the composition is of formula (IA): [ka] [In the formula, R 1 and R 2 This is as defined above. It may contain oxetane as indicated by [the symbol].

[0059] In this embodiment, R 1 and R 2 It should be noted that it is preferable that it be a C1-C6 alkyl group. 1 and R 2 These may be the same or different, but it is preferable that they be the same. An exemplary compound according to formula IA is bis[1-ethyl-3-oxetanyl(oxentanyl))methyl]ether.

[0060] In another embodiment of the present invention, although not intended to be mutually exclusive with the above, the composition is of formula (IB): [Chemical formula] [wherein, R 1 , R 2 and R 3 are as defined above] and may contain an oxetane compound represented by

[0061] Within this embodiment, R 1 and R 2 are C1-C6 alkyl; and R 3 is C1-C6 alkylene. For example, R 1 and R 2 are the same and are C1-C4 alkyl; and R 3 is C1-C4 alkylene. An exemplary compound according to formula (IAA) is 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene.

[0062] <b) Epoxide compound> The composition of the present invention contains 5 to 20% by weight of b) at least one epoxide compound based on the weight of the composition. The composition may contain, for example, 5 to 15% by weight of b) the at least one epoxide compound based on the weight of the composition. As described above, based on the total weight of the epoxide compounds in the composition, at least 50% by weight is constituted by b1) at least one alicyclic epoxide. b1) The at least one alicyclic epoxide compound may reasonably constitute at least 65% by weight, and further 100% by weight, of the component b).

[0063] <b1) Alicyclic epoxide compound> The alicyclic epoxide compounds contained in the composition, or each alicyclic epoxide compound, comprises at least one epoxy group which may take the following forms: a terminal epoxy group; a glycidyl ether (e.g., -O-CH2-epoxide); or an epoxide condensed to a C5-7 cycloalkyl group.

[0064] Exemplary alicyclic epoxide compounds include: mono-epoxy-substituted alicyclic hydrocarbons, e.g., cyclohexene oxide, vinylcyclohexene monooxide, (+)-cis-limonene oxide, (+)-cis,trans-limonene oxide, (-)-cis,trans-limonene oxide, cyclooctene oxide, cyclododecene oxide, and α-pinene oxide; vinylcyclohexene diepodes; limonene diepodes; glycidyl ethers of alicyclic alcohols; glycidyl esters of alicyclic monocarboxylic acids; diglycidyl ethers of alicyclic diols, e.g., cyclopentanediol and cyclohexanediol; and glycidyl esters of alicyclic polycarboxylic acids comprising at least two carboxylic acid groups and not containing other groups that react with the epoxide group.

[0065] Without intending to limit the present invention, suitable alicyclic epoxy resins include: cyclohexanedimethanol diglycidyl ether; bis(3,4-epoxycyclohexylmethyl) adipate; bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate; bis(2,3-epoxycyclopentyl) ether; 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate; 1,4-cyclohexanedimethanol diglycidyl ether; diglycidyl 1,2-cyclohexanedicarboxylate; bis(2,3-epoxypropyl)cyclohexane-1,2-dicarboxylate; and alicyclic epoxy resins obtained by hydrogenation of aromatic bisphenol A diglycidyl ether (BADGE) epoxy resin.

[0066] Preferably, the alicyclic epoxy has two C 5-6containing a cycloalkyl group, where each is independently condensed with an epoxide, for example bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis(2,3-epoxycyclopentyl) ether, or 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate, etc.

[0067] Examples of commercially available alicyclic epoxide compounds that may be mentioned are: Cyracure® UVR6105, UVR6107, UVR6110, and UVR6128 (manufactured by Dow Chemical); Syna Epoxy S-06E (manufactured by Synasia), and Celloxide 2021P (manufactured by Daicel Corporation).

[0068] <b2) Aliphatic and aromatic epoxide compounds> In addition to the necessarily present alicyclic resin, the composition of the present invention may optionally contain b2) at least one further epoxide compound. The further epoxide compounds used herein may include monofunctional epoxy resins, multifunctional or polyfunctional epoxy resins, and combinations thereof. The epoxy resin may be a pure compound, but may equally be a mixture of epoxy-functional compounds, including mixtures of compounds having different numbers of epoxy groups per molecule. The further epoxy resin may be saturated or unsaturated, aliphatic, aromatic or heterocyclic, and may be substituted. Further, the epoxy resin may be a monomer or a polymer.

[0069] Without intending to limit the present invention, exemplary non-alicyclic monoepoxide compounds include: alkylene oxides; epoxy-substituted aromatic hydrocarbons; monoepoxy-substituted alkyl ethers of monohydric alcohols or phenols, e.g., glycidyl ethers of aliphatic and aromatic alcohols; monoepoxy-substituted alkyl esters of monocarboxylic acids, e.g., glycidyl esters of aliphatic and aromatic monocarboxylic acids; monoepoxy-substituted alkyl esters of polycarboxylic acids in which other carboxyl groups are esterified with alkanols; alkyl and alkenyl esters of epoxy-substituted monocarboxylic acids; epoxy alkyl ethers of polyhydric alcohols in which other OH groups are esterified or etherified with carboxylic acids or alcohols; and monoesters of polyhydric alcohols and epoxy monocarboxylic acids in which other OH groups are esterified or etherified with carboxylic acids or alcohols.

