WO2021053993A1 - Générateur d'acide et composition durcissable le contenant - Google Patents

Générateur d'acide et composition durcissable le contenant Download PDF

Info

Publication number
WO2021053993A1
WO2021053993A1 PCT/JP2020/030342 JP2020030342W WO2021053993A1 WO 2021053993 A1 WO2021053993 A1 WO 2021053993A1 JP 2020030342 W JP2020030342 W JP 2020030342W WO 2021053993 A1 WO2021053993 A1 WO 2021053993A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid generator
group
curable composition
synthesis
examples
Prior art date
Application number
PCT/JP2020/030342
Other languages
English (en)
Japanese (ja)
Inventor
篤志 白石
Original Assignee
サンアプロ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by サンアプロ株式会社 filed Critical サンアプロ株式会社
Priority to JP2021546542A priority Critical patent/JP7177281B2/ja
Publication of WO2021053993A1 publication Critical patent/WO2021053993A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to an acid generator suitable for forming a cured product having excellent curability, heat resistance, and heat-resistant yellowing, a curable composition containing the acid generator, and a cured product using the same.
  • onium salts such as iodonium and sulfonium salts are known as cationic polymerization initiators that cure cationically polymerizable compounds such as epoxy compounds by irradiation with active energy rays such as heat, light, and electron beams.
  • an electronic device is equipped with a small and thin image sensor, and the image sensor is generally composed of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and an optical element such as a lens.
  • a cationic curable composition is preferably used as compared with a radical curable composition because curing inhibition by oxygen does not occur and shrinkage during curing is small.
  • the optical elements mounted on electronic devices are required to have heat resistance and heat-resistant yellowing that can be mounted by soldering by a reflow method for the purpose of improving manufacturing efficiency.
  • the use of lead has been restricted due to consideration for the environment, and soldering has been performed using lead-free solder. Therefore, higher heat resistance (about 270 ° C.) and heat-resistant yellowing are required. became.
  • An acid consisting of an anion having a specific structure with aluminum as the central element as a cationic polymerization initiator (acid generator) that does not contain toxic metals and has high cationic polymerization performance and cross-linking reaction performance such as SbF 6 -salt. Generators have been proposed (Patent Documents 5 and 6). However, although it is excellent in curability, there is a problem that the transparency is lowered after the heat resistance test of the cured product, and its application to members requiring the above optical characteristics has not progressed.
  • an object of the present invention is excellent in curability, and excellent in heat resistance and heat-resistant yellowing by applying light irradiation or heat treatment (that is, the shape is maintained even under high temperature conditions such as soldering by a reflow method). It is an object of the present invention to provide an acid generator suitable for forming a cured product (which is capable of forming a cured product which is resistant to yellowing) and a curable composition containing the same. Another object of the present invention is to provide a cured product obtained by curing the curable composition, which has curability, heat resistance, and heat-resistant yellowing.
  • the present inventor has found that an anion having a specific structure can be used as an acid generator in the process of examining an anion having aluminum as a central element, and has completed the present invention as a result of diligent studies to solve the above problems. It is a thing.
  • the present invention is a curable composition containing an acid generator containing an onium salt represented by the following general formula (1), and the acid generator and a cationically polymerizable compound.
  • R 1 to R 3 are phenyl groups which may independently have an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or a substituent, and R 1 Part or all of the hydrogen atoms bonded to at least one group of ⁇ R 3 are replaced with fluorine atoms, and 30% to 70% of the total hydrogen atoms bonded to the groups of R 1 to R 3 are Substituted with a fluorine atom; E represents an element of valence n selected from S, I, N or P, n is an integer of 1 to 3 and R 4 is an organic group attached to E.
  • the number of R 4 is n + 1, (n + 1 ) number of R 4 may respectively be the same or different from each other, two or more R 4 may bond directly or -O -, - S -, - SO -, - SO 2 -, - NH -, - CO -, - COO -, - CONH-, may form a ring structure containing an element E through an alkylene group or a phenylene group.
  • the present invention also provides a cured product obtained by curing the curable composition described above.
  • the optical element can be mounted on the board by reflow soldering together with other parts, and an optical device equipped with the optical element can be manufactured with excellent work efficiency. .. It can also be used for in-vehicle electronic devices that require heat resistance.
  • the acid generator of the present invention contains an onium salt represented by the following general formula (1).
  • R 1 to R 3 are phenyl groups which may independently have an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or a substituent, and R 1 Part or all of the hydrogen atoms bonded to at least one group of ⁇ R 3 are replaced with fluorine atoms, and 30% to 70% of the total hydrogen atoms bonded to the groups of R 1 to R 3 are Substituted with a fluorine atom; E represents an element of valence n selected from S, I, N or P, n is an integer of 1 to 3 and R 4 is an organic group attached to E.
  • the number of R 4 is n + 1, (n + 1 ) number of R 4 may respectively be the same or different from each other, two or more R 4 may bond directly or -O -, - S -, - SO -, - SO 2 -, - NH -, - CO -, - COO -, - CONH-, may form a ring structure containing an element E through an alkylene group or a phenylene group.
  • examples of the alkyl group having 1 to 8 carbon atoms in R 1 to R 3 include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl and the like.
  • Branched alkyl groups isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl, etc.
  • cycloalkyl groups (, etc.) Cyclopropyl, cyclobutyl, cyclopentyl can be mentioned.
  • the alkenyl group having 2 to 8 carbon atoms in R 1 to R 3 includes a linear or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2). -Butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc.), and cycloalkenyl groups (2-cyclohexenyl). And 3-cyclohexenyl, etc.).
  • the phenyl group which may have a substituent in R 1 to R 3 is an alkyl having 1 to 8 carbon atoms as a part of the hydrogen atom in the phenyl group in addition to the phenyl group. It represents a group, an alkenyl group having 2 to 8 carbon atoms, a nitro group, an alkoxy group represented by -OR 5 , an alkylthio group represented by -SR 6 , or a group substituted with a chlorine atom or a bromine atom.
  • examples of the alkyl group having 1 to 8 carbon atoms and the alkenyl group having 2 to 8 carbon atoms are the same as those described in R 1 to R 3 of the general formula (1).
  • alkoxy group represented by -OR 5 alkylthio group represented by -SR 6 include an alkyl group of R 5 ⁇ R 6 as 1 to 8 carbon atoms, specifically the Alkyl groups having 1 to 8 carbon atoms can be mentioned.
  • Alkoxy groups represented by -OR 5 include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and 2-. Methylbutoxy and the like can be mentioned.
  • Examples of the alkylthio group represented by -SR 6 include methylthio, ethylthio, butylthio, hexylthio, cyclohexylthio and the like.
  • an alkyl group having 1 to 8 carbon atoms preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group represented by -OR 5, chlorine atom, or bromine It is an atom, more preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 2 to 4 carbon atoms, or a chlorine atom.
