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WO2018110179A1 - Dérivé de peroxycinnamate et composition polymérisable le contenant - Google Patents

Dérivé de peroxycinnamate et composition polymérisable le contenant Download PDF

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Publication number
WO2018110179A1
WO2018110179A1 PCT/JP2017/040778 JP2017040778W WO2018110179A1 WO 2018110179 A1 WO2018110179 A1 WO 2018110179A1 JP 2017040778 W JP2017040778 W JP 2017040778W WO 2018110179 A1 WO2018110179 A1 WO 2018110179A1
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Prior art keywords
group
meth
compound
general formula
polymerizable composition
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PCT/JP2017/040778
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English (en)
Japanese (ja)
Inventor
昌樹 林
諒介 糸山
章世 小島
叶涵 喬
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NOF Corp
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NOF Corp
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Priority to JP2018556512A priority Critical patent/JP7031605B2/ja
Priority to CN201780054662.9A priority patent/CN109689624B/zh
Priority to KR1020197010032A priority patent/KR20190091439A/ko
Publication of WO2018110179A1 publication Critical patent/WO2018110179A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/38—Peroxy compounds the —O—O— group being bound between a >C=O group and a carbon atom, not further substituted by oxygen atoms, i.e. esters of peroxy acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/40—Peroxy compounds containing nitrogen atoms
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • 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
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical

Definitions

  • the present invention relates to a peroxycinnamate derivative, a polymerizable composition containing a polymerization initiator containing the compound and a radical polymerizable compound, a cured product thereof, and a method for producing the cured product.
  • radical polymerization initiators that generate radicals by light, heat, or oxidation-reduction are widely used as polymerization initiators.
  • the photopolymerization initiator can generate a radical by bond cleavage or hydrogen abstraction reaction by absorbing active energy rays such as light, and is used as a polymerization initiator for a radical polymerizable compound.
  • ⁇ -hydroxyacetophenone derivatives, ⁇ -aminoacetophenone derivatives, acylphosphine oxide derivatives, halomethyltriazine derivatives, benzyl ketal derivatives, thioxanthone derivatives, and the like are used.
  • the photopolymerizable composition comprising the photopolymerization initiator and the radical polymerizable compound as described above is quickly cured by light irradiation, from the viewpoint of fast curability and low VOC, a coating agent, paint, printing ink, It is applied to applications such as photosensitive printing plates, adhesives, and various photoresists.
  • Patent Document 1 discloses a polymerization initiator containing, as an active ingredient, a benzophenone group-containing peroxyester having a peroxide bond (—O—O—) in a molecule that generates radicals by light or heat.
  • Patent Document 2 discloses an adhesive composition comprising the polymerization initiator and a radical polymerizable compound, and by dual cure that performs curing by irradiation with light at room temperature and subsequent curing by heating, The adhesive exhibits strong adhesive strength and high durability.
  • Dual cure type polymerizable compositions include, for example, curing of polymerizable compositions containing light-absorbing and scattering pigments and fillers at high concentrations, and black frames and touch panels around protective covers in flat panel display manufacturing processes. It is also effective for curing areas where light does not reach, such as the bottom of electrodes.
  • the present invention provides a peroxycinnamate derivative having both photopolymerizability capable of efficiently absorbing light having a wavelength of 365 nm or the like emitted from a lamp to generate radicals and thermal polymerizability. Is.
  • the present invention provides a polymerizable composition containing a polymerization initiator containing the peroxycinnamate derivative and a radical polymerizable compound, a cured product thereof, and a method for producing the cured product.
  • the present invention relates to the general formula (1): (In the formula (1), n represents an integer of 1 to 3, and R 1 is an independent substituent, which is a substituent represented by the general formula (2): R—X—, a nitro group, or A cyano group, wherein X represents an oxygen atom or a sulfur atom, and R may have any one or more of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. .
  • R 1 represents a hydrocarbon group having 1 to 6 carbon atoms, or, R 1 is adjacent two of said general formula (2): .R 2 representing a hydrocarbon group that forms a 5- or 6-membered ring by R-X- is A hydrogen atom or a methyl group, R 3 and R 4 are independently a methyl group or an ethyl group, R 5 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an optionally substituted alkyl group.
