Photocurable adhesive composition

Abstract

The present invention relates to a photocurable adhesive composition comprising at least one first hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of less than 250 g / eq; at least one second hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of 250 g / eq or more; at least one dimer acid-modified epoxy resin; at least one core-shell toughening agent; at least one polyol component; and at least one cationic photoinitiator. The cured product of the photocurable adhesive composition of the present invention exhibits excellent acid resistance and elongation properties, and is therefore suitable for use in protecting glass edges during glass slimming processes.

Description

[Technical Field]

[0001] Technical Field The present invention relates to a photocurable adhesive composition comprising at least one first hydroxyl-terminated, epoxidized, unsaturated polyolefin having an epoxide equivalent weight of less than 250 g / eq; at least one second hydroxyl-terminated, epoxidized, unsaturated polyolefin having an epoxide equivalent weight of 250 g / eq or greater; at least one dimer acid-modified epoxy resin; at least one core-shell toughening agent; at least one polyol component; and at least one cationic photoinitiator. The cured product of the photocurable adhesive composition of the present invention exhibits excellent acid resistance and elongation properties, making it suitable for use in protecting glass edges during glass slimming processes. [Background technology]

[0002] Background of the Invention As electronic devices become more widespread, there is a demand for thinner and lighter electronic devices. One way to achieve this goal is to thin the flat panel displays (FPDs) used in these devices. TFT-LCDs, the main type of FPD, typically form a box that encapsulates liquid crystal between two pieces of glass. The edges of the TFT-LCD are sealed with UV-curable adhesive to prevent etching solutions from penetrating the box. Because etching solutions often contain strong acids, glass protected by conventional UV-curable adhesives can only be thinned to about 0.3 mm.

[0003] Furthermore, curved or rounded corner glass is becoming increasingly popular and is the trend for future displays in electronic devices. Traditional UV-curable adhesives are not flexible enough to be applied to protect curved or rounded corner glass. Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there is a need to develop new light-curing adhesives with improved acid resistance and elasticity to better seal and protect the glass during the glass slimming process. [Means for solving the problem]

[0005] Summary of the Invention The present invention relates to a photocurable adhesive composition, comprising: a) at least one first hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of less than 250 g / equivalent; b) at least one second hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of 250 g / eq or greater; c) at least one dimer acid modified epoxy resin; d) at least one core-shell toughener; e) at least one polyol component; and f) at least one cationic photoinitiator; where: the weight ratio of the first hydroxyl-terminated epoxidized unsaturated polyolefin to the second hydroxyl-terminated epoxidized unsaturated polyolefin is 2:5 to 6:5; The amount of core-shell toughener is 3 to 15 wt. %, based on the total weight of the adhesive composition; and The amount of the polyol component is 1 to 9 wt % based on the total weight of the adhesive composition.

[0006] The present invention also relates to a method for producing a photocurable adhesive composition.

[0007] The present invention also relates to a cured product of the photocurable adhesive composition, which has excellent acid resistance and elongation properties.

[0008] The present invention also relates to articles bonded or sealed with the cured product of the photocurable adhesive composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] Detailed Description of the Invention In the following passages, the present invention will be described in more detail. Each aspect so described may be combined with any other aspect, unless expressly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature indicated as being preferred or advantageous.

[0010] In the context of the present invention, the terms used shall be construed in accordance with the following definitions, unless the context dictates otherwise.

[0011] As used herein, the singular forms "a," "an," and "the" include both singular and plural referents unless the context clearly dictates otherwise.

[0012] As used herein, the terms "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," or "containing," and "contains," and are inclusive or open-ended and do not exclude additional, unrecited members, elements, or process steps.

[0013] The recitation of numerical endpoints includes all values ​​and fractions subsumed within each range, as well as the recited endpoints.

[0014] All references cited herein are incorporated by reference in their entirety.

[0015] Unless otherwise defined, all terms used in disclosing the present invention, including technical and scientific terms, have the meanings commonly understood by one of ordinary skill in the art to which this invention belongs. As a further guide, term definitions are included to better understand the teachings of the present invention.