[0070] For example, the following glycidyl ethers may be mentioned as monoepoxide compounds particularly suitable for use herein: methyl glycidyl ether; ethyl glycidyl ether; propyl glycidyl ether; butyl glycidyl ether; pentyl glycidyl ether; hexyl glycidyl ether; octyl glycidyl ether; 2-ethylhexyl glycidyl ether; allyl glycidyl ether; benzyl glycidyl ether; phenyl glycidyl ether; 4-tert-butylphenyl glycidyl ether; 1-naphthyl glycidyl ether; 2-naphthyl glycidyl ether; 2-chlorophenyl glycidyl ether; 4-chlorophenyl glycidyl ether; 4-bromophenyl glycidyl ether; 2,4,6-trichlorophenyl glycidyl ether; 2,4,6-tribromophenyl glycidyl ether; pentafluorophenyl glycidyl ether; o-cresyl glycidyl ether; m-cresyl glycidyl ether; and p-cresyl glycidyl ether.

[0071] In one embodiment, the monoepoxide compound is given by the following formula (II): [ka] [In the formula, R 7 , R 8 , R 9 and R 10 They may be the same or different, and include hydrogen, halogen atoms, C1-C8 alkyl groups, and C2-C 12 Alkenyl, C6-C 18 Aryl group or C7-C 18 Independently selected from the aralkyl group, however, R 8 and R 9 [Provided that at least one of them is not hydrogen.] Follow the rules.

[0072] R 7 , R 8 and R 10 It is preferably hydrogen, R 9 is either a phenyl group or a C1-C8 alkyl group, more preferably a C1-C4 alkyl group.

[0073] In this embodiment, exemplary monoepoxides include: ethylene oxide; 1,2-propylene oxide (propylene oxide); 1,2-butylene oxide; cis-2,3-epoxybutane; trans-2,3-epoxybutane; 1,2-epoxypentane; 1,2-epoxyhexane; 1,2-heptylene oxide; decene oxide; butadiene oxide; isoprene oxide; and styrene oxide.

[0074] Again, without the intention of limiting the present invention, a suitable polyepoxide compound useful as component b2) may be a liquid, solid, or a solution in a solvent. Furthermore, it is desirable that such a polyepoxide compound has an epoxide equivalent of 100 to 700 g / eq., for example, 120 to 320 g / eq. Generally, diepoxide compounds having an epoxide equivalent of less than 500 g / eq. or even less than 400 g / eq. are preferred. This is mainly from a cost standpoint, as low molecular weight epoxy resins require more limited processing in their purification during production.

[0075] Examples of types or groups of polyepoxide compounds that can be polymerized in the present invention include: glycidyl ethers of polyhydric alcohols and polyhydric phenols; glycidyl esters of polycarboxylic acids; and epoxidized polyethylene unsaturated hydrocarbons, esters, ethers, and amides.

[0076] Suitable diglycidyl ether compounds may be aromatic or aliphatic in nature, and such may be derivable from dihydric phenols and dihydric alcohols. Useful classes of such diglycidyl ethers include diglycidyl ethers of aliphatic diols, e.g., 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, and 1,12-dodecanediol; bisphenol A diglycidyl ethers; bisphenol F diglycidyl ethers; diglycidyl o-phthalate, diglycidyl isophthalate, and diglycidyl terephthalate; polyalkylene glycol diglycidyl ethers, especially polypropylene glycol diglycidyl ethers; and polycarbonate diol glycidyl ethers. Other suitable diepoxides that can be mentioned include biunsaturated fatty acid C1-C 18 Examples include alkyl ester diepoxides; butadiene diepoxides; and polybutadiene diglycidyl ethers.

[0077] Further exemplary polyepoxide compounds include, but are not limited to, glycerol polyglycidyl ether; trimethylolpropane polyglycidyl ether; pentaerythritol polyglycidyl ether; diglycerol polyglycidyl ether; polyglycerol polyglycidyl ether; and sorbitol polyglycidyl ether.

[0078] The glycidyl esters of polycarboxylic acids useful in the present invention are derived from polycarboxylic acids that contain at least two carboxylic acid groups and do not contain other groups that react with the epoxide group. Polycarboxylic acids can be aliphatic, aromatic, and heterocyclic. Preferred polycarboxylic acids contain 18 or fewer carbon atoms per carboxylic acid group, and suitable examples include, but are not limited to: oxalic acid; sebacic acid; adipic acid; succinic acid; pimelic acid; suberic acid; glutaric acid; dimer and trimer acids of unsaturated fatty acids, e.g., dimer and trimer acids of linseed fatty acids; phthalic acid; isophthalic acid; terephthalic acid; trimellitic acid; trimesic acid; phenylene-diacetic acid; chlorendic acid; diphenic acid; naphthalic acid; polyacid-terminated esters of dibasic acids and aliphatic polyols; polymers and copolymers of (meth)acrylic acid; and crotonic acid.

[0079] Specific examples of polyepoxide compounds include: bisphenol A epoxy resins, e.g., DER(registered trademark) 331, DER(registered trademark) 332, DER(registered trademark) 383, JER(registered trademark) 828, and Epotec YD 128; bisphenol F epoxy resins, e.g., DER(registered trademark) 354; bisphenol A / F epoxy resin blends, e.g., DER(registered trademark) 353; aliphatic glycidyl ethers, e.g., DER(registered trademark) 736; polypropylene glycol diglycidyl ethers, e.g., DER(registered trademark) 732; solid bisphenol A epoxy resins, e.g., DER(registered trademark) 661 and DER(registered trademark) 664UE; solutions of solid bisphenol A epoxy resins, e.g., DER(registered trademark) 671-X75; epoxy novolac resins, e.g., DEN(registered trademark) 438; epoxidized phenol novolac resins, e.g., Epalloy 2850, etc.; brominated epoxy resins, e.g., DER(registered trademark) 542, etc.; castor oil triglycidyl ether, e.g., ERISYS(registered trademark) GE-35H, etc.; polyglycerol-3-polyglycidyl ether, e.g., ERISYS(registered trademark) GE-38, etc.; and sorbitol glycidyl ether, e.g., ERISYS(registered trademark) GE-60, etc.