  • Medium R 1 ⁇ R 3 from the viewpoint of ready availability of starting material, preferably an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a phenyl group and, It is an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a phenyl group substituted with a chlorine atom. Further, it is more preferable that the total number of carbon atoms in R 1 to R 3 is 4 to 9.
  • the groups in R 1 to R 3 in the formula (1) may be the same or different, and a part or all of the hydrogen atoms bonded to at least one group are substituted with fluorine atoms, and R 1 to R 1 to 30% to 70% of all the hydrogen atoms bonded to the group of R 3 are those substituted with a fluorine atom.
  • This is called the fluorine substitution rate.
  • the fluorine substitution rate needs to be 30% to 70%. If the fluorine substitution rate is less than 30%, the anion formed becomes unstable and it becomes difficult to use it as an acid generator, which is unsuitable.
  • anion structure of the acid generator represented by the general formula (1) for example, those represented by the following chemical formulas (A-1) to (A-14) can be preferably exemplified.
  • R 4 in the formula (1) represents an organic group bonded to E, and may be the same or different.
  • alkyl group R 4 ⁇ 1 carbon atoms in 18, straight-chain alkyl group (methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- octyl, n- decyl, n- dodecyl, n- Tetradecyl, n-hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3- Tetramethylbutyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), crosslinked cyclic alkyl groups
  • alkenyl groups of R 4 having 2 to 18 carbon atoms in a straight or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl -1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2-cyclohexenyl, 3-cyclohexenyl, etc.) and aryl Examples include alkenyl groups (styryl, cinnamyl, etc.).
  • the aryl groups of R 4 C 6 -C in 14 (following carbon number of the substituent is not included), a monocyclic aryl group (such as phenyl), condensed polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl, Anthraquinolyl, fluorenyl, naphthoquinolyl, etc.) and aromatic heterocyclic hydrocarbon groups (thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, etc.
  • a monocyclic aryl group such as phenyl
  • condensed polycyclic aryl group naphthyl, anthracenyl, phenanthrenyl, Anthraquinolyl, fluorenyl, naphthoquinolyl, etc.
  • aromatic heterocyclic hydrocarbon groups
  • the aryl group includes an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a nitro group.
  • an alkoxy group represented by -OR 5 an alkylthio group represented by -SR 6 , an acyl group represented by R 7 CO-, an acyloxy group represented by R 8 COO-, and -NR 9 the amino group represented by R 10, a R 5 ⁇ R 10 are mentioned an alkyl group having 1 to 8 carbon atoms and an alkyl group having 1 to 8 carbon atoms among the alkyl groups mentioned specifically ..
  • R 5 to R 10 include aryl groups having 6 to 14 carbon atoms, and specific examples thereof include the above-mentioned aryl groups having 6 to 14 carbon atoms.
  • Alkoxy groups represented by -OR 5 include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and 2-. Methylbutoxy and the like can be mentioned.
  • Examples of the aryloxy group represented by ⁇ OR 5 include phenoxy and naphthoxy.
  • Examples of the alkylthio group represented by -SR 6 include methylthio, ethylthio, butylthio, hexylthio, cyclohexylthio and the like.
  • Examples of the arylthio group represented by -SR 6 include phenylthio, naphthylthio, biphenylthio, 2-thioxanthonylthio and the like.
  • Examples of the acyl group represented by R 7 CO- include acetyl, propanoyl, butanoyl, pivaloyl and benzoyl.
  • Examples of the amino group represented by ⁇ NR 9 R 10 include methylamino, ethylamino, propylamino, dimethylamino, diethylamino, methylethylamino, dipropylamino, dipropylamino and piperidino.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • cationic polymerization initiating ability aspect preferred are an alkyl group having 1 to 18 carbon atoms, an aryl group and a nitro group having 6 to 14 carbon atoms, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, -OR
  • An alkoxy group represented by 5 an arylthio group represented by -SR 6 , an acyl group represented by R 7 CO-, an acyloxy group represented by R 8 COO-, or 6 to 6 carbon atoms substituted with a chlorine atom. It is an aryl group of 14.
  • an alkyl group having 1 to 18 carbon atoms a phenyl group and a hydroxyl group
  • an alkyl group having 1 to 18 carbon atoms an alkoxy group represented by -OR 5
  • arylthio group represented by -SR 6 an acetyl group
  • Benzoyl group phenyl group substituted with acetoxy group.
  • the two or more R 4 may bond directly or -O -, - S -, - SO -, - SO 2 -, - NH -, - CO -, - COO -, - CONH-, an alkylene group or a phenylene group
  • a ring structure containing the element E may be formed through the ring.
  • E in formula (1) is, S (sulfur), I (iodine) is selected from N (nitrogen) or P (phosphorus), represents an element of valency n, and with an organic radical R 4 onium Form [E + ].
  • n represents the valence of the element E and is an integer of 1 to 3.
  • Corresponding onium ions are ammonium, phosphonium, sulfonium, and iodonium. Of these, ammonium, phosphonium, sulfonium, and iodonium, which are stable and easy to handle, are preferable, and sulfonium and iodonium, which are excellent in cationic polymerization performance and cross-linking reaction performance, are more preferable.
  • ammonium ions include tetraalkylammoniums such as tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, and tetraethylammonium; N, N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidi.
  • Pyrrolidiniums such as Nium, N, N-diethylpyrrolidinium; N, N'-dimethylimidazolinium, N, N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3 Imidazolinium such as 4-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidinium such as N, N'-dimethyltetrahydropyrimidinium; N, N'-dimethylmol Morphorinium such as holinium; piperidinium such as N, N'-diethylpiperidinium; pyridinium such as N-methylpyridinium, N-benzylpyridinium, N-phenacylpyridium; N, N'-dimethylimidazolium, etc.
  • Imidazolium such as N-methylquinolium, N-benzylquinolium, N-phenacylquinolium; isoquinolium such as N-methylisoquinolium; thiazonium such as benzylbenzothiazonium, phenacylbenzothiazonium Acridium such as benzylacrydium and phenacylacrydium can be mentioned.
  • phosphonium ions include tetraarylphosphoniums such as tetraphenyl phosphonium, tetra-p-tolyl phosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, and tetrakis (4-methoxyphenyl) phosphonium.
  • tetraarylphosphoniums such as tetraphenyl phosphonium, tetra-p-tolyl phosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, and tetrakis (4-methoxyphenyl) phosphonium.
  • Triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, triphenylbutylphosphonium; triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacilphosphonium , Tetraalkylphosphoniums such as tributylphenacilphosphoniums and the like.
  • sulfonium ion examples include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, and tris (4).
  • iodonium ions include diphenyl iodonium, di-p-tolyl iodonium, di (4-tert-butylphenyl) iodonium, di (4-dodecylphenyl) iodonium, di (4-methoxyphenyl) iodonium, (4-methoxyphenyl) iodonium.
  • Phenyl Iodonium Di (4-decyloxyphenyl) Iodonium, 4- (2-Hydroxytetradecyloxy) Phenylphenyl Iodonium, 4-Isopropylphenyl (p-Trill) Iodonium, Phenyl (2,4,6- Examples include iodonium ions such as trimethoxyphenyl) iodonium and 4-isobutylphenyl (p-tolyl) iodonium.
  • the onium salt represented by the formula (1) of the present invention can be produced by a metathesis method.
  • the compound decomposition method is, for example, New Experimental Chemistry Course 14-I (1978, Maruzen) p-448; Advance in Composer Science, 62, 1-48 (1984); New Experimental Chemistry Course 14-III (1978, Maruzen). ) Pp1838-1846; Organic Sulfur Chemistry (Synthetic Reactions, 1982, Chemistry), Chapter 8, pp237-280; Nihon Kagaku Magazine, 87, (5), 74 (1966); , Japanese Patent Application Laid-Open No. 61-212554, Japanese Patent Application Laid-Open No. 61-100557, Japanese Patent Application Laid-Open No.
