WO2009067112A1 - Redox-induced cationically polymerizable compositions with low cure temperature - Google Patents
Redox-induced cationically polymerizable compositions with low cure temperature Download PDFInfo
- Publication number
- WO2009067112A1 WO2009067112A1 PCT/US2007/085272 US2007085272W WO2009067112A1 WO 2009067112 A1 WO2009067112 A1 WO 2009067112A1 US 2007085272 W US2007085272 W US 2007085272W WO 2009067112 A1 WO2009067112 A1 WO 2009067112A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- cationically
- polymeπzable
- electron
- vinyl
- Prior art date
Links
- 0 CCC(COC1)*1O Chemical compound CCC(COC1)*1O 0.000 description 4
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
Definitions
- This invention relates to a redox-induced cationically polyme ⁇ zable composition that exhibits reduced cure temperature and to a method for reducing the cure temperature of a cationically polyme ⁇ zable composition.
- processing speed leads to higher throughput and lower assembly costs
- processing speed can be increased if the adhesive, coating, or encapsulant can be cured quickly at a relatively low curing temperature
- a common mode of eiectronic packaging involves affixing semiconductor devices onto substrates by means of an adhesive or encapsulant.
- the more prominent uses are the bonding of integrated circuit chips to metal lead frames or organic substrates, and the bonding of circuit packages or assemblies to printed wire boards, including, for example, die attach for array package, die attach for RFID package, and component attach for ink jet cartridge assembly.
- low temperature cure assembly can minimize jetting trajectory distortion and improve printing quality
- temperature-sensitive components or substrates such as, the paper-based antenna in RFID application and camera sensor in organic substrates
- low temperature interconnect is very desirable
- polyme ⁇ zable compositions that cure at low temperatures, preferably iess than 100 0 C
- This invention is a polyme ⁇ zable composition
- a polyme ⁇ zable composition comprising ( ⁇ ) a cationicaliy polyme ⁇ zable resin, ( ⁇ ) an onium salt, (in) an azo or peroxide initiator, and (iv) an electron-rich vinyl resin
- this invention is a polyme ⁇ zable composition
- a polyme ⁇ zable composition comprising (i) a cationicaiiy polymerizable resin, ( ⁇ ) an onium salt, (iii) an azo or peroxide initiator, and (iv) a catalytic or substoichiometric amount of an electron-rich vinyl resin
- this invention is method for reducing the cure temperature of a cationicaiiy poSyme ⁇ zable resin, in which the cure of the resin is catalyzed by the addition of an onium salt and an azo or peroxide initiator to the resin, the method comprising adding an electron-rich vinyl resin to the mixture of resin, onium salt and azo or peroxide initiator
- this invention is method for reducing the cure temperature of a cationicaiiy polymerizable resin, in which the cure of the resin is catalyzed by the addition of an onium salt and an azo or peroxide initiator to the resin, the method comprising adding a catalytic or substoichiometric amount of an eiectron-rich vinyl resin to the mixture of resin, onium salt and azo or peroxide initiator
- a curable resin is one that is polyme ⁇ zable with or without crosslinking Curable and poiyme ⁇ zable are used interchangeably and a cationically curable resin or composition is one that is poiyme ⁇ zable Any cationically polyme ⁇ zable resin may be used in the above reaction
- Exemplary cationically polymerizable resins include oxetanes, epoxies, spiroorthocarbonates, spiroorthoesters, and benzoxazines, or a mixture of any of those
- Suitable oxetane resins are those disclosed in US patents 7,034,064, 6,982,338, 6,953,862, 6,943,258, 6,753,434, and those available from Toagosei Corporation under the tradenames OXT-221 , OXT-121 , OXT-101 , OXT-212, OXT-211 , CHOX 1 OX-SC, PNOX-1009, having the structures
- Suitable epoxy resins include bisphenol epoxies, naphthalene epoxies, and aliphatic type epoxies
- Commercially available materials include bisphenol type epoxy resins (for example, those sold under the tradenames EPICLON 830LVP, 830CRP, 835LV, 850CRP, available from Dainippon Ink & Chemicals, lnc ), naphthalene type epoxy resins (for example, those sold under the tradenames EPICLON HP4032, available from Dainippon Ink & Chemicals, lnc ), aliphatic epoxy resins (for example, those sold under the tradenames ARALDITE CYI 79, 184, 192, 175, 179, available from Ciba Specialty Chemicals, EPOXY 1234, 249, 206, available from Dow Corporation, and EHPE-3150, available from Daicel Chemical Industries, Ltd )
- epoxy resins include cycloaliphatic epoxy resins, for example, 3,4- epoxy-cyciohexylmethyl 3,4-epoxycyclohexanecarboxylate , available as ERL-4221 from Union carbide and ARALDITE CY-179, available from Ciba-Geigy, diglycidylester of hexahydro-phthahc anhydride, available as CY-184 from Ciba-Geigy, b ⁇ s(3,4- epoxycyclohexylmethyl)-ad ⁇ pate, available as ERL-4229 from Union carbide, and other bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, epoxy novolac resins, biphenyl type epoxy resins, naphthalene type epoxy resins, and dicyclopentadienephenol type epoxy resins, all commercially available from different sources
- Exemplary spiroorthocarbonate and vinyl spiroorthocarbonates include those having the following structures
- Exemplary electron-rich vinyl spirocarbonates include those having the following structures:
- Exemplary spiroorthoesters include
- Suitable benzoxazines include those compounds containing the structure
- R and R are any organic moiety, including another benzoxazine structure
- Exemplary benzoxazine compounds include those of the formulae
- R 1 is a divalent radical that may be aliphatic, aromatic, or a combination of aliphatic and aromatic, and that may contain heteroatoms, such as oxygen, nitrogen, sulfur, phosphorous, or halogen, or that may be a single bond, or that may be S, S 2 , SO, SO 2 , O, or CO, and R 2 is hydrogen, an alkyl or substituted alkyl, an aromatic or substituted aromatic
- the benzoxazine may also be present in a polymeric species, such as depicted in the following structure: which R 1 is as described above, ⁇ is an integer that will vary depending on the polymeric composition from which the benzoxazine depends, and each Q is a polymeric entity, for example, polyurethane, polyether, polyester, poly(butad ⁇ ene) or polystyre ⁇ ic
- Exemplary onium salts include iodonium salts, sulfonium salts, diazonium salts, ammonium salts or a mixture of those salts
- the onium salt is an
- X is any suitable counter anion, for example, a halogen anion, CF 3 SO 3 , C 6 H 5 SO 3 ' , NO 3 " , AsF 6 " , SbF 6 " , FeCI 4 “ , SbCI 6 “ , BF 4 " , PF 6 “ , and (C 6 F 5 )B "
- iodonium salts include (p-lsopropylphenyj)(p- methylphenyl) iodonium tetrak ⁇ s(pentafluorophenyl)borate from Gelest as RHODORSIL 2074, and bisdodecyl phenyliodonium hexafluoroantimonate as UV 9380 from General Electric
- the onium salts are used in an effective amount In one embodiment, an effective amount is in the range of 0 1 to 10% by weight of the total resin
- Exemplary azo initiators include, for example, azoisobutylonit ⁇ le, 2,2"- azobispropane, 2,2'-azobis(2-methylbutanenitnle), and m.m'-azoxystyrene
- azo initiators are those available from Wako Specialty Company, such as those sold under the tradenames VA-044, VA-057, VA-085, V-70, VF-096, V-65, V-601 , V-59, V-40, VF-096, V-30, and those available from Akzo Nobel, such as those sold under the tradenames PERKADOX ACCN, PERKADOX AIBN 1 PERKADOX AMBN-GR, and those available from Dupont, such as those sold under the tradenames VAZO-52, VAZO-64, VAZO-67 and VAZO-88