[0080] Separately from the above, component b) of the composition is, in a particular embodiment, of formula: [ka] [In the formula, Each R is independently selected from methyl or ethyl; and n is between 1 and 10. It is desirable to include a glycidoxyalkylalkoxysilane having the following properties.

[0081] Exemplary silanes include, but are not limited to, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltriethoxysilane; and 8-glycidoxyoctyltrimethoxysilane. When present, the epoxide-functional silane preferably constitutes less than 20% by weight, more preferably less than 10% by weight or less than 5% by weight, based on the total weight of the epoxide compound.

[0082] The present invention also does not prevent the curable composition from further comprising one or more cyclic monomers selected from the group consisting of cyclic carbonates; cyclic anhydrides; and lactones. The disclosures of the following cited references may be useful in disclosing suitable cyclic carbonate-functional compounds. U.S. Patent No. 3,535,342; U.S. Patent No. 4,835,289; U.S. Patent No. 4,892,954; British Patent No. GB-A-1,485,925 and EP-A-0 119840. However, such cyclic comonomers preferably constitute less than 20% by weight, more preferably less than 10% by weight or less than 5% by weight, based on the total weight of the epoxide compound b).

[0083] <c) Ionic photoacid generator> The composition of the present invention contains c) at least one ionic photoacid generator (PAG) of 0.1 to 5% by weight based on the weight of the composition. When irradiated with light energy, the ionic photoacid generator undergoes a fragmentation reaction to release one or more molecules of Lewis acid or Bronsted acid, catalyzing the ring-opening and the addition of pendant oxetane and epoxide groups to form crosslinks. Useful photoacid generators are thermally stable, do not undergo thermally induced reactions with the copolymer being formed, and are readily soluble or dispersible in the curable composition.

[0084] Examples of cations that can be used as the cationic moiety of the ionic PAG of the present invention include organo-onium cations, such as those described in U.S. Patents 4,250,311, 3,113,708, 4,069,055, 4,216,288, 5,084,586, 5,124,417, and 5,554,664. The references particularly include onium salts centered on aliphatic or aromatic Group IVA and Group VIIA (CAS version), and it should be noted that onium salts centered on I-, S-, P-, Se-, N-, and C-, such as those selected from sulfoxonium, iodonium, sulfonium, selenonium, pyridinium, carbonium, and phosphonium.

[0085] As is known in the art, the properties of the counteranions in ionic photoacid generators (PAGs) can affect the rate and extent of cationic addition polymerization of epoxide groups, for example, the order of reactivity among commonly used nucleophilic anions is SbF6 > AsF6 > PF6 > BF4. The influence of the anion on reactivity is due to three main factors that those skilled in the art should compensate for in the present invention: (1) the acidity of the protonic or Lewis acid produced; (2) the degree of ion-pair separation in the propagating cation chain; and (3) the susceptibility of the anion to fluoride abstraction and, consequently, to chain termination.

[0086] Examples of ionic photoacid generators useful in the compositions of the present invention include Irgacure® 250, Irgacure® PAG290, and GSID26-1 (manufactured by BASF SE); Cyracure® UVI-6990 and Cyracure® UVI-6974 (manufactured by Union Carbide); Degacure® Kl 85 (manufactured by Degussa); Optomer® SP-55, Optomer® SP-150, and Optomer® SP-170 (manufactured by Adeka); GE UVE 1014 (manufactured by General Electric); and SarCat® CD 1012, SarCat® KI-85, SarCat® CD 1010 and CD SarCat® 1011 (manufactured by Sartomer) may be mentioned.

[0087] <d) Free radical photoinitiator> The composition of the present invention may optionally further contain a free radical photoinitiator. For example, the composition may contain 0 to 10% by weight of d) at least one free radical photoinitiator, based on the weight of the composition, and this compound initiates the polymerization or curing of the composition upon irradiation with actinic rays. The composition may contain, for example, 0.1 to 10% by weight or 0.1 to 8% by weight of the free radical photoinitiator.

[0088] Free radical photoinitiators are generally classified into two types: those that form radicals by cleavage, known as "Norrish Type I," and those that form radicals by hydrogen abstraction, known as "Norrish Type II." Norrish Type II photoinitiators require a hydrogen donor that functions as a free radical source. Because their initiation is based on a bimolecular reaction, Norrish Type II photoinitiators are generally slower than Norrish Type I photoinitiators, which are based on single-molecule radical formation. On the other hand, Norrish Type II photoinitiators exhibit better light absorption properties in the near-ultraviolet spectroscopy region. Those skilled in the art should be able to select an appropriate free radical photoinitiator based on the chemical beam used for curing and the sensitivity of the photoinitiator at that wavelength.

[0089] Preferred free radical photoinitiators are selected from the group consisting of benzoylphosphine oxides, aryl ketones, benzophenones, hydroxylated ketones, 1-hydroxyphenyl ketones, ketals, and metallocenes. For completeness, combinations of two or more of these photoinitiators are not excluded in the present invention.