  • the solvent water or an organic solvent can be used.
  • the organic solvent include hydrocarbons (hexane, heptane, toluene, xylene, etc.), cyclic ethers (tetrahexyl, dioxane, etc.), chlorine-based solvents (chloroform, dichloromethane, etc.), alcohols (methanol, ethanol, isopropyl alcohol, etc.), ketones (methanol, ethanol, isopropyl alcohol, etc.), ketones ( Includes acetone, methyl ethyl ketone and methyl isobutyl ketone, etc.), nitriles (acetriform, etc.) and polar organic solvents (dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, etc.). These solvents may be used alone or in combination of two or more.
  • the desired onium salt thus produced is separated by crystals or oil.
  • an oily substance it is obtained by separating the precipitated oily substance from the organic solvent solution and further distilling off the organic solvent contained in the oily substance.
  • crystals it is obtained by separating the precipitated solid from the organic solvent solution and further distilling off the organic solvent contained in the solid.
  • the desired onium salt thus obtained can be purified by a method such as recrystallization or washing with water or a solvent, if necessary.
  • Purification by recrystallization dissolves the target onium salt in a small amount of organic solvent, and separation from the organic solvent is performed by directly (or after concentrating) the poor solvent in the organic solvent solution containing the target onium salt. In addition, it can be carried out by precipitating the desired onium salt.
  • the poor solvent used here include chain ethers (diethyl ether, dipropyl ether, etc.), esters (ethyl acetate, butyl acetate, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.) and aromatic hydrocarbons (toluene and cyclohexane, etc.).
  • Xylene, etc. is included.
  • Purification can also be performed by utilizing the difference in solubility depending on the temperature. Purification can be performed by recrystallization (a method utilizing the difference in solubility due to cooling, a method of adding a poor solvent to precipitate, and a combination thereof).
  • the target product is an oil (when it does not crystallize)
  • the oil can be purified by washing with water or a poor solvent.
  • the structure of the thus obtained onium salts generally analytical techniques, for example, 1 H, 13 C, 19 F, the nuclear magnetic resonance spectrum, such as that identified by like infrared absorption spectrum or elemental analysis Can be done.
  • the acid generator of the present invention may be used alone or in combination of two or more.
  • the onium salt (acid generator) represented by the formula (1) may be dissolved in advance in a solvent that does not inhibit the polymerization or cross-linking reaction in order to facilitate dissolution in the cationically polymerizable compound.
  • the solvent examples include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; ethylene glycol and ethylene glycol.
  • Polyhydric alcohols such as monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether.
  • cyclic ethers such as dioxane; ethyl acetate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate , Methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl Esters such as acetate and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene can be mentioned.
  • the ratio of the solvent used is preferably 15 to 1000 parts by weight, more preferably 30 to 1000 parts by weight, based on 100 parts by weight of the onium salt (acid generator) represented by the formula (1) of the present invention. It is 500 parts by weight.
  • the solvent used may be used alone or in combination of two or more.
  • the curable composition of the present invention comprises the above acid generator and a cationically polymerizable compound.
  • Examples of the cationically polymerizable compound that is a constituent of the curable composition include cyclic ethers (epoxides and oxetane, etc.), ethylenically unsaturated compounds (vinyl ether, styrene, etc.), bicycloorthoesters, spirooltocarbonates, spirooltoesters, and the like.
  • cyclic ethers epoxides and oxetane, etc.
  • ethylenically unsaturated compounds vinyl ether, styrene, etc.
  • bicycloorthoesters e.g., spirooltocarbonates, spirooltoesters, and the like.
  • JP-A-11-060996, JP-A-09-302269, JP-A-2003-026993, JP-A-2002-206017 Japanese Patent Application Laid-Open No.
  • Japanese Patent Application Laid-Open No. 10-212343 Japanese Patent Application Laid-Open No. 2000-119306
  • Japanese Patent Application Laid-Open No. 10-67812 Japanese Patent Application Laid-Open No. 2000-186071, Japanese Patent Application Laid-Open No. 08-85775, Japanese Patent Application Laid-Open No. 08-134405, Kai 2008-20838, Japanese Patent Application Laid-Open No. 2008-20389, Japanese Patent Application Laid-Open No. 2008-20841, Japanese Patent Application Laid-Open No. 2008-26660, Japanese Patent Application Laid-Open No. 2008-26644, Japanese Patent Application Laid-Open No.
  • epoxide known epoxides and the like can be used, and aromatic epoxides, alicyclic epoxides, heterocyclic epoxides and aliphatic epoxides are included.
  • aromatic epoxide examples include glycidyl ethers of monovalent or polyvalent phenols (phenols, bisphenol A, phenol novolacs and compounds having alkylene oxide adducts thereof) having at least one aromatic ring.
  • the alicyclic epoxide is a compound obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, (3).
  • heterocyclic epoxide examples include heterocycles other than epoxy groups in the molecule [for example, tetrahydrofuran ring, tetrahydropyran ring, morpholin ring, chroman ring, isochroman ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, aziridine ring, pyrolysine ring.
  • Isocyanurate 1- (2-methylpropenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxidepropyl) isocyanurate, diallyl monoglycidyl isocyanurate , 1,3-Diallyl-5- (2-methylepoxidepropyl) isocyanurate, 1,3-bis (2-methylpropenyl) -5-glycidyl isocyanurate, 1,3-bis (2-methylpropenyl) -5 -(2-Methylepoxidepropyl) isocyanurate, triglycidyl isocyanurate, tris (2-methylepoxidepropyl) isocyanurate, 1,3,4,6-tetraglycidyl glycoluryl, 1,3,4,6-tetrakis ( 2-Methylepoxide propyl) glycol uryl, 1-allyl-3,4,6-trig
  • Aliphatic epoxides include aliphatic polyhydric alcohols, polyglycidyl ethers of this alkylene oxide adduct (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), and aliphatic polybasic acids. Examples thereof include polyglycidyl esters (diglycidyl tetrahydrophthalate, etc.) and epoxidized long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).
  • oxetane known ones and the like can be used, for example, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-3).
  • Oxetanylmethyl) ether 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, oxetanylsilsesquioxetane, phenol novolac oxetane, etc.
  • Oxetanylmethyl) ether 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, oxetanylsil
  • ethylenically unsaturated compound known cationically polymerizable monomers and the like can be used, and includes aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene and cationically polymerizable nitrogen-containing monomers.
  • Examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether and the like.
  • aromatic monovinyl ether examples include 2-phenoxyethyl vinyl ether, phenyl vinyl ether and p-methoxyphenyl vinyl ether.
  • polyfunctional vinyl ether examples include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.
  • styrene examples include styrene, ⁇ -methylstyrene, p-methoxystyrene, p-tert-butoxystyrene and the like.
  • Examples of the cationically polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.
  • Bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2.2.2] octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo. -[2.2.2] Octane and the like can be mentioned.