- the azo initiators are used in an effective amount In one embodiment an effective amount ranges from 0 1 to 10% by weight of the total resin
- Exemplary peroxide initiators include those commercially available from Akzo Nobel, such as those sold under the tradenames PERKADOX and TRIGONOX Other peroxide initiators are suitable, provided they generate radicals with the vinyl resin for reaction with the onium salt
- Exemplary peroxides include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, butyl peroctoate, dicumyl peroxide, acetyl peroxide, para- chlorobenzoyl peroxide and di-t-butyl diperphthalate
- the peroxide initiators are used in an effective amount In one embodiment an effective amount ranges from 0 1 to 10% by weight of the total resin content
- Exemplary electron-rich vinyl resins include vinyl ethers, spirocyctic vinyl ethers, styrenics (compounds containing a styrene moiety), cinnamyls (in this specification and claims compounds containing a cinnamyl moiety), N-v ⁇ nylam ⁇ des, and N-vinylamines
- Suitable vinyl ether resins include, for example, poly(butad ⁇ enes), poly(carbonates), poiy(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, ester, or ether, which also contain vinyl ether functionality
- Suitable commercially available vinyl ether resins include cyclohexane-dimethanol divinylether, dodecylvinylether, cyclohexyl vinylether, 2-ethylhexyl vinylether, dipropyleneglycol divinylether, hexanediol divinylether, octadecylvinylether, and butandiol divinylether, available from International Specialty Products (ISP), vinyl ethers sold under the tradenames VECTOMER 4010, 4020, 4030, 4040, 4051 , 4210, 4220
- Suitable spirocyciic vinyl ethers include, for example, those having the structures
- Suitable styrenic resins include, for example, those disclosed in US patents 6,953,862, 6,908,969, 6,908,957, 6,809,155, 6,803,406, 6,716,992, 6,441 ,213, 6,441 ,121, 6,307,001 , 6,300,456, and those commercially available styrene, substituted styrenics, divinyl benzene, diphenylethylene, and any other resins possessing styrenic functionality (hereinafter styrenics) Such resins can be, for example, polyesters, carbamates, ureas Exemplary styrenic resins include compounds having the following structures in which R is an aliphatic or aromatic hydrocarbon, including those with heteroatoms.
- Suitable cinnamyl resins include, for example, those disclosed in US patents 6,943,258, 6,753,434, 6,716,992, 6,908,969, 6,908,957, 6,809,155, 6,803,406, 6,753,434, 6,570,032, 6,441,121, 6,307,001 , 6,300,456
- the cinnamyl compounds can be any small molecule, oligome ⁇ c, or polymeric material that contains a cinnamy! functionality
- N-vinylamide resins include, for example, N-v ⁇ nyl- pyrrohdone, N-vinylformamide, and N-vinylcaprolactone
- N-v ⁇ nylam ⁇ nes include, for example, N- vinylcarbazole, N-vinylpyrrole, N-vinylimidazole, and 2-methyl-N-v ⁇ nyl ⁇ midazole
- this invention is a method for polymerizing a cationically polyme ⁇ zable composition of one or more cationically polyme ⁇ zable monomers comprising reacting the cationically polyme ⁇ zable composition in the presence of an onium salt, an azo or peroxide initiator, and an electron-rich vinyl resin
- an onium salt reacting the cationically polyme ⁇ zable composition in the presence of an onium salt, an azo or peroxide initiator, and an electron-rich vinyl resin
- this invention is a method for polymerizing a cationically poiyme ⁇ zable composition of one or more cationically polyme ⁇ zable monomers comprising reacting the cationically polyme ⁇ zable composition in the presence of an o ⁇ ium salt, an azo or peroxide initiator, and a catalytic or substoichiometric amount of an electron-rich vinyl resin
- an o ⁇ ium salt an azo or peroxide initiator
- a catalytic or substoichiometric amount of an electron-rich vinyl resin The components of such cationically polyme ⁇ zable composition are as described earlier in this specification
- this invention is a method for lowering the cure temperature of a cationically polyme ⁇ zable composition
- a cationically polyme ⁇ zable composition comprising one or more cationically polyme ⁇ zable monomers, an onium salt, and an azo or peroxide initiator, the method comprising adding to the cationically polyme ⁇ zable composition an electron-rich vinyl resin.
- the components of such cationically polymerizable composition are as described earlier in this specification
- this invention is a method for lowering the cure temperature of a cationicaliy polymerizable composition comprising one or more cationically polymerizable monomers, an onium salt, and an azo or peroxide initiator, the method comprising adding to the cationically polymerizable composition a catalytic or substoichiometric amount of an electron-rich vinyl resin
- a catalytic or substoichiometric amount of an electron-rich vinyl resin The components of such cationically polymerizable composition are as described earlier in this specification.
- this invention is a two-part cationicaiiy polymerizable composition, one part comprising cationically poiyme ⁇ zable monomer and an onium salt, and the second part comprising cationically poiyme ⁇ zable monomer and an azo or peroxide initiator Either the first part or the second part, or both, will contain an electron- rich vinyl resin.
- the components of these parts have been described earlier in this specification The two parts may be mixed mechanically just before dispensing
- this invention is a two-part cationically polymerizable composition, one part comprising cationically polymerizabie monomer and an onium salt, and the second part comprising cationically polyme ⁇ zable monomer and an azo or peroxide initiator
- Either the first part or the second part, or both, will contain a catalytic or substoichiometric amount of an electron-rich vinyl resin
- the components of these parts have been described earlier in this specification The two parts may be mixed mechanically just before dispensing.
- the polymerization of one or more cationically polymenzable monomers in which the polymerization mix further comprises an onium salt, an azo or peroxide initiator, and an electron-rich vinyl resin, can be performed in the presence of one or more other vinyl monomers, such as, acrylates, methacrylat.es, maleimides, maleates, or fumarates, or a mixture of those ⁇ that is, vinyl monomers that are not typically denominated as electron-rich)
- the azo or peroxide initiator will initiate the radical polymerization of these other vinyl monomers
- the cationic polymerization of the cationic polyme ⁇ zable materials and the radical polymerization of these vinyl monomers can occur simultaneously or independently, depending on the choice of specific azo or peroxide initiator and the temperature at which the initiator decomposes and forms the initiating radical species In any case, the initiators can be chosen so that curing occurs at 100 D C or lower
- the polymerization of one or more cationically polymenzable monomers, in which the polymerization mix further comprises an onium salt, an azo or peroxide initiator, and an electron-rich vinyl resin can be performed in the presence of a substoichiometric amount of one or more other vinyl monomers, such as, acrylates, methacrylates, maleimides, maleates, or fumarates, or a mixture of those
- the cationic polymerization is initiated by a cationic macroinitiator generated by radical polymerization and followed by oxidation as shown in the below reaction scheme.