[0016] Hydroxyl-terminated epoxidized unsaturated polyolefin The photocurable composition of the present invention comprises at least one first hydroxyl-terminated, epoxidized, unsaturated polyolefin having an epoxide equivalent weight of less than 250 g / eq and at least one second hydroxyl-terminated, epoxidized, unsaturated polyolefin having an epoxide equivalent weight of 250 g / eq or greater, wherein the weight ratio of the first hydroxyl-terminated, epoxidized, unsaturated polyolefin to the second hydroxyl-terminated, epoxidized, unsaturated polyolefin is 2:5 to 6:5.

[0017] The hydroxyl-terminated epoxidized unsaturated polyolefin of the present invention refers to a polyolefin having at least one non-aromatic double bond, at least one epoxy group, and at least one terminal hydroxyl group per molecule. Preferably, the hydroxyl-terminated epoxidized unsaturated polyolefin contains at least two terminal hydroxyl groups per molecule.

[0018] In some embodiments of the present invention, the hydroxyl-terminated epoxidized unsaturated polyolefin is a hydroxyl-terminated epoxidized polydiene, which is preferably selected from hydroxyl-terminated epoxidized polyisoprene, hydroxyl-terminated epoxidized polybutadiene, hydroxyl-terminated epoxidized copolymers of isoprene and butadiene, hydroxyl-terminated epoxidized copolymers of butadiene and ethylene, hydroxyl-terminated epoxidized copolymers of butadiene and propylene, and hydroxyl-terminated epoxidized terpolymers of butadiene, ethylene, and propylene. Specific examples of hydroxyl-terminated epoxidized unsaturated polyolefins are shown below.

[0019] TIFF0007785090000001.tif26154

[0020] In the formula, p and q represent the number of repeats of the epoxidized olefin monomer unit in [ ]; p and q are integers of 0 or greater, and p and q cannot both be 0 at the same time; m and n represent the number of repeats of the unsaturated comonomer unit in [ ]; m and n are integers of 0 or greater, and m and n cannot both be 0 at the same time.

[0021] An example of a commercially available first hydroxyl-terminated epoxidized unsaturated polyolefin is, for example, EPOLEAD PB3600 available from Daicel Corporation.

[0022] Examples of commercially available second hydroxyl-terminated epoxidized unsaturated polyolefins are, for example, Poly bd 600E and 605E available from Cray Valley.

[0023] In some embodiments of the present invention, the first hydroxyl-terminated epoxidized unsaturated polyolefin preferably has an epoxide equivalent weight of from 100 to 230 g / eq, more preferably from 150 to 200 g / eq, measured according to ISO 3001-1997.

[0024] In some embodiments of the present invention, the second hydroxyl-terminated epoxidized unsaturated polyolefin preferably has an epoxide equivalent weight of 260 to 600 g / eq, more preferably 280 to 380 g / eq, measured according to ISO 3001-1997.

[0025] In some embodiments of the present invention, the amount of the first hydroxyl-terminated epoxidized unsaturated polyolefin is preferably 5 to 20 wt %, more preferably 8 to 14 wt %, based on the total weight of the photocurable adhesive composition.

[0026] In some embodiments of the present invention, the amount of the second hydroxyl-terminated epoxidized unsaturated polyolefin is preferably 8 to 25 wt %, more preferably 10 to 20 wt %, based on the total weight of the photocurable adhesive composition.

[0027] In some embodiments of the present invention, when the weight ratio of the first hydroxyl-terminated epoxidized unsaturated polyolefin to the second hydroxyl-terminated epoxidized unsaturated polyolefin is 4:5 to 1:1, the elongation properties of the cured product of the photocurable adhesive composition can surprisingly be further improved.

[0028] Dimer acid modified epoxy resin The photocurable adhesive composition of the present invention contains at least one dimer acid-modified epoxy resin. The dimer acid-modified epoxy resin of the present invention refers to a resin obtained by reacting at least one carboxyl group in the dimer acid structure with a multifunctional epoxy resin. The dimer acid is a dimer of an unsaturated fatty acid such as oleic acid, elaidic acid, cetoleic acid, sorbic acid, or linoleic acid. The epoxy resin is not limited and may be any common epoxy resin known in the art.

[0029] The epoxy equivalent of the dimer acid-modified epoxy resin is not particularly limited, but in some embodiments, the dimer acid-modified epoxy resin preferably has an epoxy equivalent of 300 to 600 g / eq as measured in accordance with ISO 3001-1997.