  • spiro orthocarbonate examples include 1,5,7,11-tetraoxaspiro [5.5] undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane. Be done.
  • Spiro orthoesters include 1,4,6-trioxaspiro [4.4] nonane, 2-methyl-1,4,6-trioxaspiro [4.4] nonane and 1,4,6-trioxas. Pyro [4.5] decane and the like can be mentioned.
  • a polyorganosiloxane having at least one cationically polymerizable group in one molecule can be used (Japanese Patent Laid-Open No. 2001-348482, JP-A-2000-281965, JP-A-7-242828, JP. Japanese Unexamined Patent Publication No. 2008-195931, Journal of Polymer. Sci., Part A, Polymer. Chem., Vol. 28,497 (1990), etc.). These polyorganosiloxanes may be linear, branched, or cyclic, or may be a mixture thereof.
  • cationically polymerizable compounds epoxides, oxetane and vinyl ethers are preferable, and epoxides and oxetanees are more preferable, and alicyclic epoxides and oxetanees are particularly preferable. Further, these cationically polymerizable compounds may be used alone or in combination of two or more.
  • the content of the onium salt (acid generator) represented by the formula (1) of the present invention in the curable composition is preferably 0.05 to 20 parts by weight, more preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. It is preferably 0.1 to 10 parts by weight. Within this range, the polymerization of the cationically polymerizable compound becomes more sufficient, and the physical properties of the cured product become even better. This content is determined by various factors such as the properties of the cationically polymerizable compound, the type and irradiation amount of the active energy ray (when the active energy ray is used), the heating temperature, the curing time, the humidity, and the thickness of the coating film. Determined by consideration and not limited to the above range.
  • the curable composition of the present invention may contain known additives (sensitizers, pigments, fillers, conductive particles, antistatic agents, flame retardants, defoamers, flow modifiers, photostabilizers, if necessary. Agents, antioxidants, adhesion-imparting agents, ion-supplementing agents, anti-coloring agents, solvents, non-reactive resins, radically polymerizable compounds, etc.) can be contained.
  • sensitizer known sensitizers (Japanese Patent Laid-Open No. 11-279212, JP-A-09-183960, etc.) can be used, and benzoquinone ⁇ 1,4-benzoquinone, 1,2-benzoquinone, etc. ⁇ ; naphthoquinone ⁇ 1,4-naphthoquinone, 1,2-naphthoquinone, etc. ⁇ ; Anthracene ⁇ 2-methylanthracene, 2-ethylanthracene, etc. ⁇ , anthracene ⁇ anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9, 10-Diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc. ⁇ ; pyrene; 1,2-benzanthracene; perylene; tetracene; coron
  • the content of the sensitizer is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, based on 100 parts by weight of the acid generator.
  • pigment known pigments and the like can be used, and examples thereof include inorganic pigments (titanium oxide, iron oxide, carbon black, etc.) and organic pigments (azo pigments, cyanine pigments, phthalocyanine pigments, quinacridone pigments, etc.).
  • inorganic pigments titanium oxide, iron oxide, carbon black, etc.
  • organic pigments azo pigments, cyanine pigments, phthalocyanine pigments, quinacridone pigments, etc.
  • the content of the pigment is preferably 0.5 to 400,000 parts by weight, more preferably 10 to 150,000 parts by weight, based on 100 parts by weight of the acid generator.
  • filler known fillers and the like can be used, and molten silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate, lithium aluminum silicate and the like can be used. Can be mentioned.
  • the content of the filler is preferably 50 to 600,000 parts by weight, more preferably 300 to 200,000 parts by weight, based on 100 parts by weight of the acid generator.
  • conductive particles known conductive particles can be used, and metal particles such as Ni, Ag, Au, Cu, Pd, Pb, Sn, Fe, Ni, and Al, and plated metals obtained by further metal-plating these metal particles. Particles, plated resin particles obtained by metal-plating resin particles, and particles of a conductive substance such as carbon can be used.
  • the content of the conductive particles is preferably 50,000 to 30,000 parts by weight, more preferably 100 to 20,000 parts by weight, based on 100 parts by weight of the acid generator.
  • antistatic agent known antistatic agents and the like can be used, and examples thereof include non-ionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents and polymer antistatic agents. ..
  • the content of the antistatic agent is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight, based on 100 parts of the acid generator.
  • a known flame retardant or the like can be used, and an inorganic flame retardant ⁇ antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide , Magnesium hydroxide and calcium aluminate ⁇ ; brominated flame retardants ⁇ tetrabromophthalic anhydride, hexabromobenzene and decabromobiphenyl ethers, etc. ⁇ ; and phosphate ester flame retardants ⁇ tris (tribromophenyl) phosphate, etc. ⁇ Be done.
  • the content of the flame retardant is preferably 0.5 to 40,000 parts by weight, more preferably 5 to 10,000 parts by weight, based on 100 parts by weight of the acid generator.
  • the defoaming agent a known defoaming agent or the like can be used, and an alcohol defoaming agent, a metal soap defoaming agent, a phosphoric acid ester defoaming agent, a fatty acid ester defoaming agent, a polyether defoaming agent, a silicone defoaming agent. And mineral oil defoamers and the like.
  • known fluidity adjusters and the like can be used, and examples thereof include hydrogenated castor oil, polyethylene oxide, organic bentonite, colloidal silica, amidowax, metal soap and acrylic acid ester polymer.
  • known light stabilizers and the like can be used, and ultraviolet absorption type stabilizers ⁇ benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof, etc. ⁇ ; radical supplement type stabilizers ⁇ hindered amine, etc. ⁇ ; and quenching. Examples include type stabilizers ⁇ nickel complexes, etc. ⁇ .
  • antioxidants and the like can be used, and examples thereof include phenol-based antioxidants (monophenol-based, bisphenol-based and polymer phenol-based, etc.), sulfur-based antioxidants, phosphorus-based antioxidants, and the like. Be done.
  • adhesion-imparting agent a known adhesion-imparting agent or the like can be used, and examples thereof include a coupling agent, a silane coupling agent, and a titanium coupling agent.
  • ion catching agent known ion catching agents and the like can be used, and examples thereof include organic aluminum (alkoxyaluminum, phenoxyaluminum and the like) and the like.
  • antioxidants are effective, and phenol-based antioxidants (monophenol-based, bisphenol-based, high-molecular-weight phenol-based, etc.), sulfur-based oxidation. Examples thereof include antioxidants and phosphorus-based antioxidants.
  • the content of each is 0 with respect to 100 parts of the acid generator. It is preferably 1 to 20000 parts by weight, more preferably 0.5 to 5000 parts by weight.
  • the solvent is not limited as long as it can be used for dissolving a cationically polymerizable compound or adjusting the viscosity of an energy ray-curable composition, and the above-mentioned solvent for an acid generator can be used.
  • the content of the solvent is preferably 50 to 2000000 parts by weight, more preferably 200 to 500,000 parts by weight, based on 100 parts by weight of the acid generator.
  • Non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, styrene butadiene block copolymer hydrogenated material, and (meth) acrylic acid ester.
  • Examples include coalescence and polyurethane.
  • the number average molecular weight of these resins is preferably 1000 to 500,000, more preferably 5000 to 100,000 (the number average molecular weight is a value measured by a general method such as GPC).
  • the content of the non-reactive resin is preferably 5 to 400,000 parts by weight, more preferably 50 to 150,000 parts by weight, based on 100 parts by weight of the acid generator.