- the electron-rich vinyl resin should be present in slight excess in comparison to the other vinyl resin.
- This embodiment works well in a two part system, in which one part contains the cationically polymerizable resin and the second contains the electron-rich vinyl resin and the other vinyl resin.
- Suitable acrylate and methacrylate resins include those having the generic
- X 2 is an aromatic or aliphatic group.
- exemplary X 2 entities include poly(butadienes), poly-(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, ester, or ether.
- Commercially available materials include butyl (meth)acrylate, isobutyl (meth)acryiate, 2-ethyi hexyl (meth)acrylate, isodecyl (meth)acrylate, n-laury!
- the acrylate resins are selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl meth acrylate, poly(butadiene) with acrylate functionality and poly(butadiene) with methacrylate functionality.
- Suitable maleitnide resins include those having the generic structure
- X 1 is an aliphatic or aromatic group.
- exemplary X 1 entities include, poly(butadienes), poly(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, ester, or ether. These types of resins are commercially available and can be obtained, for example, from Dainippon Ink and Chemical, Inc.
- Additional suitable maleimide resins include, but are not limited to, solid aromatic bismaleimide (BMI) resins, particularly those having the structure
- Suitable bismaleimide resins having aromatic bridging groups are commercially available, and can be obtained, for example, from Sartomer (USA) or HOS-Technic GmbH (Austria).
- maleimide resins include:
- C 36 represents a linear or branched chain hydrocarbon chain (with or without cyclic moieties) of 36 carbon atoms;
- Suitable fumarates and maleates include, for example, dioctyl maleate, dibutyl maieate, dioctyl fumarate, and dibutyi fumarate.
- the cationically polymerizable composition may further comprise an additional monofu ⁇ ctional and/or polyfunctional cationicaily polymerizable resin, and/or a reactive cationically polymerizable diluent.
- the cationically polymerizable composition may further comprise a filler.
- suitable nonconductive fillers include alumina, aluminum hydroxide, silica, fused silica, fumed silica, vermiculite, mica, wollastonite, calcium carbonate, titania, sand, glass, barium sulfate, zirconium, carbon black, organic fillers, and haiogenated ethylene polymers, such as, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidene chloride, and vinyl chloride.
- suitable conductive fillers include carbon black, graphite, gold, silver, copper, platinum, palladium, nickel, aluminum, silicon carbide, boron nitride, diamond, and alumina.
- the filler particles may be of any appropriate size ranging from nano size to several mm. Appropriate filler sizes can be determined by the practitioner, but, in general, will be within the range of 20 nanometers to 100 microns. The choice of such size for any particular end use is within the expertise of one skilled in the art. Filler may be present in any effective amount, and typically, an effective amount will range from 10 to 90% by weight of the total composition. More than one filler type may be used in a composition and the fillers may or may not be surface treated.
- the worklife of the composition can be lengthened by the addition of an epoxy resin or a radical inhibitor.
- the epoxy resin will be present in an amount of 1 to 90% by weight of total resin.
- Suitable epoxy resins are those previously disclosed in this specification.
- the radical inhibitor will be present in an amount of 10ppm to 2000ppm.
- Suitable radical inhibitors include, for example, hydroquinone, methylhydroqui ⁇ one, t- butylcatechol, phenothiazine, and NPAL having the structure
- EXAMPLE 1 EFFECT OF ELECTRON-RICH VINYL COMPOUND ON CURE TEMPERATURE OF CATIONICALLY POLYMERIZABLE COMPOSITION
- a cationically polymerizable composition was prepared as a control to contain oxetane (OXT-221) having the structure shown above in this specification, an iodonium salt (RHODORSIL-2074), and an azo initiator (VAZO-52). Additional compositions were prepared to contain the control composition and a catalytic amount of vinyl ether I, vinyl ether II, or a styrene compound, having the structures shown below. Samples of the compositions were cured and their peak temperature (Tpeak) recorded. Other samples of the same composition were stored at room temperature and gel times recorded to measure worklife.
- OXT-221 oxetane
- RHODORSIL-2074 iodonium salt
- VAZO-52 azo initiator
- Additional compositions were prepared to contain the control composition and a catalytic amount of vinyl ether I, vinyl ether II, or a styrene compound, having the structures shown below. Samples of the compositions were cured and their peak temperature (T
- EXAMPLE 2 EFFECT OF EPOXY OR RADICAL INHIBITOR ON WORKLIFE OF CATIONICALLY POLYMERIZABLE COMPOSITION
- epoxy or a radical inhibitor was added to the formulations.
- a control cationically polymerizable composition was prepared to contain oxetane (OXT-221) having the structure shown above, an iodonium salt (RHODORSIL), an azo initiator (VAZO-52) and vinyl ether I or N having the structures shown above.
- RHODORSIL iodonium salt
- VAZO-52 azo initiator
- vinyl ether I or N having the structures shown above.
- epoxy resin or methyihydroquinone (MeHQ) as a radical inhibitor.
- the epoxy resins used were a cycloaliphatic epoxy sold under the tradename CYRACURE UVR6128 from Dow chemicals or epoxy resin sold under the tradename EPON 834 from Hexion chemicals.
- EXAMPLE 3 EFFECT OF PEROXIDE INITIATOR ON THE CURE TEMPERATURE OF CATIONICALLY POLYMERIZABLE COMPOSITIONS
- Azo initiators can liberate N 2 gas upon decomposition, which is undesirable in applications where low outgassing is required.
- the successful substitution of peroxides for the azo initiators will be dependent on the peroxide chosen.
- Cationically polymerizable compositions were prepared as in the previous examples with the substitution of benzoyl peroxide and a commercial peroxide sold under the tradename TRIGONOX-23 for the azo initiators. The formulations of the compositions and the results are reported in TABLE 3. The data show that the (TRIGONOX) peroxide was more effective than benzoyl peroxide as an initiator.
Abstract
A cationically polymerizable composition comprising (i) a cationically polymerizable resin, (ii) an onium salt, (iii) an azo or peroxide initiator, exhibits a lower cure temperature upon the addition of (iv) a catalytic or substoichiometric amount of an electron -rich vinyl resin to the reaction.
Description
REDOX-INDUCED CATIONICALLY POLYMERIZABLE COMPOSITIONS WITH LOW CURE TEMPERATURE
BACKGROUND OF THE INVENTION
[0001] This invention relates to a redox-induced cationically polymeπzable composition that exhibits reduced cure temperature and to a method for reducing the cure temperature of a cationically polymeπzable composition.