[0030] Examples of commercially available dimer acid-modified epoxy resins include YD-171 and YD-172 available from Kukdo Chemical Co., Ltd.; and jER871 and jER872 available from Mitsubishi Chemical Corporation.

[0031] In some embodiments of the present invention, the amount of dimer acid-modified epoxy resin is preferably 3 to 25 wt %, more preferably 10 to 20 wt %, based on the total weight of the photocurable adhesive composition.

[0032] Core-shell reinforcement The photocurable adhesive composition of the present invention contains at least one core-shell toughening agent to enhance the elongation properties of the cured product of the photocurable adhesive composition. The core-shell toughening agent used in the present invention may be any core-shell polymer (also called core-shell rubber) known in the art. Typically, a core-shell rubber has a core comprising a polymeric material with rubber properties and a shell grafted to or crosslinked to the core. The core of the core-shell rubber may be selected from acrylic rubber, silicone rubber, and diene rubber. The shell of the core-shell rubber may be selected from acrylic polymers, acrylic copolymers, styrene polymers, and styrene copolymers. Core-shell rubbers include, but are not limited to, acrylonitrile butadiene styrene (ABS), methacrylate butadiene styrene (MBS), methacrylate acrylonitrile butadiene styrene (MABS), and the like.

[0033] Examples of commercially available core-shell tougheners include, for example, MX-550, MX-551, and MX-553 available from Kaneka Corporation.

[0034] In some embodiments of the present invention, the amount of core-shell toughening agent is 3 to 15 wt %, preferably 6 to 10 wt %, based on the total weight of the photocurable adhesive composition.

[0035] Polyol component The photocurable composition of the present invention comprises at least one polyol component. The term "polyol" in the present invention refers to a compound containing two or more hydroxyl groups. The polyol component of the present invention may be any common polyol other than the hydroxyl-terminated epoxidized unsaturated polyolefin described above in the present invention. Examples of polyol components include, but are not limited to, polyether polyols, polyester polyols, and polymer polyols.

[0036] Examples of commercially available polyol components are, for example, WANOL F-3135 available from Wanhua Chemical; TEP-330N available from the No. 3 Petrochemical Plant of Tianjin Petrochemical Company; GEP-330N available from Sinopec Shanghai Gaoqiao Petrochemical Company; and Voranol 220-110N available from Dow.

[0037] In some embodiments of the present invention, the amount of the polyol component is 1 to 9 wt %, preferably 3 to 8 wt %, based on the total weight of the photocurable adhesive composition.

[0038] Cationic Photoinitiators The photocurable adhesive composition of the present invention contains at least one cationic photoinitiator to initiate the polymerization of the epoxy resin. The cationic photoinitiator forms an excited state upon irradiation and then decays to release a radical cation. This radical cation reacts with a hydrogen atom donor to generate a protonic acid that initiates the crosslinking reaction.

[0039] The most commonly used cationic photoinitiators are organic halonium salts, iodonium salts, or sulfonium salts. In some embodiments of the present invention, organic iodonium salts or organic sulfonium salts are preferably incorporated into the photocurable adhesive composition. The anions in these salts generally have low nucleophilicity and include, but are not limited to, SbF6, PF6, AsF6, BF4, B(CF5)4, or Ga(CF5)4. The iodonium salt may be selected from, for example, diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate, 4-octyloxyphenylphenyliodonium hexafluoroantimonate, 4-(2-hydroxytetradecyloxyphenyl)phenyliodonium hexafluoroantimonate, and 4-(1-methylethyl)phenyl 4-methylphenyliodonium tetrakis(pentafluorophenyl)borate. The sulfonium salt may be selected from, for example, 4-thiophenylphenyldiphenylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, and triarylsulfonium hexafluoroantimonate. The cationic photoinitiators can be used alone or in combination.

[0040] Examples of commercially available cationic photoinitiators include, for example, Irgacure 290 available from BASF; UVI-6976, 6992 available from Nantong Synasia New Material Co., Ltd; and UVI 6976 available from Dow.

[0041] In some embodiments of the present invention, the amount of cationic photoinitiator is 0.1 to 10 wt %, preferably 3 to 5 wt %, based on the total weight of the photocurable adhesive composition.