[0090] Particularly preferred free radical photoinitiators are selected from the group consisting of: benzoin dimethyl ether; 1-hydroxycyclohexyl phenyl ketone; benzophenone; 4-chlorobenzophenone; 4-methylbenzophenone; 4-phenylbenzophenone; 4,4'-bis(diethylamino)benzophenone; 4,4'-bis(N,N'-dimethylamino)benzophenone (Michler ketone); isopropylthioxanthone; 2-hydroxy-2-methylpropiophenone (Daracur 1173); 2-methyl-4-(methylthio)-2-morpholinopropiophenone; methylphenylglyoxylate; methyl 2-benzoyl benzoate; tert-butyl-peroxybenzoate; 2-ethylhexyl 4-(dimethylamino)benzoate; ethyl 4-(N,N-dimethylamino)benzoate; phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; and ethylphenyl(2,4,6-trimethylbenzoyl)phosphine phosphate. Herein again, certainly, combinations of two or more of these photoinitiators are not excluded in the present invention.

[0091] When the composition of the present invention contains a free radical photoinitiator, irradiation of the curable composition generates active species from the photoinitiator that initiate the curing reaction. Once these species are generated, the curing chemistry follows the same thermodynamic laws as any chemical reaction. The reaction rate can be accelerated by heat. The practice of using heat treatment to accelerate the chemical ray curing of monomers is well known in the art.

[0092] The use of cationic and optionally free radical photoinitiators in the present invention can generate residual compounds from (photo)chemical reactions in the final cured product. The residues can be detected by conventional analytical techniques such as infrared spectroscopy, ultraviolet spectroscopy, and NMR spectroscopy; gas or liquid chromatography; and mass spectrometry. Thus, the present invention can include a cured matrix (co)polymer and a detectable amount of residues from the cationic photoinitiator and the free radical photoinitiator. The residues are present in small amounts and usually do not interfere with the desirable physicochemical properties of the final cured product.

[0093] As will be recognized by those skilled in the art, a photosensitizer can be incorporated into the composition to improve the efficiency of using the energy supplied by the photoinitiators (components c) and d) herein). The term "photosensitizer" is used, according to its standard meaning, to represent any substance that increases the rate of photoinitiated polymerization or shifts the wavelength at which polymerization occurs. The photosensitizer is desirably used in an amount of 0 to 25% by weight based on the total weight of the photoinitiators in the composition.

[0094] <e) Near-infrared absorbing dye> The composition of the present invention includes at least one near-infrared absorbing dye, and it is desirable that this dye be present at a concentration sufficient to strongly absorb the activating radiation. The required or preferred concentration of a given near-infrared absorbing dye will vary depending on both the dye compound itself and the photoacid generator (PAG) present. However, it is typical for the composition to include 0.01 to 5% by weight, for example 0.1 to 1% by weight, of the near-infrared absorbing dye based on the weight of the composition.

[0095] Those skilled in the art will know of many near-infrared absorption dyes. In this specification, it is preferable to use dyes that are non-reactive and non-bleaching when combined with at least one photoacid generator (PAG), but bleach when exposed to activating radiation. Near-infrared absorption dyes include, but are not limited to, nitroso compounds and their metal complexes; methine dyes; cyanine dyes; merocyanine dyes; complex cyanine dyes; complex merocyanine dyes; holopolar cyanine dyes; hemicyanine dyes; styryl dyes; hemioxonol dyes; squalium dyes; thiol nickel complexes including cobalt, platinum, and palladium complexes; phthalocyanine dyes; triallylmethane dyes; triphenylmethane dyes; indolium dyes including their borate complexes; xanthene dyes; fluorescein dyes; rhodol dyes; rhodamine dyes; immonium dyes; diammonium dyes; naphthoquinone dyes; antroquinone dyes; porphyrin derivative dyes; and boron dipyromethane (BODIPY) dyes.

[0096] In particular, the following dyes, which may be used alone or in combination, may be mentioned: 3,3'-Diethylthiatrichabocyanine iodide ("DTTC"); 1,1'-Diethyl-4,4'-iodidecarbocyanine (cryptocyanine); Indocyanine green (ICG); Non-sulfonated cyanine dyes, e.g., cyanine 5 (Cy5), cyanine 5.5 (Cy5.5), cyanine 7 (Cy7), and cyanine 7.5 (Cy7.5) (manufactured by Lumiprobe); S0772 indolium tetafluroborate dye (manufactured by Few Chemicals) (λ max=858 nm); S2514 (CAS No. 2173178-46-4), (manufactured by Few Chemicals); methylene blue; sipeptide; sipeptide-glucosamine; silicon rhodamine; 5-aminolevulinic acid (5-ALA); and IRDye® 700, IRDye® 750, IRDye® 800CW and IRDye® 800RS (manufactured by Li-Cor).

[0097] <f) particulate filler> The composition of the present invention contains 50 to 90% by weight of f) particulate filler based on the weight of the composition. The composition may contain, for example, 50 to 80% by weight or 60 to 80% by weight of particulate filler based on the weight of the composition.

[0098] The desired viscosity of the curable composition to be formed can be determined by the amount of filler used. Considering the latter consideration, the total amount of filler should not prevent the composition from being easily applied by the selected method of applying the composition to the substrate. For example, the photocurable composition of the present invention intended to be applied to a specific location by printing or injection preferably has a viscosity of 1000 to 50,000, preferably 10,000 to 20,000 mPas.