[0002] In many manufacturing processes, processing speed leads to higher throughput and lower assembly costs When the use of an adhesive, coating, or encapsulant is part of the manufacturing process, processing speed can be increased if the adhesive, coating, or encapsulant can be cured quickly at a relatively low curing temperature
[0003] In the electronics packaging industry, for example, low temperature, fast (snap) cure adhesives and encapsulants are desired for various applications. A common mode of eiectronic packaging involves affixing semiconductor devices onto substrates by means of an adhesive or encapsulant. The more prominent uses are the bonding of integrated circuit chips to metal lead frames or organic substrates, and the bonding of circuit packages or assemblies to printed wire boards, including, for example, die attach for array package, die attach for RFID package, and component attach for ink jet cartridge assembly. For ink jet cartridge, low temperature cure assembly can minimize jetting trajectory distortion and improve printing quality For temperature-sensitive components or substrates, such as, the paper-based antenna in RFID application and camera sensor in organic substrates, low temperature interconnect is very desirable Thus, there is a need for polymeπzable compositions that cure at low temperatures, preferably iess than 1000C
SUMMARY OF THE INVENTION
[0004] This invention is a polymeπzable composition comprising (ι) a cationicaliy polymeπzable resin, (ιι) an onium salt, (in) an azo or peroxide initiator, and (iv) an
electron-rich vinyl resin
[0005] In another embodiment, this invention is a polymeπzable composition comprising (i) a cationicaiiy polymerizable resin, (ιι) an onium salt, (iii) an azo or peroxide initiator, and (iv) a catalytic or substoichiometric amount of an electron-rich vinyl resin
[0006] In another embodiment, this invention is method for reducing the cure temperature of a cationicaiiy poSymeπzable resin, in which the cure of the resin is catalyzed by the addition of an onium salt and an azo or peroxide initiator to the resin, the method comprising adding an electron-rich vinyl resin to the mixture of resin, onium salt and azo or peroxide initiator
[0007] In another embodiment, this invention is method for reducing the cure temperature of a cationicaiiy polymerizable resin, in which the cure of the resin is catalyzed by the addition of an onium salt and an azo or peroxide initiator to the resin, the method comprising adding a catalytic or substoichiometric amount of an eiectron-rich vinyl resin to the mixture of resin, onium salt and azo or peroxide initiator
DETAILED DESCRIPTION OF THE INVENTION
[0008] The reaction scheme for the cationic polymerization using onium salt and an azo initiator, in the presence of an electron-rich vinyl species, occurs as depicted here-
[0009] Peroxide can also be used to generate a radical for reaction with the onium salt
[0010] As used within this specification and claims, a curable resin is one that is polymeπzable with or without crosslinking Curable and poiymeπzable are used interchangeably and a cationically curable resin or composition is one that is poiymeπzable Any cationically polymeπzable resin may be used in the above reaction Exemplary cationically polymerizable resins include oxetanes, epoxies, spiroorthocarbonates, spiroorthoesters, and benzoxazines, or a mixture of any of those
[0011] Suitable oxetane resins are those disclosed in US patents 7,034,064, 6,982,338, 6,953,862, 6,943,258, 6,753,434, and those available from Toagosei Corporation under the tradenames OXT-221 , OXT-121 , OXT-101 , OXT-212, OXT-211 , CHOX1 OX-SC, PNOX-1009, having the structures
OXT-101 OXT-221 OXT-212
[0012] Suitable epoxy resins include bisphenol epoxies, naphthalene epoxies, and aliphatic type epoxies Commercially available materials include bisphenol type epoxy resins (for example, those sold under the tradenames EPICLON 830LVP, 830CRP, 835LV, 850CRP, available from Dainippon Ink & Chemicals, lnc ), naphthalene type epoxy resins (for example, those sold under the tradenames EPICLON HP4032, available from Dainippon Ink & Chemicals, lnc ), aliphatic epoxy resins (for example, those sold under the tradenames ARALDITE CYI 79, 184, 192, 175, 179, available from Ciba Specialty Chemicals, EPOXY 1234, 249, 206, available from Dow Corporation, and EHPE-3150, available from Daicel Chemical Industries, Ltd )
[0013] Other suitable epoxy resins include cycloaliphatic epoxy resins, for example, 3,4- epoxy-cyciohexylmethyl 3,4-epoxycyclohexanecarboxylate , available as ERL-4221 from Union carbide and ARALDITE CY-179, available from Ciba-Geigy, diglycidylester of hexahydro-phthahc anhydride, available as CY-184 from Ciba-Geigy, bιs(3,4- epoxycyclohexylmethyl)-adιpate, available as ERL-4229 from Union carbide, and other bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, epoxy novolac resins, biphenyl type epoxy resins, naphthalene type epoxy resins, and dicyclopentadienephenol type epoxy resins, all commercially available from different sources
[0014] Exemplary spiroorthocarbonate and vinyl spiroorthocarbonates include those having the following structures
[0015] Exemplary electron-rich vinyl spirocarbonates include those having the following structures:
[0016] Exemplary spiroorthoesters include
[0017] An exemplary electron-rich vinyl spiroorthoester is
[0018] Suitable benzoxazines include those compounds containing the structure
[0019] Exemplary benzoxazine compounds include those of the formulae
in which R1 is a divalent radical that may be aliphatic, aromatic, or a combination of aliphatic and aromatic, and that may contain heteroatoms, such as oxygen, nitrogen, sulfur, phosphorous, or halogen, or that may be a single bond, or that may be S, S2, SO, SO2, O, or CO, and R2 is hydrogen, an alkyl or substituted alkyl, an aromatic or substituted aromatic
[0020] Specific suitable benzoxazine compounds include
[0021] In addition to compounds such as the above, the benzoxazine may also be present in a polymeric species, such as depicted in the following structure:
which R1 is as described above, π is an integer that will vary depending on the polymeric composition from which the benzoxazine depends, and each Q is a polymeric entity, for example, polyurethane, polyether, polyester, poly(butadιene) or polystyreπic
[0022] Exemplary onium salts include iodonium salts, sulfonium salts, diazonium salts, ammonium salts or a mixture of those salts In one embodiment, the onium salt is an
X iodonium salt of the formula © in which R is independently seiected from phenyl, halophenyl, (for example, chlorophenyl) and C1-C20 alkylphenyl (for example, dodecyl phenyl) X is any suitable counter anion, for example, a halogen anion, CF3SO3 , C6H5SO3 ', NO3 " , AsF6 ", SbF6 ", FeCI4 ", SbCI6 ", BF4 ", PF6 ", and (C6F5)B"
[0023] Commercially available iodonium salts include (p-lsopropylphenyj)(p- methylphenyl) iodonium tetrakιs(pentafluorophenyl)borate from Gelest as RHODORSIL 2074, and bisdodecyl phenyliodonium hexafluoroantimonate as UV 9380 from General Electric The onium salts are used in an effective amount In one embodiment, an effective amount is in the range of 0 1 to 10% by weight of the total resin
[0024] Exemplary azo initiators include, for example, azoisobutylonitπle, 2,2"- azobispropane, 2,2'-azobis(2-methylbutanenitnle), and m.m'-azoxystyrene Commercially available azo initiators are those available from Wako Specialty Company, such as those sold under the tradenames VA-044, VA-057, VA-085, V-70, VF-096, V-65, V-601 , V-59, V-40, VF-096, V-30, and those available from Akzo Nobel, such as those sold under the tradenames PERKADOX ACCN, PERKADOX AIBN1 PERKADOX AMBN-GR, and those available from Dupont, such as those sold under the tradenames VAZO-52, VAZO-64, VAZO-67 and VAZO-88 The azo initiators are used in an effective amount In one embodiment an effective amount ranges from 0 1 to 10% by weight of the total resin
content
[0025] Exemplary peroxide initiators include those commercially available from Akzo Nobel, such as those sold under the tradenames PERKADOX and TRIGONOX Other peroxide initiators are suitable, provided they generate radicals with the vinyl resin for reaction with the onium salt Exemplary peroxides include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, butyl peroctoate, dicumyl peroxide, acetyl peroxide, para- chlorobenzoyl peroxide and di-t-butyl diperphthalate The peroxide initiators are used in an effective amount In one embodiment an effective amount ranges from 0 1 to 10% by weight of the total resin content
[0026] Exemplary electron-rich vinyl resins include vinyl ethers, spirocyctic vinyl ethers, styrenics (compounds containing a styrene moiety), cinnamyls (in this specification and claims compounds containing a cinnamyl moiety), N-vιnylamιdes, and N-vinylamines
[0027] Suitable vinyl ether resins include, for example, poly(butadιenes), poly(carbonates), poiy(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, ester, or ether, which also contain vinyl ether functionality Suitable commercially available vinyl ether resins include cyclohexane-dimethanol divinylether, dodecylvinylether, cyclohexyl vinylether, 2-ethylhexyl vinylether, dipropyleneglycol divinylether, hexanediol divinylether, octadecylvinylether, and butandiol divinylether, available from International Specialty Products (ISP), vinyl ethers sold under the tradenames VECTOMER 4010, 4020, 4030, 4040, 4051 , 4210, 4220, 4230, 4060, 5015 available from Sigma-Aldrich, lnc
[0028] Suitable spirocyciic vinyl ethers include, for example, those having the structures
[0029] Suitable styrenic resins include, for example, those disclosed in US patents
6,953,862, 6,908,969, 6,908,957, 6,809,155, 6,803,406, 6,716,992, 6,441 ,213, 6,441 ,121, 6,307,001 , 6,300,456, and those commercially available styrene, substituted styrenics, divinyl benzene, diphenylethylene, and any other resins possessing styrenic functionality (hereinafter styrenics) Such resins can be, for example, polyesters, carbamates, ureas Exemplary styrenic resins include compounds having the following structures in which R is an aliphatic or aromatic hydrocarbon, including those with heteroatoms.