[0042] Optional additives The photocurable adhesive composition may further comprise optional additives. The selection of suitable additives for the photocurable adhesive composition of the present invention depends on the specific intended use of the photocurable adhesive composition and can be determined for each case by one skilled in the art.

[0043] <Reactive epoxy diluent> The photocurable adhesive composition of the present invention may optionally contain at least one reactive epoxy diluent, which helps to adjust the flow characteristics of the adhesive composition. The reactive epoxy diluent of the present invention refers to a compound containing at least one epoxy group in its molecular structure, and is different from the hydroxyl-terminated epoxidized unsaturated polyolefin and dimer acid-modified epoxy resin described above in the present invention. Preferably, the reactive epoxy diluent has a viscosity of less than 3000 CPS at 25°C, e.g., 10 to 2000 CPS, 50 to 1000 CPS, or 100 to 500 CPS, as measured in accordance with ASTM D1084-2016. Suitable reactive epoxy diluents include, but are not limited to, aliphatic epoxy resins (such as propylene glycol diglycidyl ether and pentaerythritol polyglycidyl ether), cycloaliphatic epoxy resins (such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis(3,4-epoxycyclohexylmethyl)adipate), and heterocyclic epoxy resins (such as triglycidyl isocyanurate).

[0044] The epoxy equivalent weight of the reactive epoxy diluent is not particularly limited, but in some embodiments, the reactive epoxy diluent preferably has an epoxy equivalent weight of less than 250 g / eq, such as 50 g / eq, 100 g / eq, and 200 g / eq, measured according to ISO 3001-1997.

[0045] Examples of commercially available reactive epoxy diluents are, for example, Epodil 749, 757 available from Air Products; Araldite CY179, 184, 192 available from Ciba Specialty Chemicals; Aron Oxetane OXT 101 available from Toagosei Co., Ltd.; and Syna-Epoxy S21, 27, 28 available from Nantong Synasia New Material Co., Ltd.

[0046] In some embodiments of the present invention, the amount of reactive epoxy diluent is 0 to 60 wt %, preferably 15 to 50 wt %, based on the total weight of the photocurable adhesive composition.

[0047] <Coupling agent> The photocurable adhesive composition of the present invention may optionally contain at least one coupling agent. The coupling agent of the present invention may be any common coupling agent known in the art. The coupling agent may be selected from silane coupling agents, titanate coupling agents, and the like. The coupling agents of the present invention may be used alone or in combination. Silane coupling agents include epoxy-containing alkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; amino-containing alkoxysilanes such as gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltriisopropoxysilane, and gamma-aminopropylmethyldimethoxysilane; and mercapto-containing alkoxysilanes such as 3-mercaptopropyltrimethoxysilane. Titanate-based coupling agents include i-propoxytitanium tri(isostearate).

[0048] Examples of commercially available coupling agents include, for example, KMB403, KMB603 available from Shin-Etsu Chemical Co., Ltd.; SILQUEST A187, SILQUEST A1120 available from Momentive; KH570 available from Dowcorning; and GENIOSIL GF9 available from Wacker Chemie AG.

[0049] In some embodiments of the present invention, the amount of coupling agent is preferably 0 to 5 wt %, more preferably 1 to 3 wt %, based on the total weight of the photocurable adhesive composition.

[0050] <Coloring agent> The photocurable adhesive composition of the present invention may optionally contain at least one colorant, examples of which include, but are not limited to, inorganic or organic colorants such as ferric oxide, brick powder titanium dioxide, bromothymol blue, brilliant blue, and fenothalin.

[0051] Examples of commercially available colorants are, for example, Stan-Tone 25EPX01 Red and Solvent Red 24 available from Dintex Dyechem. In some embodiments of the present invention, the amount of colorant is preferably 0 to 1 wt %, more preferably 0.1 to 0.2 wt %, based on the total weight of the photocurable adhesive composition.

[0052] Other optional additives that may be used in the photocurable adhesive composition of the present invention include, but are not limited to, biocides, fillers, and mixtures thereof.