  • non-reactive resin When a non-reactive resin is contained, it is desirable to dissolve the non-reactive resin in a solvent in advance in order to easily dissolve the non-reactive resin with a cationically polymerizable compound or the like.
  • Known radically polymerizable compounds include ⁇ Photopolymer Social gathering edition "Photopolymer Handbook” (1989, Industrial Research Council), General Technology Center edition “UV / EB Curing Technology” (1982, General Technology Center), Radtech Research. "UV / EB Curing Materials” (1992, CMC) edited by the Society, “Causes of Curing Failure / Inhibition in UV Curing and Countermeasures” (2003, Technical Information Association) ⁇ , etc. It can be used and includes monofunctional monomers, bifunctional monomers, polyfunctional monomers, epoxy (meth) acrylates, polyester (meth) acrylates and urethane (meth) acrylates.
  • the content of the radically polymerizable compound is preferably 5 to 400,000 parts by weight, more preferably 50 to 150,000 parts by weight, based on 100 parts by weight of the acid generator.
  • radical polymerization initiator that initiates polymerization by heat or light in order to increase the molecular weight of these by radical polymerization.
  • radical polymerization initiator known radical polymerization initiators and the like can be used, and thermal radical polymerization initiators (organic peroxides, azo compounds, etc.) and photoradical polymerization initiators (acetophenone-based initiators, benzophenone-based initiators, etc.) Michler ketone-based initiators, benzoin-based initiators, thioxanthone-based initiators, acylphosphine-based initiators, etc.) are included.
  • thermal radical polymerization initiators organic peroxides, azo compounds, etc.
  • photoradical polymerization initiators acetophenone-based initiators, benzophenone-based initiators, etc.
  • Michler ketone-based initiators Michler ketone-based initiators
  • benzoin-based initiators benzoin-based initiators
  • thioxanthone-based initiators thioxanthone-based initiators
  • acylphosphine-based initiators etc.
  • the content of the radical polymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the radically polymerizable compound. ..
  • a cationically polymerizable compound, an acid generator and, if necessary, an additive are uniformly mixed and dissolved at room temperature (about 20 to 30 ° C.) or, if necessary, heating (about 40 to 90 ° C.). It can be prepared by kneading with 3 rolls or the like.
  • the curable composition of the present invention can be cured by irradiating it with energy rays to obtain a cured product.
  • the energy ray may be any as long as it has the energy to induce the decomposition of the acid generator of the present invention, but it may be a low pressure, medium pressure, high pressure or ultra high pressure mercury lamp, metal halide lamp, LED lamp, excimer lamp, carbon arc lamp. , fluorescent lamps, semiconductor solid-state laser, argon laser, the He-Cd laser, KrF excimer laser, ArF excimer laser or F 2 ultraviolet to visible light region derived from a laser or the like (wavelength: about 100 to about 800 nm) energy ray is preferred .
  • the energy ray radiation having high energy such as an electron beam or an X-ray can also be used.
  • the energy ray irradiation time is affected by the intensity of the energy ray and the permeability of the energy ray to the energy ray curable composition, but at room temperature (about 20 to 30 ° C.), about 0.1 to 10 seconds is sufficient. Is. However, when the energy ray permeability is low or the film thickness of the energy ray curable composition is thick, it may be preferable to take a longer time.
  • the energy ray-curable compositions are cured by cationic polymerization 0.1 seconds to several minutes after the energy ray irradiation, but if necessary, after the energy ray irradiation, the room temperature (about 20 to 30 ° C.) to 250 It is also possible to aftercure by heating at ° C for several seconds to several hours.
  • the curable composition of the present invention can be cured by heating to obtain a cured product.
  • heating method for curing conventionally known methods such as heat circulation heating, infrared heating, and high frequency heating can be used.
  • the heating temperature required for curing is not particularly limited as long as the curing proceeds sufficiently and does not deteriorate the substrate, but is preferably in the range of 50 to 250 ° C, more preferably 80 to 200 ° C.
  • the heating time depends on the heating temperature, it is preferably several minutes to several hours from the viewpoint of productivity.
  • the cured product obtained by curing the curable composition of the present invention has excellent heat resistance, and the 5% weight loss temperature is, for example, 260 ° C. or higher, preferably 280 ° C. or higher, and particularly preferably 300 ° C. or higher.
  • the 5% weight loss temperature is determined by differential thermal-thermogravimetric simultaneous measurement (TG-DTA). Therefore, the shape can be maintained even under high temperature conditions such as soldering by the reflow method.
  • the cured product obtained by curing the curable composition of the present invention has excellent transparency, and the yellowness (YI) of the cured product before being subjected to the heat resistance test is, for example, 1.5 or less. Further, the cured product obtained by curing the curable composition of the present invention can suppress yellowing and maintain transparency even under high temperature conditions such as soldering by a reflow method, and has been subjected to a heat resistance test.
  • the yellowness (YI) of the later cured product is, for example, 1.5 or less.
  • the method for measuring the yellowness is as described in the examples.
  • An optical element containing a cured product obtained by curing the curable composition of the present invention as a constituent element has both excellent heat resistance and heat-resistant yellowing.
  • optical elements used for lenses, prisms, LEDs, organic EL elements, semiconductor lasers, transistors, solar cells, CCD image sensors, optical waveguides, optical fibers, alternative glasses (for example, display substrates, hard disk substrates, polarizing films) and the like. is preferably used as.
  • the optical element containing the cured product obtained by curing the curable composition of the present invention as a constituent element has excellent heat resistance, it can be mounted together with other parts by reflow processing at the time of substrate mounting. Is. It can also be used for in-vehicle electronic devices that require heat resistance.
  • Examples of the optical device provided with the above optical elements include portable electronic devices such as mobile phones, smartphones, and tablet PCs; near-infrared sensors, millimeter-wave radars, LED spot lighting devices, near-infrared LED lighting devices, and mirror monitors. , Instrument panels, head-mounted display (projection type) combiners, head-up display combiners, and other in-vehicle electronic devices.
  • parts mean parts by weight and% means% by weight.
  • Synthesis Example 2 Synthesis of Lithium Tetrakis (2-Pentafluoroethyl-2-Propoxy) Aluminate (A-2)
  • A-2 Synthesis of Lithium Tetrakis (2-Pentafluoroethyl-2-Propoxy) Aluminate
  • 16.0 g of 2-trifluoromethyl-2-propanol was added to 2-pentafluoroethyl-2.
  • -A white solid was obtained in the same manner as in Synthesis Example 1 except that it was changed to 22.3 g of propanol (15.6 g). It was confirmed by 1 H-NMR and F-NMR that this white solid was (A-2) (yield 84%, fluorine substitution rate 45%).
  • Synthesis Example 3 Synthesis of Lithium Tetrakis (2-Heptafluoropropyl-2-Propoxy) Aluminate (A-3)
  • A-3 Synthesis of Lithium Tetrakis (2-Heptafluoropropyl-2-Propoxy) Aluminate (A-3)
  • 16.0 g of 2-trifluoromethyl-2-propanol was added to 2-heptafluoropropyl-2.
  • -A white solid was obtained in the same manner as in Synthesis Example 1 except that it was changed to 28.5 g of propanol (18.0 g). It was confirmed by 1 H-NMR and F-NMR that this white solid was (A-3) (yield 76%, fluorine substitution rate 54%).