[0030] Suitable cinnamyl resins include, for example, those disclosed in US patents 6,943,258, 6,753,434, 6,716,992, 6,908,969, 6,908,957, 6,809,155, 6,803,406, 6,753,434, 6,570,032, 6,441,121, 6,307,001 , 6,300,456 The cinnamyl compounds can be any small molecule, oligomeπc, or polymeric material that contains a cinnamy! functionality
[0031] Suitable commercially available N-vinylamide resins include, for example, N-vιnyl- pyrrohdone, N-vinylformamide, and N-vinylcaprolactone
[0032] Suitable commercially available N-vιnylamιnes include, for example, N- vinylcarbazole, N-vinylpyrrole, N-vinylimidazole, and 2-methyl-N-vιnylιmidazole
[0033] In another embodiment, this invention is a method for polymerizing a cationically polymeπzable composition of one or more cationically polymeπzable monomers comprising reacting the cationically polymeπzable composition in the presence of an onium salt, an azo or peroxide initiator, and an electron-rich vinyl resin The components
of such cationically poiymeπzable composition are as described earlier in this specification
[0034] In another embodiment, this invention is a method for polymerizing a cationically poiymeπzable composition of one or more cationically polymeπzable monomers comprising reacting the cationically polymeπzable composition in the presence of an oπium salt, an azo or peroxide initiator, and a catalytic or substoichiometric amount of an electron-rich vinyl resin The components of such cationically polymeπzable composition are as described earlier in this specification
[0035] In another embodiment, this invention is a method for lowering the cure temperature of a cationically polymeπzable composition comprising one or more cationically polymeπzable monomers, an onium salt, and an azo or peroxide initiator, the method comprising adding to the cationically polymeπzable composition an electron-rich vinyl resin. The components of such cationically polymerizable composition are as described earlier in this specification
[0036] In another embodiment, this invention is a method for lowering the cure temperature of a cationicaliy polymerizable composition comprising one or more cationically polymerizable monomers, an onium salt, and an azo or peroxide initiator, the method comprising adding to the cationically polymerizable composition a catalytic or substoichiometric amount of an electron-rich vinyl resin The components of such cationically polymerizable composition are as described earlier in this specification.
[0037] In another embodiment, this invention is a two-part cationicaiiy polymerizable composition, one part comprising cationically poiymeπzable monomer and an onium salt, and the second part comprising cationically poiymeπzable monomer and an azo or peroxide initiator Either the first part or the second part, or both, will contain an electron- rich vinyl resin. The components of these parts have been described earlier in this specification The two parts may be mixed mechanically just before dispensing
[0038] In another embodiment, this invention is a two-part cationically polymerizable composition, one part comprising cationically polymerizabie monomer and an onium salt,
and the second part comprising cationically polymeπzable monomer and an azo or peroxide initiator Either the first part or the second part, or both, will contain a catalytic or substoichiometric amount of an electron-rich vinyl resin The components of these parts have been described earlier in this specification The two parts may be mixed mechanically just before dispensing.
[0039] These two part polymerizations can occur simultaneously or independently, depending on the choice of specific azo or peroxide initiator and the temperature at which the initiator decomposes and forms the initiating radical species. Both the cationic polymerization of the cationic polymeπzable materials and the radical polymerization of the viny! monomers will occur below 100°C with the appropriate choice of initiator
[0040] In other embodiments, the polymerization of one or more cationically polymenzable monomers, in which the polymerization mix further comprises an onium salt, an azo or peroxide initiator, and an electron-rich vinyl resin, can be performed in the presence of one or more other vinyl monomers, such as, acrylates, methacrylat.es, maleimides, maleates, or fumarates, or a mixture of those {that is, vinyl monomers that are not typically denominated as electron-rich) In this polymerization, the azo or peroxide initiator will initiate the radical polymerization of these other vinyl monomers The cationic polymerization of the cationic polymeπzable materials and the radical polymerization of these vinyl monomers can occur simultaneously or independently, depending on the choice of specific azo or peroxide initiator and the temperature at which the initiator decomposes and forms the initiating radical species In any case, the initiators can be chosen so that curing occurs at 100DC or lower
[0041 ] In other embodiments, the polymerization of one or more cationically polymenzable monomers, in which the polymerization mix further comprises an onium salt, an azo or peroxide initiator, and an electron-rich vinyl resin can be performed in the presence of a substoichiometric amount of one or more other vinyl monomers, such as, acrylates, methacrylates, maleimides, maleates, or fumarates, or a mixture of those In this embodiment, the cationic polymerization is initiated by a cationic macroinitiator generated by radical polymerization and followed by oxidation as shown in the below reaction scheme. The two polymerization processes are dependent To generate the
macroinitiator, the electron-rich vinyl resin should be present in slight excess in comparison to the other vinyl resin. This embodiment works well in a two part system, in which one part contains the cationically polymerizable resin and the second contains the electron-rich vinyl resin and the other vinyl resin.