[0053] In a preferred embodiment, the photocurable adhesive composition comprises: (a) 8% to 14% by weight of at least one first hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of less than 250 g / equivalent; (b) 10% to 20% by weight of at least one second hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of 250 g / equivalent or greater; (c) 10 wt% to 20 wt% of at least one dimer acid-modified epoxy resin; (d) 6 wt.% to 10 wt.% of at least one core-shell toughening agent; (e) 3% to 8% by weight of at least one polyol component; (f) 3% to 5% by weight of at least one cationic photoinitiator; (g) 15% to 50% by weight of at least one reactive epoxy diluent; (h) 1% to 3% by weight of at least one coupling agent; and (i) 0% to 0.2% by weight of at least one colorant; where: The weight percentages of all components add up to 100% by weight; and The weight ratio of the first hydroxyl-terminated epoxidized unsaturated polyolefin to the second hydroxyl-terminated epoxidized unsaturated polyolefin is 2:5 to 6:5.

[0054] Those skilled in the art will be able to make appropriate selections from among the various ingredients based on the description, representative examples and guidelines of the present invention to prepare compositions that achieve the desired effects.

[0055] The photocurable adhesive composition of the present invention can be prepared by uniformly mixing all of the components, preferably by the following steps. a) mixing all ingredients except the photoinitiator and colorant together to form a premix; b) adding colorant to the premix while continuously stirring; and c) adding a photoinitiator into the premix and mixing all ingredients under yellow light and vacuum.

[0056] The photocurable adhesive composition of the present invention can be applied to a substrate via a scalper, sprayer, dispenser, or extruder, and cured under UV light. Suitable substrates include, but are not limited to, metals (steel, stainless steel, carbon steel, iron, copper, aluminum, zinc, etc., including alloys thereof), carbon fiber, glass fiber, glass, wood, plastic, woven materials, nonwoven materials, and mixtures thereof.

[0057] In some embodiments of the present invention, the photocurable adhesive composition has a viscosity of 2000 to 3000 mj / cm 2 Intensity (2200, 2500, 2700mJ / cm 2 It is preferable that the adhesive is cured by an LED 365 (such as a LED 365) for 10 to 30 seconds (such as 15 or 20 seconds).

[0058] The cured product of the photocurable adhesive composition has excellent elongation properties and is particularly useful for protecting curved glass or glass with rounded corners during the glass slimming process. Furthermore, glass protected with the cured product of the photocurable adhesive composition can be thinned to approximately 0.2 mm due to the excellent acid resistance of the cured product of the photocurable adhesive composition.

[0059] In some embodiments of the present invention, the cured product of the photocurable adhesive composition preferably has an elongation at break, measured according to ASTM D638, of 10% or more, more preferably 15% or more, and even more preferably 20% or more. [Example]

[0060] Working Example: The present invention will be further described and illustrated with reference to the following examples. The examples are intended to help those skilled in the art better understand and practice the present invention, but are not intended to limit the scope of the present invention. All numerical values ​​in the examples are by weight unless otherwise specified. [Example]

[0061] Examples 1-16 The following materials were used in the examples: YD-171 (dimer acid modified epoxy resin, available from Kukdo Chemical Co., Ltd.); MX553 (a 30% concentration of 100 nm PBd core-shell rubber (CSR) particles in a low-viscosity, low-chlorine cycloaliphatic epoxy resin, available from Kaneka Corporation); EPOLEAD PB3600 (hydroxyl-terminated epoxidized unsaturated polyolefin with an epoxide equivalent weight of 193 g / eq, available from Daicel Corporation); Poly bd 605E (hydroxyl-terminated epoxidized unsaturated polyolefin with an epoxide equivalent weight of 300 g / eq, available from Cray Valley); Stan-Tone 25EPX01 Red (colorant, available from PolyOne); Voranol 220-110N (polyol, available from Dow); Syna epoxy 28 (bis(3,4-epoxycyclohexylmethyl) adipate with a viscosity of 500-650 CPS at 25°C, available from Nantong Synasia New Material Co., Ltd.); Aron Oxetane OXT 101 (3-ethyl-3-hydroxymethyl oxetane with a viscosity of 17 to 22 CPS at 25°C, manufactured by Toagosei Co., Ltd.); SILQUEST A187 (epoxy-functional silane, available from Momentive); UVI 6976 (mixture of triarylsulfonium hexafluoroantimonates in propylene carbonate, available from Dow):