  • Synthesis Example 4 Synthesis of lithium tetrakis (hexafluoro-tert-butoxy) aluminate (A-4)
  • A-4 Synthesis of lithium tetrakis (hexafluoro-tert-butoxy) aluminate (A-4)
  • 16.0 g of 2-trifluoromethyl-2-propanol was converted to 22.8 g of hexafluoro-tert-butanol.
  • a white solid was obtained in the same manner as in Synthesis Example 1 except for the modification (16.0 g). It was confirmed by 1 H-NMR and F-NMR that this white solid was (A-4) (yield 84%, fluorine substitution rate 67%).
  • Synthesis Example 5 Synthesis of Lithium Tetrakis (2-Vinyl-Hexafluoro-2-Propoxy) Aluminate (A-5)
  • a slightly yellow solid was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 24.3 g of -2-propanol (15.7 g). It was confirmed by 1 H-NMR and F-NMR that this slightly yellow solid was (A-5) (yield 78%, fluorine substitution rate 67%).
  • Synthesis Example 6 Synthesis of Lithium Tetrakis (2-allyl-Hexafluoro-2-Propoxy) Aluminate (A-6)
  • A-6 Synthesis of Lithium Tetrakis (2-allyl-Hexafluoro-2-Propoxy) Aluminate (A-6)
  • 16.0 g of 2-trifluoromethyl-2-propanol was added to 2-allyl-hexafluoro.
  • a slightly yellow solid was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 26.0 g of -2-propanol (13.2 g). It was confirmed by 1 H-NMR and F-NMR that this slightly yellow solid was (A-6) (yield 61%, fluorine substitution rate 55%).
  • Synthesis Example 7 Synthesis of Lithium Tetrakis (2-Phenyl-Hexafluoro-2-Propoxy) Aluminate (A-7)
  • a white solid was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 30.5 g of -2-propanol (17.5 g). It was confirmed by 1 H-NMR and F-NMR that this white solid was (A-7) (yield 70%, fluorine substitution rate 55%).
  • Synthesis Example 8 Synthesis of Lithium Tetrakis (2-Pentafluorophenyl-2-Propoxy) Aluminate (A-8)
  • Synthesis Example 1 16.0 g of 2-trifluoromethyl-2-propanol was added to 2-pentafluorophenyl-2.
  • -A white solid was obtained in the same manner as in Synthesis Example 1 except that it was changed to 33.3 g of propanol (15.9 g). It was confirmed by 1 H-NMR and F-NMR that this white solid was (A-8) (yield 68%, fluorine substitution rate 45%).
  • Synthesis Example 9 Synthesis of Lithium Tetrakis (2-p-Trill-Hexafluoro-2-Propoxy) Aluminate (A-9)
  • Synthesis Example 1 16.0 g of 2-trifluoromethyl-2-propanol was added to 2-p-.
  • a pale yellow solid was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 32.3 g of trill-hexafluoro-2-propanol (12.5 g). It was confirmed by 1 H-NMR and F-NMR that this pale yellow solid was (A-9) (yield 47%, fluorine substitution rate 46%).
  • Synthesis Example 10 Synthesis of lithium tetrakis (2-p-chlorophenyl-hexafluoro-2-propoxy) aluminate (A-10)
  • A-10 Synthesis of lithium tetrakis (2-p-chlorophenyl-hexafluoro-2-propoxy) aluminate (A-10)
  • 16.0 g of 2-trifluoromethyl-2-propanol was added to 2-p-.
  • a pale yellow solid was obtained in the same manner as in Synthesis Example 1 except that it was changed to 34.8 g of chlorophenyl-hexafluoro-2-propanol (12.8 g). It was confirmed by 1 H-NMR and F-NMR that this pale yellow solid was (A-10) (yield 45%, fluorine substitution rate 60%).
  • Synthesis Example 12 Synthesis of lithium tris (2-phenyl-hexafluoro-2-propoxy) (nonafluoro-tert-butoxy) aluminate (A-12)
  • 13.6 g of hexafluoro-tert-butanol was added in 2-.
  • a pale yellow solid was prepared in the same manner as in Synthesis Example 11 except that 18.3 g of phenyl-hexafluoro-2-propanol and 6.4 g of 2-trifluoromethyl-2-propanol were changed to 11.8 g of nonafluoro-tert-butanol. Obtained (13.6 g). It was confirmed by 1 H-NMR and F-NMR that this pale yellow solid was (A-12) (yield 55%, fluorine substitution rate 64%).
  • Synthesis Example 13 Synthesis of lithium tris (2-trifluoromethyl-2-propoxy) (nonafluoro-tert-butoxy) aluminate (A-13)
  • Synthesis Example 11 13.6 g of hexafluoro-tert-butanol was added to 2-tri.
  • a white solid was obtained in the same manner as in Synthesis Example 11 except that 9.6 g of fluoromethyl-2-propanol and 6.4 g of 2-trifluoromethyl-2-propanol were changed to 11.8 g of nonafluoro-tert-butanol. 7.1 g). It was confirmed by 1 H-NMR and F-NMR that this white solid was (A-13) (yield 44%, fluorine substitution rate 50%).
  • the reaction solution was cooled to room temperature, poured into 500 g of ion-exchanged water, extracted with 500 g of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral.
  • the dichloromethane layer was transferred to a rotary evaporator and the solvent was evaporated to give a brown liquid product.
  • Examples 2 to 13 Synthesis of acid generators (AG102 to AG113)
  • the lithium salt (A-1) was changed to the lithium salt (A-2) to (A-13), but the same as in Example 1.
  • acid generators (AG102 to AG113) were obtained, respectively.
  • Example 14 Synthesis of thiodi-p-phenylenebis (diphenylsulfonium) di [tetrakis (2-trifluoromethyl-2-propoxy)] aluminate (AG201)
  • the method (thiodi-p) of Patent Document Japanese Patent Laid-Open No. 2013-227368).
  • -A method for synthesizing phenylene bis (diphenylsulfonium) bis (hexafluorophosphate)) was used as a reference to obtain an acid generator (AG201) using a lithium salt (A-1) instead of potassium hexafluorophosphate.
  • reaction solution was cooled to room temperature, poured into 100 mL of ion-exchanged water, extracted with 100 g of dichloromethane, and washed with water until the pH of the aqueous layer became neutral.
  • the dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown solid. This was washed with ethyl acetate / hexane, and the organic solvent was concentrated to obtain 20 g of [4- (4-biphenylthio) phenyl] -4-biphenylphenylsulfonium methanesulfonate (intermediate-2).
  • Example 40 (4-Isopropylphenyl) Trilliodonium Tetrakiss (2-trifluoromethyl-2-propoxy) Aluminate (A401) Synthesis Add 20 g of 4-methyliodobenzene to a reaction vessel, and further add 50 g of acetic acid and 10 g of sulfuric acid. 10 g of potassium persulfate was added little by little at 15 ° C. or lower while cooling in an ice-water bath. The reaction was carried out at 20 ° C. for 4 hours, and 24.4 g of cumene (isopropylbenzene) was added dropwise thereto so as not to exceed 20 ° C. Then, it was reacted at room temperature for 20 hours.
  • reaction solution was added to 500 parts of an aqueous solution containing an equimolar lithium salt (A-1), and the mixture was further stirred for 3 hours.
  • 500 parts of dichloromethane was added thereto. After standing, the aqueous layer was removed by liquid separation, and the organic layer was washed 5 times with 100 parts of water. Dichloromethane was concentrated and recrystallized from cyclohexane to obtain an acid generator (A401).
  • Examples 54 to 65 Synthesis of acid generators (AG502 to AG513)
  • the acid generators were obtained in the same manner as in Example 53, except that they were changed to lithium salts (A-2) to (A-13). (AG502 to AG513) were obtained.
  • Example 66 Synthesis of phenyl (2,4,6-trimethoxyphenyl) iodonium tetrakis (2-trifluoromethyl-2-propoxy) aluminate (AG601) Phenyl (2,4,6-trimethoxyphenyl) in a reaction vessel. 5.4 g of iodonium p-toluenesulfonate and 50 g of dichloromethane were added. While stirring, 50 parts of an aqueous solution containing an equimolar lithium salt (A-1) was added, and the mixture was stirred at room temperature for 8 hours. After standing, the aqueous layer was removed by liquid separation, and the organic layer was further washed with 50 parts of water 5 times. An acid generator (AG601) was obtained by distilling off the organic solvent under reduced pressure.
  • A-1 equimolar lithium salt
  • Example 66 the acid generators were obtained in the same manner as in Example 66, except that they were changed to lithium salts (A-2) to (A-13). (AG602 to AG613) were obtained.