  • a peroxycinnamate derivative represented by the following formula:
  • the present invention also includes (a) a polymerization initiator containing the peroxycinnamate derivative and (b) a polymerizable composition containing a radical polymerizable compound, and a cured product formed from the polymerizable composition,
  • the present invention relates to a method for producing a cured product.
  • the peroxycinnamate derivative of the present invention can generate radicals efficiently with respect to light having a wavelength of 365 nm and the like emitted from a lamp, and has a peroxide bond in the molecule, so that it is useful as a light and thermal polymerization initiator. It is. Therefore, the polymerizable composition containing the peroxycinnamate derivative and the radical polymerizable compound can be cured well by light irradiation, and can be cured well by heat even in a dark part where light does not reach.
  • the peroxycinnamate derivative of the present invention can be represented by the following general formula (1).
  • n represents an integer of 1 to 3
  • R 1 is an independent substituent, which is a substituent represented by the general formula (2): R—X—, a nitro group, or A cyano group, wherein X represents an oxygen atom or a sulfur atom, and R may have any one or more of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton.
  • R 1 represents a hydrocarbon group having 1 to 6 carbon atoms, or, R 1 is adjacent two of said general formula (2): .R 2 representing a hydrocarbon group that forms a 5- or 6-membered ring by R-X- is A hydrogen atom or a methyl group, R 3 and R 4 are independently a methyl group or an ethyl group, R 5 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an optionally substituted alkyl group. Represents an aromatic hydrocarbon group of
  • n is represented by an integer of 1 to 3, and represents the number of R 1 side chains on the phenyl group ring. n is preferably 1 or 2 from the viewpoint of easy synthesis of the peroxycinnamate derivative.
  • R 1 is an independent substituent, and represents a substituent represented by the general formula (2): R—X—, a nitro group, or a cyano group.
  • R—X— represents an oxygen atom or a sulfur atom
  • R represents a hydrocarbon having 1 to 6 carbon atoms which may have any one or more of an ether bond, a thioether bond, and a hydroxyl group at the terminal in the carbon skeleton. Represents a group.
  • R 1 represents a hydrocarbon group that forms a 5- to 6-membered ring by two adjacent general formulas (2): R—X—.
  • R 1 is an independent substituent from the viewpoint of high sensitivity to light of the lamp, and represents a substituent represented by the general formula (2): R—X—, and X represents an oxygen atom.
  • R is a hydrocarbon group having 1 to 6 carbon atoms which may have any one or more of an ether bond and a hydroxyl group at the terminal in the carbon skeleton, or R 1 is adjacent to It is preferably a hydrocarbon group that forms a 5- to 6-membered ring by the two general formulas (2): R—X—.
  • R 1 include, for example, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, cyclopentyloxy Group, n-hexyloxy group, cyclohexyloxy group, 2-hydroxyethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2- (2-hydroxyethoxy) ethoxy group, 2- ( 2-ethoxyethoxy) ethoxy group, 1,2-dihydroxypropoxy group, methylenedioxy group, ethylenedioxy group and other alkoxy groups; methylsulfanyl group, ethylsulfanyl group, hexylsulfanyl group, 2-methoxyethylsulfanyl group, 2 -(2-Methoxyethoxy
  • R 1 is a methoxy group, an ethoxy group, a 2-hydroxyethoxy group, a methylene diene group. An oxy group is preferred.
  • R 2 represents a hydrogen atom or a methyl group.
  • R 2 is preferably a hydrogen atom from the viewpoint of increasing the decomposition temperature of the peroxycinnamate derivative and increasing the storage stability of the polymerizable composition.
  • R 3 and R 4 independently represent a methyl group or an ethyl group.
  • R 3 and R 4 are preferably methyl groups from the viewpoint of increasing the decomposition temperature of the peroxycinnamate derivative and increasing the storage stability of the polymerizable composition.
  • R 5 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 9 carbon atoms which may have an alkyl group.
  • the alkyl group may be linear or branched.
  • Specific examples of R 5 include a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, a methylcyclohexyl group, a phenyl group, and an isopropylphenyl group.
  • a methyl group, an ethyl group, a propyl group, a 2,2-dimethylpropyl group, and a phenyl group are preferable from the viewpoint of easy synthesis of the peroxycinnamate derivative.