[0062] TIFF0007785090000002.tif34140

[0063] A photocurable adhesive composition was prepared as an example (Ex.) using the ingredients and weight percentages according to Table 1 by the following steps. a) Dimer acid-modified epoxy resin (YD-171), core-shell toughening agent (MX553), hydroxyl-terminated epoxidized unsaturated polyolefin (EPOLEAD PB3600 and / or Poly bd 605E), polyol component (Voranol 220-110N), reactive epoxy diluent (Syna Epoxy 28 and Aron Oxetane OXT 101), and coupling agent (SILQUEST A187) are mixed at a speed of 1000 r / min for 30 seconds, then at a speed of 2000 r / min for 60 seconds to form a premix. b) Add colorant (Stan-Tone 25EPX01 Red) to the premix and mix for 30 seconds at a speed of 1000 r / min, then mix for 60 seconds at a speed of 2000 r / min. c) Under yellow light and vacuum (the vacuum was controlled at about -0.09 MPa), add the photoinitiator (UVI6976) to the premix, and mix all the components at a speed of 1000 r / min for 30 seconds, then at a speed of 2000 r / min for 60 seconds.

[0064] The light-curable adhesive samples were subjected to various tests, the results of which are shown in Tables 2-3.

[0065] TIFF0007785090000003.tif71170

[0066] TIFF0007785090000004.tif71170

[0067] Test Method <Acid resistance> The photocurable adhesive sample was coated onto a glass substrate to form a wet film approximately 200 μm thick, and the glass coated with the wet film was then exposed to Hg-UV light (786 mj / cm). 2 ) for 20 seconds to cure.

[0068] The film-coated glass substrate was immersed in a sulfuric acid solution (35% by weight) for 24 hours in an environment of 23°C and 50% humidity.

[0069] The acid resistance of the film was evaluated as follows. The acid resistance of the cured light-curable adhesive sample was rated as "pass" if the film was free of corrosion, bubbles, or discoloration and could be easily peeled from the glass in a continuous manner without cracking; and The acid resistance of the cured light-curable adhesive sample was rated "fail" if the film was corroded, blistered, discolored, or broke during the peeling process.

[0070] <Elongation characteristics> The light-curable adhesive samples were cured and tested using the following procedure. a) A mold (size: 200 x 200 x 1 mm) is placed on a horizontally placed glass substrate. b) The mold is filled with the light-curable adhesive sample to form a 1 mm thick wet film. c) A second glass substrate is placed on top of the mold, sealing the wet film between the two glass substrates. d) The encapsulated wet film was irradiated with Hg-UV light (786 mj / cm 2 ) and irradiate for 20 seconds. e) Turn the encapsulated wet film over and expose it to Hg-UV light (786 mj / cm 2 ) for another 20 seconds. f) The encapsulated wet film was turned over again and exposed to Hg-UV light (786 mj / cm 2 ) for 20 seconds to form a dry film. g) Prepare sample films from the dry film according to ASTM D638. h) Store the sample film at 23°C and 50% humidity for 24 hours before testing; and i) Measure the elongation at break of the sample film according to ASTM D638.

[0071] Test results TIFF0007785090000005.tif16148

[0072] TIFF0007785090000006.tif16146

[0073] The acid resistance of the cured light-curable adhesive samples is reported in Tables 2a and 2b. When the first hydroxyl-terminated epoxidized unsaturated polyolefin (EPOLEAD PB3600) was missing from the light-curable adhesive composition sample or when too much polyol component (Voranol 220-110N) was added to the light-curable adhesive composition sample, the acid resistance of the cured light-curable adhesive sample was poor.