  • Example 105 Synthesis of 4-acetoxyphenyldimethylsulfonium tetrakis (2-trifluoromethyl-2-propoxy) aluminate (AG901) 3.4 g of 4-acetoxyphenyldimethylsulfonium hexafluorophosphate was dissolved in 50 g of dichloromethane and equimolar. 30 g of an aqueous solution containing the lithium salt (A-1) of No. 1 was mixed at room temperature, and the mixture was stirred as it was for 3 hours. The dichloromethane layer was washed 5 times with water by a liquid separation operation, and then transferred to a rotary evaporator to distill off the solvent to obtain an acid generator (AG901).
  • Examples 119 to 130 Synthesis of acid generators (AG1002 to AG1013) Acid generators in the same manner as in Example 118, except that they were changed to lithium salts (A-2) to (A-13) in Example 118. (AG1002 to AG1013) were obtained.
  • Example 123 Comparative Example 12-Synthesis of 4-acetoxyphenyldimethylsulfonium tetrakis (nonafluoro-tert-pentoxy) aluminate (AG923)
  • A-23) was used instead of the lithium salt (A-1).
  • An acid generator (AG923) was obtained in the same manner as in Example 105 (fluorine substitution rate 81%).
  • EP-1 2,2-bis (4-glycidyloxyphenyl) propane
  • EP-2 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate
  • EP-3 3-ethyl-3- ⁇ [(3-Epoxyoxetane-3-yl) methoxy] methyl ⁇ oxetane
  • the curability of the obtained cured product was confirmed based on the presence or absence of tackiness on the surface. The presence or absence of tackiness was judged by palpation. Evaluation Criteria ⁇ : There was no tackiness on the surface and there was no change in the surface shape of the cured product ⁇ : There was no tackiness on the surface, but the surface shape of the cured product changed ⁇ : The surface had tackiness
  • Transparency-1 A spacer made of Teflon (registered trademark) having a length of 20 mm, a width of 20 mm, and a thickness of 0.1 mm was prepared and sandwiched between slide glasses (trade name "S2111", manufactured by Matsunami Glass Co., Ltd.). The curable composition was cast into the gaps, irradiated with light in the same manner as described above, and left at room temperature for 60 minutes after the light irradiation to obtain a cured product. Transparency -1 was evaluated by measuring the transparency (YI) of the obtained cured product using a spectrophotometer (trade name "U-3900", manufactured by Hitachi High-Technologies Corporation). As for the yellowness (YI), the value of the 2 degree field of view in the D65 light source was read.
  • YI yellowness
  • Heat-resistant transparency (transparency-2)] Heat resistance based on the reflow temperature profile (maximum temperature: 270 ° C) described in the JEDEC standard using a tabletop reflow furnace (manufactured by Shinapec) for the cured product obtained by the same method as the above [Transparency-1] evaluation. After the test was carried out three times in succession, the heat-resistant transparency (transparency-2) was evaluated by measuring the transparency (YI) in the same manner as described above.
  • the curable composition obtained by the present invention is excellent in cationic polymerization ability by light irradiation and excellent in heat resistance and transparency of the obtained cured product.
  • the fluorine content of the anion portion in the acid generator of the present invention particularly affects the heat resistance and transparency, and is compared with Examples 131 to 169 (fluorine content of 70% or less) in Tables 7 to 8 and Comparative Examples 17 to 20 (fluorine).
  • Examples 188 to 226 in Tables 9 to 10 with Comparative Examples 33 to 36 it is effective for heat resistance and transparency that the fluorine content of the anion is 70% or less. You can see that.
  • EP-1 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate
  • EP-2 2,2-bis (4-glycidyloxyphenyl) propane
  • EP-3 3-ethyl-3- ⁇ [(3-Epoxyoxetane-3-yl) methoxy] methyl ⁇ oxetane
  • the curability of the obtained cured product was confirmed based on the presence or absence of tackiness on the surface. The presence or absence of tackiness was judged by palpation. Evaluation Criteria ⁇ : There was no tackiness on the surface and there was no change in the surface shape of the cured product ⁇ : There was no tackiness on the surface, but the surface shape of the cured product changed ⁇ : The surface had tackiness
  • Transparency-1 A spacer made of Teflon (registered trademark) having a length of 20 mm, a width of 20 mm, and a thickness of 0.1 mm was prepared and sandwiched between slide glasses (trade name "S2111", manufactured by Matsunami Glass Co., Ltd.). A curable composition was cast into the gap and heated in the same manner as described above to obtain a cured product. Transparency -1 was evaluated by measuring the transparency (YI) of the obtained cured product using a spectrophotometer (trade name "U-3900", manufactured by Hitachi High-Technologies Corporation). As for the yellowness (YI), the value of the 2 degree field of view in the D65 light source was read.
  • YI yellowness
  • Heat-resistant transparency (transparency-2)] Heat resistance based on the reflow temperature profile (maximum temperature: 270 ° C) described in the JEDEC standard using a tabletop reflow furnace (manufactured by Shinapec) for the cured product obtained by the same method as the above [Transparency-1] evaluation. After the test was carried out three times in succession, the heat-resistant transparency (transparency-2) was evaluated by measuring the transparency (YI) in the same manner as described above.
  • the curable composition obtained by the present invention is excellent in cationic polymerization ability by heat and excellent in heat resistance and transparency of the obtained cured product.
  • the fluorine content of the anion portion in the acid generator of the present invention particularly affects the heat resistance and transparency, and is compared with Examples 245 to 270 (fluorine content of 70% or less) and Comparative Examples 49 to 52 (fluorine content) in Table 11.
  • Examples 283 to 308 and Comparative Examples 65 to 68 in Table 12 greater than 70%
  • a fluorine content of an anion of 70% or less is effective for heat resistance and transparency.
  • the curable composition of the present invention Since the curable composition of the present invention has the above-mentioned structure, it is excellent in curability, and by subjecting it to light irradiation or heat treatment, a cured product having excellent curability, transparency, heat resistance, and heat-resistant yellowing is formed. Can be done. Therefore, the curable composition of the present invention comprises an optical element material (lens or prism material, encapsulant, optical waveguide forming material, adhesive, optical fiber forming material, imprint material, alternative glass forming material, etc.), resist, coating. It can be suitably used as an agent or the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne : un générateur d'acide qui est approprié pour la formation d'un produit durci qui a une excellente aptitude au durcissement, une excellente résistance à la chaleur et une excellente résistance au jaunissement thermique ; une composition durcissable qui contient ce générateur d'acide ; et un produit durci qui est obtenu à l'aide de cette composition durcissable. La présente invention concerne un générateur d'acide qui contient un sel d'onium représenté par la formule générale (1). (Dans la formule, chacun de R1 à R3 représente indépendamment un groupe alkyle ayant de 1 à 8 atomes de carbone, un groupe alcényle ayant de 2 à 8 atomes de carbone ou un groupe phényle éventuellement substitué ; une partie ou la totalité des atomes d'hydrogène liés à au moins l'un des groupes R1 à R3 sont substitués par des atomes de fluor, et de 30 % à 70 % de tous les atomes d'hydrogène liés aux groupes R1 à R3 sont substitués par des atomes de fluor ; E représente un élément de valence n sélectionné parmi S, I, N et P ; n représente un nombre entier de 1 à 3 ; et R4représente un groupe organique lié à E.)
PCT/JP2020/030342 2019-09-19 2020-08-07 Générateur d'acide et composition durcissable le contenant WO2021053993A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021546542A JP7177281B2 (ja) 2019-09-19 2020-08-07 酸発生剤、およびこれを含む硬化性組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019170044 2019-09-19
JP2019-170044 2019-09-19