  • the method for producing the peroxycinnamate derivative represented by the general formula (1) is not particularly limited, but the peroxycinnamate derivative can be synthesized according to a known peroxyester synthesis method described in JP-A No. 51-115411. it can.
  • a cinnamic acid derivative is reacted with a chlorinating agent such as thionyl chloride, phosphorus trichloride, or phosgene as shown in the following reaction formula.
  • a chlorinating agent such as thionyl chloride, phosphorus trichloride, or phosgene as shown in the following reaction formula.
  • the step of obtaining a cinnamic acid chloride derivative hereinafter also referred to as step (A)
  • step of reacting the obtained cinnamic acid chloride derivative and hydroperoxide in the presence of an alkali hereinafter, step) (B) is also included.
  • purification process may be included.
  • R 1 , R 2 , R 3 , R 4 and R 5 are the same as those in the general formula (1).
  • a commercially available product can be used as the cinnamic acid derivative. If there is no commercially available product, it can be synthesized according to a known synthesis method described in paragraph [0230] of JP2013-520490A.
  • the chlorinating agent is preferably reacted in an amount of 1 mol or more, more preferably 1.1 mol or more, with respect to 1 mol of cinnamic acid derivative, from the viewpoint of increasing the yield of the target product, and the solvent is added. It can also be reacted using a large excess amount, but it is preferably 10 mol or less, and preferably 5 mol or less.
  • the reaction temperature is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and 150 ° C. or lower from the viewpoint of increasing the yield of the target product. Preferably, it is 80 degrees C or less.
  • the reaction time varies depending on the raw materials, reaction temperature, etc., and thus cannot be determined unconditionally, but is usually from 30 minutes to 20 hours from the viewpoint of improving the yield of the target product.
  • a peroxycinnamate derivative is obtained by the step (B) of reacting the cinnamic acid chloride derivative obtained in the above step (A) with hydroperoxide in the presence of an alkali.
  • Hydroperoxide is preferably reacted in an amount of 0.8 mol or more, more preferably 1.0 mol or more, with respect to 1 mol of cinnamic acid chloride derivative, from the viewpoint of increasing the yield of the target product, and It is preferable to make it react 3.0 mol or less, and it is preferable to react 1.5 mol or less.
  • Hydroperoxide is commercially available, and when there is no commercial product, it can be synthesized according to a known synthesis method described in JP-A No. 58-72557.
  • the reaction temperature is preferably ⁇ 10 ° C. or higher, more preferably 0 ° C. or higher, and 40 ° C. or lower from the viewpoint of increasing the yield of the target product. Is preferable, and it is more preferable that it is 30 degrees C or less.
  • the reaction time varies depending on the raw materials, reaction temperature, etc., and thus cannot be determined unconditionally, but is usually from 10 minutes to 6 hours from the viewpoint of increasing the yield of the target product.
  • the alkali used is not particularly limited, but sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, pyridine, ⁇ -picoline, ⁇ -picoline, Examples thereof include dimethylaminopyridine, triethylamine, tributylamine, N, N-diisopropylethylamine, 1,5-diazabicyclo [4.3.0] -5-nonene.
  • the alkali is preferably used in an amount of 0.8 mol or more, more preferably 0.9 mol or more, from the viewpoint of increasing the yield of the target product per mol of hydroperoxide, and 2.0 It is preferable to use less than or equal to mol, and more preferably less than or equal to 1.5 mol.
  • the reaction can be performed without using an organic solvent.
  • an organic solvent is not particularly limited because the solubility varies depending on the type of peroxycinnamate derivative.
  • aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
  • Examples include ethers such as tetrahydrofuran and dioxane, esters such as ethyl acetate and butyl acetate, and halogenated hydrocarbons such as methylene chloride and chloroform.
  • the said organic solvent may be used independently and may use 2 or more types together.
  • the amount of the organic solvent used is usually about 30 to 500 parts by mass with respect to 100 parts by mass of the total amount of raw materials.
  • the organic solvent may be removed after step (B) to take out the peroxycinnamate derivative, and the peroxycinnamate derivative is diluted with the organic solvent in order to improve handling and reduce the risk of thermal decomposition. It may be used as a product.
  • the steps (A) and (B) can be performed under normal pressure and under air, but may be performed under a nitrogen stream or under a nitrogen atmosphere.