[0099] Generally, there is no intention to particularly limit the shape of the particles employed as the filler, and particles such as acicular, spherical, elliptical, cylindrical, bead-shaped, cubic, or plate-shaped may be used alone or in combination. Furthermore, it is assumed that aggregates of two or more types of particles may be used. Similarly, there is no particular intention to limit the size of the particles employed as the filler. However, conventionally, such fillers have an average particle size (d50) of 0.1 to 1000 μm, for example 1 to 500 μm, measured by the laser diffraction / scattering method.

[0100] Examples of fillers include, but are not limited to, graphite, carbon black, calcium carbonate, calcium oxide, calcium chloride, calcium hydroxide (lime powder), calcium sulfate, fused silica, amorphous silica, precipitated and / or exothermic silicic acid, zeolite, bentonite, wollastonite, magnesium carbonate, magnesium sulfate, diatomaceous earth, barium sulfate, barium oxide, alumina, aluminum nitride, boron nitride, clay, talc, titanium dioxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass beads, glass powder, and other mineral materials. Organic fillers, particularly wood fibers, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, shredded straw, chaff, crushed walnut shells, and other shredded fibers may also be used: poly(tetrachloroethylene), poly(chlorotrifluoroethylene), and poly(vinylidene chloride) powders may also be used. Furthermore, short fibers such as glass fibers, glass filaments, polyacrylonitrile, carbon fibers, Kevlar fibers, or polyethylene fibers can also be added.

[0101] Suitable fillers are hollow spheres having a mineral shell or a plastic shell. These may be, for example, hollow glass spheres commercially available under the trade name Glass Bubbles®. Plastic hollow spheres such as Expancel® or Dualite® may also be used, which are described in EP 0 520 426 B1. These consist of inorganic or organic material and have a diameter of 1 mm or less, preferably 500 μm or less.

[0102] The use of core-shell rubber particles as fillers is also permitted. The terms “core-shell rubber” or CSR are used in accordance with their standard meaning in the art to refer to a rubber particle core formed by a polymer mainly comprising an elastomer or rubbery polymer, and a shell layer formed by a polymer graft-polymerized onto the core. The shell layer partially or completely covers the surface of the rubber particle core during the graft polymerization process. By weight, the core preferably constitutes at least 50% by weight of the core-shell rubber particles.

[0103] Core-shell rubber can be selected from commercially available products, including Paraloid TMS-2670J, EXL 2650A, EXL 2655, and EXL2691 A (manufactured by Dow Chemical Company); Clearstrength® XT100 (manufactured by Arkema Inc.); Kane Ace® MX series, particularly MX 120, MX 125, MX 130, MX 136, MX 551, and MX 553 (manufactured by Kaneka Corporation); and METABLEN SX-006 (manufactured by Mitsubishi Rayon).

[0104] Fillers that impart thixotropy to a composition may be preferred in many applications. Such fillers are also described as rheological adjuvants, such as hydrogenated castor oil, fatty acid amides, or swelling plastics such as PVC.

[0105] In one embodiment of the present invention, component e) of the composition comprises or comprises amorphous silica particles having an average particle diameter (d50) of 5 to 100 μm, for example, 5 to 50 μm, as measured by laser diffraction / scattering. For illustrative purposes, the use of a commercial grade of amorphous silica, commercially available under the trade name Denka FB, may be mentioned.

[0106] <Additives and auxiliary ingredients> The compositions obtained in the present invention will typically further include auxiliary agents and additives that can impart improved properties to these compositions. For example, auxiliary agents and additives may impart one or more of the following: improved elastic properties; improved elastic recovery; longer effective processing time; faster curing time; and lower residual tack. Such auxiliary agents and additives include: tougheners; plasticizers; stabilizers including UV stabilizers; antioxidants; reactive diluents; desiccants or moisture removers; adhesion promoters; bactericides; flame retardants; rheological auxiliary agents; coloring pigments or coloring pastes; and / or optionally, small amounts of non-reactive diluents.

[0107] Such auxiliary agents and additives may be used in any desired combination and proportion, provided that they do not adversely affect the properties and essential characteristics of the composition. While exceptions exist in some cases, these auxiliary agents and additives should not exceed 30% by weight of the total composition, and preferably not exceed 15% by weight of the composition.

[0108] The “plasticizer” for the purposes of the present invention is a substance that reduces the viscosity of a composition and therefore facilitates its processability. Here, the plasticizer may constitute up to 10% by weight or up to 5% by weight based on the total weight of the composition, and is preferably selected from the group consisting of diurethanes; monofunctional, linear or branched C4-C16 alcohol ethers, e.g., Cetiol OE (manufactured by Cognis Deutschland GmbH, Duesseldorf); esters of abietic acid, adipic acid, sebacic acid, butyric acid, thiobutyric acid, acetic acid, propionic acid esters and citric acid; esters based on nitrocellulose and polyvinyl acetate; fatty acid esters; dicarboxylic acid esters; esters of OH group-containing or epoxidized fatty acids; glycolic acid esters; benzoic acid esters; phosphate esters; sulfonic acid esters; trimellitic acid esters; polyether plasticizers, e.g., end-cap polyethylene or polypropylene glycol; polystyrene; hydrocarbon plasticizers; chlorinated paraffin; and mixtures thereof. In principle, phthalates can be used as plasticizers, but it should be noted that these are undesirable due to their toxicological potential.