[0042] Suitable acrylate and methacrylate resins include those having the generic
which n is 1 to 6, R1 is -H or -CH3. and X2 is an aromatic or aliphatic group. Exemplary X2 entities include poly(butadienes), poly-(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, ester, or ether. Commercially available materials include butyl (meth)acrylate, isobutyl (meth)acryiate, 2-ethyi hexyl (meth)acrylate, isodecyl (meth)acrylate, n-laury! (meth)acrylate, alkyl (meth)-acrylate, tridecyl (meth)acrylate, n-stearyl (meth)acrylate, cyclohexyl(meth)-acrylate, tetrahydrofurfuryl(meth)acrylate, 2-phenoxy ethyl(meth)- acrylate, isobornyl(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1 ,6- hexanediol di(meth)acrylate, 1,9-nonandiol di(meth)acrylate, perfluorooctylethyl (meth)acryiate, 1 ,10 decandiol di{meth)acry!ate, nonylphenol polypropoxylate (meth)acrylate, and polypentoxylate tetrahydrofurfuryl acrylate, available from Kyoeisha Chemical Co., LTD; polybutadiene urethane dimethacrylate (CN302, NTX6513) and polybutadiene dimethacrylate (CN301 , NTX6039, PRO6270) available from Sartomer Company, inc; polycarbonate urethane diacrylate (ARTRESIN UN9200A) available from Negami Chemical Industries Co., LTD; acrylated aliphatic urethane oligomers (EBECRYL 230, 264, 265, 270,284, 4830, 4833, 4834, 4835, 4866, 4881 , 4883, 8402, 8800-20R, 8803, 8804) available from Radcure Specialities, Inc; polyester acrylate oligomers (EBECRYL 657, 770, 810, 830, 1657, 1810, 1830) available from Radcure Specialities, Inc.; and epoxy acrylate
resins (CN104, 111 , 112, 115, 116, 117, 118, 119, 120, 124, 136) available from Sartomer Company, Inc. In one embodiment the acrylate resins are selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl meth acrylate, poly(butadiene) with acrylate functionality and poly(butadiene) with methacrylate functionality.
[0043] Suitable maleitnide resins include those having the generic structure
which n is 1 to 3 and X1 is an aliphatic or aromatic group. Exemplary X1 entities include, poly(butadienes), poly(carbonates), poly(urethanes), poly(ethers), poly(esters), simple hydrocarbons, and simple hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, ester, or ether. These types of resins are commercially available and can be obtained, for example, from Dainippon Ink and Chemical, Inc.
[0044] Additional suitable maleimide resins include, but are not limited to, solid aromatic bismaleimide (BMI) resins, particularly those having the structure
in which Q is an aromatic group. Suitable bismaleimide resins having aromatic bridging groups are commercially available, and can be obtained, for example, from Sartomer (USA) or HOS-Technic GmbH (Austria).
[0045] Other suitable maleimide resins include:
in which C36 represents a linear or branched chain hydrocarbon chain (with or without cyclic moieties) of 36 carbon atoms;
[0046] Suitable fumarates and maleates include, for example, dioctyl maleate, dibutyl maieate, dioctyl fumarate, and dibutyi fumarate.
[0047] In all embodiments, the cationically polymerizable composition may further comprise an additional monofuπctional and/or polyfunctional cationicaily polymerizable resin, and/or a reactive cationically polymerizable diluent.
[0048] Jn all embodiments, the cationically polymerizable composition may further comprise a filler. Examples of suitable nonconductive fillers include alumina, aluminum hydroxide, silica, fused silica, fumed silica, vermiculite, mica, wollastonite, calcium carbonate, titania, sand, glass, barium sulfate, zirconium, carbon black, organic fillers, and haiogenated ethylene polymers, such as, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidene chloride, and vinyl chloride. Examples of suitable conductive fillers include carbon black, graphite, gold, silver, copper, platinum, palladium, nickel, aluminum, silicon carbide, boron nitride, diamond, and alumina.
[0049] The filler particles may be of any appropriate size ranging from nano size to several mm. Appropriate filler sizes can be determined by the practitioner, but, in general, will be within the range of 20 nanometers to 100 microns. The choice of such size for any particular end use is within the expertise of one skilled in the art. Filler may be present in
any effective amount, and typically, an effective amount will range from 10 to 90% by weight of the total composition. More than one filler type may be used in a composition and the fillers may or may not be surface treated.
[0050] Other materials, such as adhesion promoters, dyes, pigments, and rheology modifiers, may be added as desired for modification of final properties. Such materials and the amounts needed are within the expertise of those skilled in the art.
[0051] In those cases in which the cationic polymerizable monomer is not an epoxy, the worklife of the composition can be lengthened by the addition of an epoxy resin or a radical inhibitor. As an additive to increase worklife, the epoxy resin will be present in an amount of 1 to 90% by weight of total resin. Suitable epoxy resins are those previously disclosed in this specification. In those cases in which a radical inhibitor is used to lengthen worklife, the radical inhibitor will be present in an amount of 10ppm to 2000ppm. Suitable radical inhibitors include, for example, hydroquinone, methylhydroquiπone, t- butylcatechol, phenothiazine, and NPAL having the structure
EXAMPLES
[0052] EXAMPLE 1. EFFECT OF ELECTRON-RICH VINYL COMPOUND ON CURE TEMPERATURE OF CATIONICALLY POLYMERIZABLE COMPOSITION
[0053] A cationically polymerizable composition was prepared as a control to contain oxetane (OXT-221) having the structure shown above in this specification, an iodonium salt (RHODORSIL-2074), and an azo initiator (VAZO-52). Additional compositions were prepared to contain the control composition and a catalytic amount of vinyl ether I, vinyl ether II, or a styrene compound, having the structures shown below. Samples of the compositions were cured and their peak temperature (Tpeak) recorded. Other samples of the same composition were stored at room temperature and gel times recorded to measure worklife.
[0054] The formulations for the compositions and the results are reported in TABLE 1. The results show that the addition of vinyl ether to the cationically polymerizable oxetane in the presence of an iodonium salt and an azo initiator decreased the cure temperature of the composition (compare entry 1 control to entry 2). Increasing the amount of iodonium salt from 1 moi% to 2 mol% (entry 3) increased the gel time, without affecting the cure temperature. Vinyl ether alone had the lowest cure temperature, but had a short gel time (entry 5). The difunctional styrenic compound, another electron-rich vinyl compound, lowered the cure temperature similarly to the vinyl ether (entry 6). Isothermal Differential Scanning Calorimetry was run on two samples: the sample shown in entry 2 with a peak temperature of 76°C cured in about 45 seconds at 850C; and the sample shown in entry 5 with a peak temperature of 65CC cured in 30 seconds at 85°C.
[0055]
[0056] EXAMPLE 2. EFFECT OF EPOXY OR RADICAL INHIBITOR ON WORKLIFE OF CATIONICALLY POLYMERIZABLE COMPOSITION
[0057] In order to improve the worklife of the compositions, epoxy or a radical inhibitor was added to the formulations. A control cationically polymerizable composition was prepared to contain oxetane (OXT-221) having the structure shown above, an iodonium salt (RHODORSIL), an azo initiator (VAZO-52) and vinyl ether I or N having the structures shown above. To this was added epoxy resin or methyihydroquinone (MeHQ) as a radical inhibitor. The epoxy resins used were a cycloaliphatic epoxy sold under the tradename CYRACURE UVR6128 from Dow chemicals or epoxy resin sold under the tradename EPON 834 from Hexion chemicals.