  • the purification step in order to remove surplus raw materials and by-products, for example, ion-exchanged water or basic such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc.
  • a step of washing with an aqueous solution and purifying the target product can be mentioned.
  • the polymerizable composition of the present invention contains (a) a polymerization initiator and (b) a radical polymerizable compound. Furthermore, the polymerizable composition can impart developability by containing (c) an alkali-soluble resin. Moreover, the polymerizable composition can contain other components in appropriate combination.
  • the polymerization initiator (a) of the present invention contains a peroxycinnamate derivative represented by the general formula (1).
  • the (a) polymerization initiator has a function of decomposing by active energy rays or heat, and the generated radicals start polymerization (curing) of the (b) radical polymerizable compound.
  • Peroxycinnamate derivatives may be used alone or in combination of two or more.
  • the (a) polymerization initiator may contain a polymerization initiator other than the peroxycinnamate derivative (hereinafter also referred to as other polymerization initiator).
  • a polymerization initiator for example, by using a polymerization initiator having an absorption band different from that of the peroxycinnamate derivative, a polymerizable composition for a lamp that emits light of a plurality of wavelengths such as a high-pressure mercury lamp. High sensitivity of objects can be achieved.
  • the types of pigments that absorb or scatter light contained in the polymerizable composition the film thickness of the cured product, etc.
  • ⁇ -Hydroxyacetophenone derivatives such as -2-methylpropiophenone, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one 2-methyl-4′-methylthio-2-morpholinopropiophenone, 2-benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (dimethyl ⁇ -aminoacetoph such as amino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one Enone derivatives; acyl phosphine oxide derivatives such as diphenyl-2,4,6-trimethylbenz
  • the content of the (a) polymerization initiator is preferably 0.1 to 40 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the (b) radical polymerizable compound. More preferably, it is 1 to 15 parts by mass. If the content of the (a) polymerization initiator is less than 0.1 parts by mass with respect to 100 parts by mass of the (b) radical polymerizable compound, the curing reaction does not proceed, which is not preferable.
  • the solubility in (b) radical polymerizable compound reaches saturation, and
  • the crystal of the polymerization initiator is precipitated during film formation of the adhesive composition and the surface of the film becomes rough, or (a) the strength of the coating film of the cured product increases due to an increase in the decomposition residue of the polymerization initiator. Is not preferred because it may decrease.
  • the ratio of another polymerization initiator is 80 mass% or less in (a) polymerization initiator, and is 50 masses. More preferably, it is% or less.
  • radically polymerizable compound (b) of the present invention a compound having an ethylenically unsaturated group can be preferably used.
  • radical polymerizable compounds include (meth) acrylic acid esters, styrenes, maleic acid esters, fumaric acid esters, itaconic acid esters, cinnamic acid esters, crotonic acid esters, and vinyl ethers. Vinyl esters, vinyl ketones, allyl ethers, allyl esters, N-substituted maleimides, N-vinyl compounds, unsaturated nitriles, olefins and the like. Among these, it is preferable to contain (meth) acrylic acid esters having high reactivity.
  • a radically polymerizable compound may be used independently and may use 2 or more types together.
  • monofunctional compounds and polyfunctional compounds can be used as the (meth) acrylic acid esters.
  • Monofunctional compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Alkyl (meth) acrylates such as acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Ester compounds of (meth) acrylic acid and alicyclic alcohols such as acrylate, 2-ethyl-2-adamantyl (meth) acrylate; aryl (meth) such as pheny
  • Monomers having the following nitrogen atoms Monomers having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate; glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether
  • a monomer having an epoxy group such as ruthenium a monomer having a phosphorus atom such as 2-((meth) acryloyloxy) ethyl phosphate; a monomer having a silicon atom such as 3- (meth) acryloxypropyltrimethoxysilane;
  • Monomers having fluorine atoms such as 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate; (Meth) acrylic acid, succinic acid mono (2- (meth) acryl
  • polyfunctional compound examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, glycerin (Meth) acrylate, glycerin propoxy tri
  • the (meth) acrylic acid esters are used to improve the sensitivity of the polymerizable composition, reduce oxygen inhibition, and improve the mechanical strength and hardness, heat resistance, durability, and chemical resistance of the cured coating film.