[0074] TIFF0007785090000007.tif21167

[0075] TIFF0007785090000008.tif21168

[0076] The elongation properties of the cured photocurable adhesive samples are reported in Tables 3a and 3b. When the weight ratio of the first hydroxyl-terminated epoxidized unsaturated polyolefin to the second hydroxyl-terminated epoxidized unsaturated polyolefin was not in the range of 2:5 to 6:5, or when the polyol component or the dimer acid-modified epoxy resin (YD-171) was missing from the photocurable adhesive composition sample, the cured photocurable adhesive sample had poor elongation properties. Preferred aspects of the present invention include the following. [1] a) at least one first hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of less than 250 g / equivalent; b) at least one second hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of 250 g / eq or greater; c) at least one dimer acid modified epoxy resin; d) at least one core-shell toughener; e) at least one polyol component; and f) at least one cationic photoinitiator; A photocurable adhesive composition comprising: where: the weight ratio of the first hydroxyl-terminated epoxidized unsaturated polyolefin to the second hydroxyl-terminated epoxidized unsaturated polyolefin is 2:5 to 6:5; The amount of the core-shell toughener is 3 wt% to 15 wt%, based on the total weight of the adhesive composition; and The amount of the polyol component is 1 to 9 wt % based on the total weight of the adhesive composition. Photocurable adhesive composition. [2] The photocurable adhesive composition according to [1], wherein the first hydroxyl-terminated epoxidized unsaturated polyolefin preferably has two terminal hydroxyl groups per molecule. [3] The photocurable adhesive composition according to [1] or [2], wherein the second hydroxyl-terminated epoxidized unsaturated polyolefin preferably has two terminal hydroxyl groups per molecule. [4] The photocurable adhesive composition according to any one of [1] to [3], wherein the first hydroxyl-terminated epoxidized unsaturated polyolefin has an epoxide equivalent weight of preferably 100 to 230 g / equivalent, more preferably 150 to 200 g / equivalent. [5] The photocurable adhesive composition according to any one of [1] to [4], wherein the second hydroxyl-terminated epoxidized unsaturated polyolefin has an epoxide equivalent weight of preferably 260 to 600 g / equivalent, more preferably 280 to 380 g / equivalent. [6] The photocurable adhesive composition according to any one of [1] to [5], wherein both the first and second hydroxyl-terminated epoxidized unsaturated polyolefins are preferably hydroxyl-terminated epoxidized polydiene. [7] The photocurable adhesive composition according to any one of [1] to [6], wherein the amount of the first hydroxyl-terminated epoxidized unsaturated polyolefin is preferably 5 to 20 wt %, more preferably 8 to 14 wt %, based on the total weight of the adhesive composition. [8] The photocurable adhesive composition according to any one of [1] to [7], wherein the amount of the second hydroxyl-terminated epoxidized unsaturated polyolefin is preferably 8 to 25 wt %, more preferably 10 to 20 wt %, based on the total weight of the adhesive composition. [9] The photocurable adhesive composition according to any one of [1] to [8], wherein the amount of the polyol component is preferably 3 to 8 wt % based on the total weight of the adhesive composition.

[10] The photocurable adhesive composition according to any one of [1] to [9], wherein the weight ratio of the first hydroxyl-terminated epoxidized unsaturated polyolefin to the second hydroxyl-terminated epoxidized unsaturated polyolefin is preferably 4:5 to 1:1.

[11] The photocurable adhesive composition according to any one of [1] to

[10] , wherein the cationic photoinitiator is selected from an organic halonium salt, an organic iodonium salt, an organic sulfonium salt, or any combination thereof.

[12] (a) 8% to 14% by weight of at least one first hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of less than 250 g / equivalent; (b) 10% to 20% by weight of at least one second hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of 250 g / equivalent or greater; (c) 10 wt% to 20 wt% of at least one dimer acid-modified epoxy resin; (d) 6 to 10 wt. % of at least one core-shell toughening agent; (e) 3 to 8 weight percent of at least one polyol component; (f) 3-5 wt. % of at least one cationic photoinitiator; (g) 15 to 50 wt. % of at least one reactive epoxy diluent; (h) 1 to 3 wt. % of at least one coupling agent; and (i) 0 to 0.2 wt. % of at least one colorant; where: The weight percentages of all components add up to 100% by weight; and The weight ratio of the first hydroxyl-terminated epoxidized unsaturated polyolefin to the second hydroxyl-terminated epoxidized unsaturated polyolefin is 2:5 to 6:5. The photocurable adhesive composition according to any one of [1] to

[11] .

[13] a) mixing all ingredients except the photoinitiator and colorant together to form a premix; b) adding colorant to the premix while continuously stirring; and c) adding a photoinitiator to the premix and mixing all ingredients under yellow light and vacuum. A method for producing the photocurable adhesive composition according to any one of [1] to

[12] , comprising:

[14] A cured product of the photocurable adhesive composition according to any one of [1] to

[13] .

[15] An article coated or bonded with a cured product of the photocurable adhesive composition according to

[14] .