[0058] The composition components and results are reported in TABLE 2 and show that the addition of epoxy to the composition stabilized the formulation and improved gel times (entries 2 and 3). The epoxy system without oxetane and a catalytic amount of vinyl ether
showed a peak temperature of 95°C with good work life (entry 4) Changing from vinyl ether I to vinyl ether Il increased the gel time slightly (entry 5), indicating that the workhfe may depend on the type of vinyl ether used Use of radical inhibitors improved the work life of the formulations, although there was an accompanying increase in the peak temperature, which corresponded to the amount of inhibitor used (entries 6, 7, 8, 9).
[0059]
[0060] EXAMPLE 3. EFFECT OF PEROXIDE INITIATOR ON THE CURE TEMPERATURE OF CATIONICALLY POLYMERIZABLE COMPOSITIONS
[0061] Azo initiators can liberate N2 gas upon decomposition, which is undesirable in applications where low outgassing is required. The successful substitution of peroxides for the azo initiators will be dependent on the peroxide chosen. Cationically polymerizable compositions were prepared as in the previous examples with the substitution of benzoyl peroxide and a commercial peroxide sold under the tradename TRIGONOX-23 for the azo initiators. The formulations of the compositions and the results are reported in TABLE 3. The data show that the (TRIGONOX) peroxide was more effective than benzoyl peroxide as an initiator.
[0062]
Claims
WHAT Is CLAIMED
1 A polymeπzabie composition comprising (ι) a cationically polymeπzable resin, (ii) an onium salt, (m) an azo or peroxide initiator, and (tv) an electron-rich vinyl resin
2 The polymeπzable composition according to claim 1 in which the cationically polymeπzable resin is selected from the group consisting of oxetanes, epoxies, spiroorthocarbonates, spiroorthoesters, and benzoxazines, or a mixture of any of those
3 The polymeπzable composition according to claim 1 in which the electron-rich vinyl resin is selected from the group consisting of viny! ethers, spirocyclic vinyl ethers, styrenics, cinnamyls, N-vinylamides, and N-vinylamines
4 The polymeπzable composition according to claim 1 in which the electron-rich vinyl resin in present in a catalytic or substoichiometπc amount
5 The polymeπzable composition according to claim 4 in which the cationically polymeπzabie resin is selected from the group consisting of oxetanes, epoxies, spiroorthocarbonates, spiroorthoesters, and benzoxazines, or a mixture of any of those
6 The polymeπzable composition according to claim 4 in which the electron-rich vinyl resin is selected from the group consisting of vinyl ethers, spirocyclic vinyl ethers, styrenics, cinnamyls, N-vinylamides, and N-vinylamines
7 A method for lowering the cure temperature of a cationically polymeπzable composition comprising (i) a cationically polymeπzable resin, (ιι) an onium salt, (in) an azo or peroxide initiator, the method comprising reacting the cationically polymeπzable composition in the presence of (ιv) an eiectron-rich vinyl resin.
8 The method according to claim 7 in which the cationically polymeπzable resin is selected from the group consisting of oxetanes, epoxies, spiroorthocarbonates, spiroorthoesters, and benzoxazines, or a mixture of any of those
9 The method according to claim 7 in which the electron-rich vinyl resin is selected from the group consisting of vinyl ethers, spirocyclic vinyl ethers, styrenics, cinnamyls, N- vinylamides, and N-vinyiamines
10 The method according to claim 7 in which the electron-rich vinyl resin in present in a catalytic or substoichiometric amount
11 The method according to claim 10 in which the cationically polymeπzable resin is selected from the group consisting of oxetanes, epoxies, spiroorthocarbonates, spiroorthoesters, and benzoxazines, or a mixture of any of those.
12 The method according to claim 10 in which the electron-rich vinyl resin is selected from the group consisting of vinyl ethers, spirocyclic vinyl ethers, styrenics, cinnamyls, N- vinyiamides, and N-vinylamines
13 A method for polymerizing a cationically polymeπzable composition comprising
(i) a cationically polymeπzable resin, (ii) an onium salt, (in) an azo or peroxide initiator, the method comprising reacting the cationically polymeπzable composition in the presence of (ιv) an eiectron-rich vinyl resin
14 The method according to claim 13 in which the cationically poiymeπzable resin is selected from the group consisting of oxetanes, epoxies, spiroorthocarbonates, spiroorthoesters, and benzoxazines, or a mixture of any of those
15 The method according to claim 13 in which the electron-rich vinyl resin is selected from the group consisting of vinyl ethers, spirocyclic vinyl ethers, styrenics, cinnamyls, N- vinylamides, and N-vinylamines
16 The method according to claim 13 in which the electron-rich vinyl resin in present in a catalytic or substoichiometπc amount
17 The method according to claim 16 in which the cationically polymeπzable resin is selected from the group consisting of oxetanes, epoxies, spiroorthocarbonates, spiroorthoesters, and benzoxazines, or a mixture of any of those
18 The method according to claim 16 in which the electron-rich vinyl resin is selected from the group consisting of vinyl ethers, spirocyclic vinyl ethers, styrenics, cinnamyls, N- vinylamides, and N-vιnylamines
20 A two-part cationically polymerizable composition, in which the first part comprises a cationically polymeπzable resin and an onium sait, the second part comprises a cationically polymerizable monomer and an azo or peroxide initiator, and either the first or the second part or both further comprise an electron-rich vinyl resin
21 The two-part cationically polymerizable composition according to claim 20 in which the electron-rich vinyl resin is present in a catalytic or substoichiometric amount
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2007/085272 WO2009067112A1 (en) | 2007-11-20 | 2007-11-20 | Redox-induced cationically polymerizable compositions with low cure temperature |
JP2010534925A JP5248623B2 (en) | 2007-11-20 | 2007-11-20 | Redox-derived cationic polymerizable composition having low curing temperature |
TW097119983A TWI423998B (en) | 2007-11-20 | 2008-05-30 | Redox-induced cationically polymerizable compositions with low cure temperature |
US12/777,351 US8324319B2 (en) | 2007-11-20 | 2010-05-11 | Redox-induced cationically polymerizable compositions with low cure temperature |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2007/085272 WO2009067112A1 (en) | 2007-11-20 | 2007-11-20 | Redox-induced cationically polymerizable compositions with low cure temperature |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/777,351 Continuation US8324319B2 (en) | 2007-11-20 | 2010-05-11 | Redox-induced cationically polymerizable compositions with low cure temperature |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009067112A1 true WO2009067112A1 (en) | 2009-05-28 |
Family
ID=40667768
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2007/085272 WO2009067112A1 (en) | 2007-11-20 | 2007-11-20 | Redox-induced cationically polymerizable compositions with low cure temperature |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP5248623B2 (en) |
TW (1) | TWI423998B (en) |
WO (1) | WO2009067112A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011530632A (en) * | 2008-08-12 | 2011-12-22 | ハンツマン・アドヴァンスト・マテリアルズ・(スイッツランド)・ゲーエムベーハー | Thermosetting composition |