[0109] For the purposes of this invention, “stabilizer” is understood to mean an antioxidant, ultraviolet stabilizer, heat stabilizer, or hydrolysis stabilizer. Herein, the stabilizer may constitute up to 10% by weight or up to 5% by weight in total, based on the total weight of the composition. Standard commercially available examples of stabilizers suitable for use herein include sterically hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; hindered amine light stabilizer (HALS) type amines; phosphorus; sulfur; and mixtures thereof.

[0110] As mentioned above in component b), the use of epoxy-functionalized silanes is possible, but it should also be noted that the adhesion of the cured adhesive to the substrate surface can be enhanced by using a compound having metal chelating properties in the composition of the present invention. Furthermore, acetacetate-functionalized modified resins sold by King Industries under the trade name K-FLEX XM-B301 are also suitable for use as adhesion promoters.

[0111] The presence of solvents and non-reactive diluents in the compositions of the present invention is not excluded if they can usefully adjust their viscosity. For example, the compositions may contain one or more of the following, but are illustrative only: xylene; 2-methoxyethanol; dimethoxyethanol; 2-ethoxyethanol; 2-propoxyethanol; 2-isopropoxyethanol; 2-butoxyethanol; 2-phenoxyethanol; 2-benzyloxyethanol; benzyl alcohol; ethylene glycol; ethylene glycol dimethyl ether; ethylene glycol diethyl ether; ethylene glycol dibutyl ether; ethylene glycol diphenyl ether; diethylene glycol; diethylene glycol monomethyl ether; diethylene glycol monoethyl ether; diethylene glycol mono-n-butyl ether; diethylene glycol dimethyl ether; diethylene glycol diethyl ether; diethylene Dipropylene glycol di-n-butyryl ether; propylene glycol butyl ether; propylene glycol phenyl ether; dipropylene glycol; dipropylene glycol monomethyl ether; dipropylene glycol dimethyl ether; dipropylene glycol di-n-butyl ether; N-methylpyrrolidone; diphenylmethane; diisopropylnaphthalene; petroleum fractions, e.g., Solvesso® products (manufactured by Exxon); alkylphenols, e.g., tert-butylphenol, nonylphenol, dodecylphenol and 8,11,14-pentadecatrienylenylphenol; styrene phenols; bisphenols; and aromatic hydrocarbon resins, especially those containing phenol groups, e.g., ethoxylated phenols or propoxylated phenols.

[0112] Separately from the above, it is preferable that the non-reactive diluent constitutes less than 10% by weight, particularly less than 5% by weight or less than 2% by weight, based on the total weight of the composition.

[0113] [Method and Application] To form a defined curable composition, components (parts) are assembled and mixed. It is crucial that the components are uniformly distributed within the adhesive composition during mixing. Such complete and effective mixing can determine the uniform distribution of any constituent particle fillers or other auxiliary materials within the polymer matrix obtained after curing.

[0114] As is known in the art, to form a curable composition, the elements of the composition are brought together and uniformly mixed under conditions that inhibit or prevent the reaction of reactive components. Such conditions will be readily understood by those skilled in the art. Therefore, it is often preferable to mix predetermined amounts of curing elements by machine, such as a static or dynamic mixer, without intentional light irradiation, rather than mixing them manually.

[0115] According to the broadest process embodiment of the present invention, the above composition is applied to a material layer and then cured in situ. Before applying the composition, it is often desirable to pre-treat the relevant surface to remove any foreign matter. If applicable, this step can facilitate the subsequent adhesion of the composition thereto. Such treatments are known in the art and can be carried out, for example, in one-step or multi-step methods comprising one or more of the following: etching with an acid and optionally an oxidizing agent suitable for the substrate; ultrasonic treatment; plasma treatment, including chemical plasma treatment, corona treatment, atmospheric pressure plasma treatment and flame plasma treatment; immersion in an aqueous alkaline degreasing bath; treatment with an aqueous cleaning emulsion; treatment with a cleaning solvent such as acetone, carbon tetrachloride or trichloroethylene; and rinsing with water, preferably deionized water or pure water.

[0116] In some embodiments, the adhesion of the composition of the present invention to a preferably pre-treated substrate can be facilitated by applying a primer thereto. Indeed, a primer composition may be necessary to ensure efficient fixing and / or curing times of the adhesive composition on an inert substrate. Those skilled in the art will be able to select a suitable primer.

[0117] The composition is then applied to the surface of a substrate that has been optionally pre-treated and optionally primed by conventional coating methods, such as printing methods including screen printing; pin transfer; and syringe coating including electro-pneumatic controlled syringes. It is recommended to apply the composition to the surface with a wet film thickness of 10 to 700 μm. Applying thinner layers within this range is more economical and can reduce the possibility of harmful thick cured areas. However, when applying thinner coatings or layers, extreme caution is necessary to avoid the formation of discontinuous cured films.

[0118] In the present invention, an energy source emitting near-infrared (nIR) radiation is always used in the curing of the applied composition. The total amount of near-infrared (nIR) radiation required to satisfactorily cure an individual adhesive or sealant composition (for example, to fix the adhesive or sealant) includes the radiation exposure angle and the thickness of the adhesive or sealant layer. It will depend on various factors. However, generally speaking, it is 1-20 W / cm². 2 A typical example is the irradiance of near-infrared (nIR) radiation, which is 1-15 W / cm². 2 For example, 5-15 W / cm² 2 The curing illuminance can be considered to be very effective. After application, the photocurable adhesive composition may be activated in typically less than 5 minutes, usually 1 to 60 seconds (e.g., 3 to 12 seconds), when irradiated using a commercially available curing device.