Publications (1)

Publication Number Publication Date
WO2021053993A1 true WO2021053993A1 (fr) 2021-03-25

Family

ID=74883466

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/030342 WO2021053993A1 (fr) 2019-09-19 2020-08-07 Générateur d'acide et composition durcissable le contenant

Country Status (2)

Country Link
JP (1) JP7177281B2 (fr)
WO (1) WO2021053993A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3184569A1 (fr) * 2015-12-23 2017-06-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Initiateurs de durcissement pour la polymerisation cationique
JP2018529831A (ja) * 2015-09-02 2018-10-11 テヒニッシュ・ウニベルズィテート・ウイーンＴｅｃｈｎｉｓｃｈｅ Ｕｎｉｖｅｒｓｉｔａｔ Ｗｉｅｎ カチオン重合性モノマーのフロンタル重合方法
JP2018532866A (ja) * 2015-09-02 2018-11-08 テヒニッシュ・ウニベルズィテート・ウイーンＴｅｃｈｎｉｓｃｈｅ Ｕｎｉｖｅｒｓｉｔａｔ Ｗｉｅｎ カチオン光重合のための新規開始剤およびその使用
JP2019085358A (ja) * 2017-11-06 2019-06-06 サンアプロ株式会社 熱酸発生剤及び硬化性組成物
CN110317320A (zh) * 2018-03-28 2019-10-11 常州格林感光新材料有限公司 阳离子型光固化化合物及包含其的组合物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018529831A (ja) * 2015-09-02 2018-10-11 テヒニッシュ・ウニベルズィテート・ウイーンＴｅｃｈｎｉｓｃｈｅ Ｕｎｉｖｅｒｓｉｔａｔ Ｗｉｅｎ カチオン重合性モノマーのフロンタル重合方法
JP2018532866A (ja) * 2015-09-02 2018-11-08 テヒニッシュ・ウニベルズィテート・ウイーンＴｅｃｈｎｉｓｃｈｅ Ｕｎｉｖｅｒｓｉｔａｔ Ｗｉｅｎ カチオン光重合のための新規開始剤およびその使用
EP3184569A1 (fr) * 2015-12-23 2017-06-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Initiateurs de durcissement pour la polymerisation cationique
JP2019085358A (ja) * 2017-11-06 2019-06-06 サンアプロ株式会社 熱酸発生剤及び硬化性組成物
CN110317320A (zh) * 2018-03-28 2019-10-11 常州格林感光新材料有限公司 阳离子型光固化化合物及包含其的组合物

Also Published As

Publication number Publication date
JPWO2021053993A1 (fr) 2021-03-25
JP7177281B2 (ja) 2022-11-22

Similar Documents

Publication Publication Date Title
EP3345951B1 (fr) Composition durcissable et article durci l'utilisant
US8227624B2 (en) Aromatic sulfonium salt compound
JP5706651B2 (ja) フッ素化アルキルリン酸スルホニウム塩、酸発生剤及び硬化性組成物
JP6924754B2 (ja) スルホニウム塩、光酸発生剤、光硬化性組成物、及びその硬化体
TWI513689B (zh) Aromatic salt compounds
JP2014205624A (ja) オニウムボレート塩系酸発生剤
WO2019225185A1 (fr) Sel de sulfonium, générateur photoacide, composition durcissable et composition de réserve
WO2011016425A1 (fr) Générateur de photoacide, composition photodurcissable et produit durci (?) à partir de celle-ci
JP7444791B2 (ja) スルホニウム塩、光酸発生剤、硬化性組成物およびレジスト組成物
JP5767040B2 (ja) スルホニウム塩、光酸発生剤、硬化性組成物およびレジスト組成物
JP7126344B2 (ja) 硬化性組成物及びそれを用いた光学素子
JP5828679B2 (ja) フッ素化アルキルリン酸オニウム塩系酸発生剤
JP7177281B2 (ja) 酸発生剤、およびこれを含む硬化性組成物
JP2013227368A (ja) 感活性エネルギー線性酸発生剤
JP6046540B2 (ja) スルホニウム塩、光酸発生剤、硬化性組成物およびレジスト組成物
WO2022130796A1 (fr) Photogénérateur d'acide et composition photosensible l'utilisant
JPWO2016132413A1 (ja) スルホニウムボレート塩、酸発生剤及び硬化性組成物
KR20230047050A (ko) 광산 발생제
JP2022135247A (ja) 硬化性組成物ならびにその硬化体
WO2022018968A1 (fr) Générateur de photoacide

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: 20866667

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021546542

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20866667

Country of ref document: EP

Kind code of ref document: A1