Claims

1. Based on the total weight of the adhesive composition a) 5 to 20 weight percent of at least one first hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of less than 250 g / equivalent; b) 8 to 25 weight percent of at least one second hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of 250 g / eq or greater; c) 3% to 25% by weight of at least one dimer acid-modified epoxy resin; d) at least one core-shell toughening agent; e) at least one polyol component; and f) at least one cationic photoinitiator; A photocurable adhesive composition comprising: where: the weight ratio of the first hydroxyl-terminated epoxidized unsaturated polyolefin to the second hydroxyl-terminated epoxidized unsaturated polyolefin is from 2:5 to 6:5; The amount of core-shell toughener is 3% to 15% by weight based on the total weight of the adhesive composition; and The amount of the polyol component is 1 to 9 wt % based on the total weight of the adhesive composition. Photocurable adhesive composition.

2. 2. The photocurable adhesive composition of claim 1, wherein the first hydroxyl-terminated epoxidized unsaturated polyolefin has two terminal hydroxyl groups per molecule.

3. 3. The photocurable adhesive composition of claim 1, wherein the second hydroxyl-terminated epoxidized unsaturated polyolefin has two terminal hydroxyl groups per molecule.

4. The photocurable adhesive composition of any one of claims 1 to 3, wherein the first hydroxyl-terminated epoxidized unsaturated polyolefin has an epoxide equivalent weight of 100 to 230 g / eq.

5. The photocurable adhesive composition of any one of claims 1 to 4, wherein the second hydroxyl-terminated epoxidized unsaturated polyolefin has an epoxide equivalent weight of 260 to 600 g / eq.

6. 6. The photocurable adhesive composition according to claim 1, wherein both the first and second hydroxyl-terminated epoxidized unsaturated polyolefins are hydroxyl-terminated epoxidized polydiene.

7. 7. The photocurable adhesive composition according to claim 1, wherein the amount of the first hydroxyl-terminated epoxidized unsaturated polyolefin is 8 to 14 wt %, based on the total weight of the adhesive composition.

8. 8. The photocurable adhesive composition according to claim 1, wherein the amount of the second hydroxyl-terminated epoxidized unsaturated polyolefin is 10 to 20 wt %, based on the total weight of the adhesive composition.

9. 9. The photocurable adhesive composition according to claim 1, wherein the amount of the polyol component is 3 to 8 wt % based on the total weight of the adhesive composition.

10. 10. The photocurable adhesive composition according to claim 1, wherein the weight ratio of the first hydroxyl-terminated epoxidized unsaturated polyolefin to the second hydroxyl-terminated epoxidized unsaturated polyolefin is from 4:5 to 1:

1.

11. The photocurable adhesive composition according to any one of claims 1 to 10, wherein the cationic photoinitiator is selected from an organic halonium salt, an organic iodonium salt, an organic sulfonium salt, or any combination thereof.

12. (a) 8% to 14% by weight of at least one first hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of less than 250 g / equivalent; (b) 10% to 20% by weight of at least one second hydroxyl-terminated epoxidized unsaturated polyolefin having an epoxide equivalent weight of 250 g / eq or greater; (c) 10% to 20% by weight of at least one dimer acid-modified epoxy resin; (d) 6 to 10 wt. % of at least one core-shell toughening agent; (e) 3 to 8 weight percent of at least one polyol component; (f) 3 to 5 wt. % of at least one cationic photoinitiator; (g) 15 to 50 wt. % of at least one reactive epoxy diluent; (h) 1 to 3 wt. % of at least one coupling agent; and (i) 0 to 0.2 wt. % of at least one colorant; where: The weight percentages of all components add up to 100% by weight; and The weight ratio of the first hydroxyl-terminated epoxidized unsaturated polyolefin to the second hydroxyl-terminated epoxidized unsaturated polyolefin is from 2:5 to 6:

5. The photocurable adhesive composition according to any one of claims 1 to 11.

13. a) mixing all ingredients except the photoinitiator and colorant together to form a premix; b) adding colorant to the premix while continuously stirring; and c) adding a photoinitiator to the premix and mixing all ingredients under yellow light and vacuum A method for producing the photocurable adhesive composition according to any one of claims 1 to 12, comprising:

14. A cured product of the photocurable adhesive composition according to any one of claims 1 to 13.

15. An article coated or bonded with a cured product of the photocurable adhesive composition of claim 14.

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