[0119] The use of near-infrared (IR) radiation in the above method does not preclude the use of further energy sources capable of emitting at least one of ultraviolet (UV) radiation, mid-infrared (IR) radiation, far-infrared (IR) radiation, visible light, X-rays, gamma rays, or electron beams (e-beams). Such supplemental irradiation may be used as a tool to achieve satisfactory curing under general laboratory, commercial, or industrial conditions, but is not considered essential. Supplemental irradiation may be applied before, during, and / or after near-infrared (IR) irradiation of the composition to be treated.

[0120] When used, the ultraviolet light emitted typically has a wavelength of 150 to 600 nm, preferably 200 to 450 nm. Useful ultraviolet light sources include, for example, ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low-intensity fluorescent lamps, metal halide lamps, microwave-driven lamps, xenon lamps, UV-LED lamps, and laser light sources such as excimer lasers and argon-ion lasers.

[0121] When an electron beam is used to cure the applied coating, the standard parameters of the operating device are an acceleration voltage of 0.1 to 100 keV; and a voltage of 10 to 10 -3 A vacuum of Pa; an electron current of 0.0001 to 1 ampere; and a power of 0.1 watts to 1 kilowatt.

[0122] The purpose of irradiation is to generate active species from the photoinitiator that initiate the curing reaction. Once these species are generated, the curing chemistry follows the same thermodynamic laws as any chemical reaction. The reaction rate can be accelerated by heat or slowed by low temperatures. Without intending to limit the present invention, complete curing of the coated curable composition is typically desirable to occur at temperatures in the range of 20°C to 50°C, preferably 20°C to 40°C. Where applicable, the temperature of the curable composition may be higher than the mixing temperature and / or coating temperature using conventional means, including microwave induction.

[0123] There is no particular intention to limit the substrates to which the adhesive or sealant composition of the present invention may be applied. Those skilled in the art will likely recognize substrates conventionally found in optoelectronic or optomechanical devices. However, other examples may include polymers such as polyvinyl chloride, polyolefins, and polycarbonates; carbon and nanocarbon substrates; metals such as Al, Pb, Sn, Ge, Si, Ti, Bi, In, Ni, and Fe; anodized metals, particularly anodized aluminum; alloys such as brass and stainless steel; semiconductor materials such as Si, GaAs, InP, GaP, GaSb, and InAs; ceramics including silica, zirconia, ceramic ferrules, piezoelectric ceramics, and dielectric ceramics; and glass including FTO / ITO glass, glass-polymer hybrid materials, and glass modified with a conductive layer thereon.

[0124] The following examples illustrate the present invention and are not intended to limit its scope. [Examples]

[0125] [Examples] In the examples, the following commercially available compounds are used. TIFF0007879872000007.tif107170

[0126] Formulations A to I were prepared according to the compositional information provided in Table 1 below. In Tables 1 and 2, "FM." indicates a formulation according to the present invention. In Tables 1 and 2, "CF" indicates a comparative formulation.

[0127] [Table 1]

[0128] Methods for determining the AE and GI of formulations: Where applicable, the nIR dye (S2514) was weighed into a speed mixer cup, then TMPO, OXT-221, and benzopicanol, where applicable, were added. The cup was held at 60°C for 30 minutes, after which A-187, Darocur 1173, Epalloy 8250, where applicable, and 50 wt% Cab-O-Sil 720 were added. The contents of the cup were mixed manually and then rapidly mixed at 2800 rpm for 2 minutes. The remainder of Cab-O-Sil 720 was added, the contents were mixed manually again, and rapidly mixed at 2800 rpm for 2 minutes. Denka FB35 was added in three portions, each addition requiring both manual stirring and stirring at 1800 rpm for 1 minute. After the resulting mixture was allowed to cool, PI2074 and Trigonox C, where applicable, were added. The mixture was degassed and mixed at high speed at 800 rpm for 1 minute to remove entrained air.

[0129] Method for formulation F: A-187, Darocur 1173, TMPO, OXT-221, and 2021P were weighed into a speed mixer cup, to which 50% by weight of Cab-O-Sil 720 was added. The contents of the cup were mixed manually, then rapidly mixed at 2800 rpm for 2 minutes. The remaining Cab-O-Sil 720 was added, the contents were mixed manually again, and rapidly mixed at 2800 rpm for 2 minutes. Carbon black was added, the contents were mixed manually again, and rapidly mixed at 2800 rpm for 2 minutes. Denka FB 35 was added in three portions, each addition requiring both manual stirring and stirring at 1800 rpm for 1 minute. After the resulting mixture was allowed to cool, PI2074 was added. The mixture was degassed and rapidly mixed at 800 rpm for 1 minute to remove entrained air.

[0130] Hardening evaluationThe curing of the formulations was monitored by dielectric analysis (DEA), in which a fixed amount of each formulation was placed between two electrodes and the same sinusoidal AC voltage was applied between the electrodes. This generated an electric field, causing ions in the material to move from one electrode to the other. During the curing process, the ion mobility and dipole rotation become more restricted, resulting in a change in the amplitude of the resulting signal. Since ionic conductivity is related to ion mobility, which is related to the viscosity of the material, ionic conductivity and its inverse value, ionic viscosity, are excellent indicators of viscosity changes during the curing process. This DEA analysis provides dielectric properties of the dielectric constant and loss coefficient of each sample as the curing progresses.