WO2014105422A1 (en) * | 2012-12-27 | 2014-07-03 | 3M Innovative Properties Company | Polymerizable composition including a benzoxazine and an acid-forming peroxide catalyst, article, and method |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019094367A (en) * | 2017-11-17 | 2019-06-20 | 丸善石油化学株式会社 | Production method of vinyl ether polymer using onium salt |
WO2020170295A1 (en) * | 2019-02-18 | 2020-08-27 | 丸善石油化学株式会社 | Method for producing vinyl ether polymer using onium salt |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001062834A1 (en) * | 2000-02-18 | 2001-08-30 | Rhodia Chimie | Surface treatment of plastic material with an organic polymerisable and/or crosslinkable composition having reactive functions |
US6805439B2 (en) * | 2001-09-06 | 2004-10-19 | Brother Kogyo Kabushiki Kaisha | Active energy beam-curable composition, ink containing the same, and printer accommodating the same ink |
WO2004099286A1 (en) * | 2003-05-07 | 2004-11-18 | Mitsui Chemicals, Inc. | Cationically photopolymerizable resin composition and optical disk surface protection material |
WO2005037876A1 (en) * | 2003-10-15 | 2005-04-28 | Toagosei Co., Ltd. | Polymer having oxetanyl group and cation-curable resin composition containing the same |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4230814A (en) * | 1979-02-12 | 1980-10-28 | General Electric Company | Heat curable compositions |
US4284753A (en) * | 1980-04-14 | 1981-08-18 | Shell Oil Company | Heat curable polyepoxide-unsaturated aromatic monomer resin compositions |
US4544732A (en) * | 1984-12-24 | 1985-10-01 | Shell Oil Company | Heat-curable composition |
US4554341A (en) * | 1985-02-27 | 1985-11-19 | Shell Oil Company | Fire retardant, fast reacting epoxy resin |
JPS62257927A (en) * | 1986-05-02 | 1987-11-10 | Asahi Glass Co Ltd | Curable epoxy resin composition |
JPH1129609A (en) * | 1997-07-08 | 1999-02-02 | Nippon Soda Co Ltd | Thermosetting composition |
US6498200B1 (en) * | 1999-01-12 | 2002-12-24 | Namics Corporation | Cationically polymerizable resin composition |
JP4392096B2 (en) * | 1999-01-12 | 2009-12-24 | ナミックス株式会社 | Cationic polymerizable resin composition |
JP2004352980A (en) * | 2003-05-07 | 2004-12-16 | Mitsui Chemicals Inc | Cationically photopolymerizable resin composition and optical disk surface protecting material |
JP4540409B2 (en) * | 2004-06-29 | 2010-09-08 | 株式会社トクヤマ | Dental polymerizable composition |
US7365106B2 (en) * | 2004-04-27 | 2008-04-29 | Tokuyama Corporation | Cationically curable composition for dental use |
JP4865246B2 (en) * | 2005-03-25 | 2012-02-01 | 株式会社カネカ | Thermal radical curing / thermal cationic curing combined curable composition |
JP2006314242A (en) * | 2005-05-12 | 2006-11-24 | Tokai Univ | Recombinant animal having variant sdhc gene derived from mammal |
JP5333175B2 (en) * | 2009-11-26 | 2013-11-06 | 富士通株式会社 | Operator support device, operator support program, and operator support method |
-
2007
- 2007-11-20 JP JP2010534925A patent/JP5248623B2/en active Active
- 2007-11-20 WO PCT/US2007/085272 patent/WO2009067112A1/en active Application Filing
-
2008
- 2008-05-30 TW TW097119983A patent/TWI423998B/en active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001062834A1 (en) * | 2000-02-18 | 2001-08-30 | Rhodia Chimie | Surface treatment of plastic material with an organic polymerisable and/or crosslinkable composition having reactive functions |
US6805439B2 (en) * | 2001-09-06 | 2004-10-19 | Brother Kogyo Kabushiki Kaisha | Active energy beam-curable composition, ink containing the same, and printer accommodating the same ink |
WO2004099286A1 (en) * | 2003-05-07 | 2004-11-18 | Mitsui Chemicals, Inc. | Cationically photopolymerizable resin composition and optical disk surface protection material |
WO2005037876A1 (en) * | 2003-10-15 | 2005-04-28 | Toagosei Co., Ltd. | Polymer having oxetanyl group and cation-curable resin composition containing the same |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011530632A (en) * | 2008-08-12 | 2011-12-22 | ハンツマン・アドヴァンスト・マテリアルズ・(スイッツランド)・ゲーエムベーハー | Thermosetting composition |
WO2014105422A1 (en) * | 2012-12-27 | 2014-07-03 | 3M Innovative Properties Company | Polymerizable composition including a benzoxazine and an acid-forming peroxide catalyst, article, and method |
US9371477B2 (en) | 2012-12-27 | 2016-06-21 | 3M Innovative Properties Company | Polymerizable composition including a benzoxazine and an acid-forming peroxide catalyst, article, and method |
CN104903382B (en) * | 2012-12-27 | 2017-06-16 | 3M创新有限公司 | Comprising benzoxazine and into the polymerisable compound of acid peroxide catalyst, product and method |
Also Published As
Publication number | Publication date |
---|---|
TW200936632A (en) | 2009-09-01 |
TWI423998B (en) | 2014-01-21 |
JP2011503340A (en) | 2011-01-27 |
JP5248623B2 (en) | 2013-07-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2948506B1 (en) | Underfill composition and packaging process using the same | |
EP1834969A2 (en) | Curable materials containing siloxane | |
EP2297238B1 (en) | Thixotropic conductive composition | |
US8324319B2 (en) | Redox-induced cationically polymerizable compositions with low cure temperature | |
JP6873489B2 (en) | Resin compositions, adhesives, encapsulants, dams, and semiconductor devices | |
EP1362901B1 (en) | Thermoset adhesive films | |
WO2009067112A1 (en) | Redox-induced cationically polymerizable compositions with low cure temperature | |
US20100210801A1 (en) | Copolymer | |
JP5881317B2 (en) | Process for producing unsaturated quaternary ammonium salt compound, and antistatic agent and antistatic composition comprising the same | |
CN111527130B (en) | Resin composition, cured product thereof, adhesive, semiconductor device, and electronic component | |
KR100758879B1 (en) | One-solution type thermosetting composition for protective film of color filter | |
JP2015021045A (en) | Optical three-dimensional contouring resin composition consisting of cyclic ether group-containing (meth)acrylate | |
JP4119834B2 (en) | Cycloalkyl vinyl ether-maleic anhydride copolymer, curing agent and curable resin composition containing the copolymer | |
WO2015012258A1 (en) | Composition, curable composition, production method therefor, and cured product | |
JP6447665B2 (en) | Method for producing resin composition | |
JP2010053170A (en) | Acrylic resin composition | |
JP2009001730A (en) | Polymer compound and production method thereof | |
JP2008201955A (en) | Thermosetting resin composition containing polyfunctional (meth)acrylate | |
EP1716124B1 (en) | Maleimide resin with cyanurate core | |
WO2024038761A1 (en) | Cured product, article provided with cured product, and method for lessening internal stress of cured product | |
EP1716215B1 (en) | Curable liquid compositions containing bisoxazoline | |
CN115003709B (en) | Compound, method for producing compound, and curable composition | |
WO2023238925A1 (en) | Radical polymerizable composition and polymerized product thereof | |
US7390430B2 (en) | Curable liquid compositions containing bisoxazoline | |
KR100782264B1 (en) | One-solution type thermosetting resin composition for protective film of color filter and color filter using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07864670 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010534925 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 07864670 Country of ref document: EP Kind code of ref document: A1 |