[0131] The results of tests performed on exemplary formulations are shown in Table 2 below. This table also includes further standard test methods where applicable. For completeness, i) the coated formulation was exposed to 365 nm wavelength radiation for 3 seconds at 1000 mW / cm². 2 ii) Expose to the applied formulation at an intensity of 12W; and, respectively, cure the exemplary formulations by exposing the coated formulations to radiation of a wavelength of 850 nm for 10 seconds, manipulating them at a distance of approximately 5 mm. A FireJet® FJ200 (manufactured by Phoseon Technology Inc.) was used for this irradiation process.

[0132] [Table 2]

[0133] Regarding Table 2, the greater the change in ionic viscosity, the higher the degree of curing obtained. It is noteworthy that only formulations containing nIR dyes reach very high temperatures during nIR curing. This high temperature is thought to promote high monomer conversion.

[0134] In consideration of the above description and examples, it will be apparent to those skilled in the art that equivalent modifications can be made without departing from the scope of the claims. The initial disclosures of this specification include at least the following aspects: [1] Based on the weight of the composition: a) The following equation (I):

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[10] The composition according to any one of [1] to [9], wherein component f) comprises amorphous silica particles having an average particle diameter (d50) of 5 to 100 μm, preferably 5 to 50 μm, as measured by laser diffraction.

[11] Use of any of the adhesive or sealant compositions described in [1] to

[10] in optoelectronic or opto-mechanical devices.

[12] First material layer; and second material layer; An adhesive structure comprising, Herein, the cured adhesive composition described in any of [1] to

[10] is an adhesive structure that is positioned between the first material layer and the second material layer and in contact with the first material layer and the second material layer.

Claims

1. Based on the weight of the composition: a) The following equation (I): 【Chemistry 1】 [In the formula, R １ and R ２ H, C １ -C ６ Alkyl, C ６ -C １８ Aryl, or C ７ -C １８ It is Aralkill; Each R ３ is independently a C １ -C １２ -alkylene group, a C ６ -C １８ -arylene group, a C ２ -C １２ -alkenylene group, or a poly(C １ -C ６ -alkyleneoxy) group; and n is an integer between 1 and 3. At least one oxetane compound, 1 to 10% by weight; b) at least one epoxide compound, 5 to 15% by weight, wherein component b) is characterized in that at least 50% by weight of the total weight of the epoxide compound is composed of b1) at least one alicyclic epoxide; c) At least one ionic photoacid generator, 0.1 to 5% by weight; d) At least one free radical photoinitiator, 0-10% by weight; e) at least one near-infrared absorbing dye, 0.01 to 5% by weight; and f) Particulate filler, 50-90% by weight A photocurable adhesive or sealant composition containing the following.

2. Based on the weight of the composition, the following applies: a) 5 to 10% by weight of at least one oxetane compound according to formula (I); b) 5 to 15% by weight of at least one epoxide compound; c) At least one ionic photoacid generator (PAG), 0.1 to 5% by weight; d) At least one free radical photoinitiator, 0.1 to 10% by weight; e) At least one near-infrared absorbing dye, 0.01 to 1% by weight; and f) Particulate filler, 50-80% by weight The composition according to claim 1, comprising:

3. Component a) is formula (IA): 【Chemistry 2】 [In the formula, R １ and R ２ H, C １ -C ６ Alkyl, C ６ -C １８ Aryl, or C ７ -C １８ It is Aralkir. The composition according to claim 1 or 2, comprising or consisting of oxetane, as shown by [the specified symbol].

4. R in equation (IA) １ and R ２ Both are C １ -C ６ The composition according to claim 3, wherein it is alkyl.

5. The composition according to claim 3, wherein component a) comprises or consists of bis[1-ethyl-3-oxetanyl)methyl] ether.

6. b1) The composition according to any one of claims 1 to 5, wherein the at least one alicyclic epoxide compound constitutes at least 65% by weight of component b).

7. The composition according to any one of claims 1 to 6, wherein the alicyclic epoxide is selected from the group consisting of bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis(2,3-epoxycyclopentyl) ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, and mixtures thereof.

8. Component b) is given by the formula: 【Transformation 3】 [In the formula, Each R is independently selected from methyl or ethyl; and n is between 1 and 10. A composition according to any one of claims 1 to 7, comprising at least one glycidoxyalkylalkoxysilane having .

9. Component b) is of formula: 【Chemistry 4】 [In the formula, Each R is independently selected from methyl or ethyl; and n is between 1 and 8. A composition according to any one of claims 1 to 7, comprising at least one glycidoxyalkylalkoxysilane having .

10. The composition according to any one of claims 1 to 9, wherein the aforementioned or each near-infrared absorbing dye in the composition is nonreactive with the at least one photoacid generator.

11. The composition according to any one of claims 1 to 10, wherein component f) comprises or consists of amorphous silica particles having an average particle diameter (d50) of 5 to 100 μm as measured by laser diffraction.

12. The composition according to any one of claims 1 to 10, wherein component f) comprises amorphous silica particles having an average particle diameter (d50) of 5 to 50 μm as measured by laser diffraction.

13. Use of the adhesive or sealant composition according to any one of claims 1 to 12 in optoelectronic or opto-mechanical devices.

14. First material layer; and second material layer; An adhesive structure comprising, Herein, the cured adhesive composition according to any one of claims 1 to 12 is an adhesive structure disposed between the first material layer and the second material layer and in contact with the first material layer and the second material layer.

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