  • an ester compound of the polyhydric alcohol and (meth) acrylic acid is preferable, and in particular, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, di Pentaerythritol hexaacrylate is preferred.
  • copolymer obtained from the said (b) radically polymerizable compound can be added to the said polymeric composition.
  • the polymerizable composition can be suitably used as a negative resist by further blending (c) an alkali-soluble resin.
  • an alkali-soluble resin As alkali-soluble resin, what is generally used for a negative resist can be used, and it will not be specifically limited if it is resin soluble in alkaline aqueous solution, However, It should be resin containing a carboxyl group. preferable.
  • Alkali-soluble resin may be used independently and may use 2 or more types together.
  • (c) alkali-soluble resin of the present invention for example, a carboxyl group-containing (meth) acrylic acid ester copolymer, a carboxyl group-containing epoxy acrylate resin, and the like are preferably used.
  • the carboxyl group-containing (meth) acrylic acid ester copolymer is at least one selected from the above-mentioned monofunctional compounds of (meth) acrylic acid esters (excluding the monomer having a carboxyl group), ) Acrylic acid, dimer of (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl benzoic acid, cinnamic acid, succinic acid mono (2- (meth) acryloyloxyethyl), phthalic acid mono Ethylenically unsaturated groups such as (2- (meth) acryloyloxyethyl), mono (2- (meth) acryloyloxyethyl) maleate, ⁇ -carboxy-polycaprolactone mono (meth) acrylate, and acid anhydrides thereof It is a copolymer containing at least one selected from the containing carboxylic acids.
  • carboxyl group-containing (meth) acrylic acid ester copolymer examples include methyl methacrylate, cyclohexyl methacrylate, methacrylic acid copolymer, benzyl methacrylate, and methacrylic acid copolymer. Further, styrene, ⁇ -methylstyrene, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, diethyl fumarate, diethyl itaconate and the like may be copolymerized.
  • the carboxyl group-containing (meth) acrylic acid ester copolymer is a reaction of ethylenically unsaturated groups, etc., from the viewpoint of achieving both the developability of the negative resist and the film properties such as heat resistance, hardness, and chemical resistance.
  • a carboxyl group-containing (meth) acrylic acid ester copolymer in which a functional group is introduced into the side chain is also preferably used.
  • an ethylenically unsaturated group into the above side chain for example, a part of the carboxyl group of the carboxyl group-containing (meth) acrylic ester copolymer, an epoxy group in the molecule such as glycidyl (meth) acrylate
  • a method of adding a compound having an ethylenically unsaturated group a method of adding an ethylenically unsaturated group-containing monocarboxylic acid such as methacrylic acid to an epoxy group- and carboxyl group-containing (meth) acrylic acid ester copolymer
  • a method of adding a compound having an isocyanate group and an ethylenically unsaturated group in a molecule such as 2- (meth) acryloyloxyethyl isocyanate to a hydroxyl group- and carboxyl group-containing (meth) acrylic acid ester copolymer.
  • carboxyl group-containing epoxy acrylate resin a compound obtained by further reacting an acid anhydride with an epoxy acrylate resin which is a reaction product of an epoxy compound and the ethylenically unsaturated group-containing carboxylic acid is preferable.
  • epoxy resin examples include (o, m, p-) cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, and bisphenyl fluorene.
  • Examples of the acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and chloredinic anhydride. , Trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, itaconic anhydride and the like.
  • the acid anhydride group remaining after the reaction is hydrolyzed to obtain a carboxyl group.
  • ethylenic double bonds can be increased by using maleic anhydride containing an ethylenically unsaturated group.
  • the acid value of the (c) alkali-soluble resin is preferably 20 to 300 mgKOH / g, and more preferably 40 to 180 mg / KOH.
  • the acid value is less than 20 mgKOH / g, the solubility in an alkaline aqueous solution is poor, and it becomes difficult to develop the unexposed area, which is not preferable.
  • the acid value is more than 300 mgKOH / g, the exposed part tends to be detached from the substrate during development, which is not preferable.
  • the weight average molecular weight of the (c) alkali-soluble resin is preferably 1,000 to 100,000, more preferably 1,500 to 30,000.
  • a weight average molecular weight of less than 1,000 is not preferred because the heat resistance and hardness of the exposed area are poor.
  • the weight average molecular weight can be measured by a gel permeation chromatography (GPC) method.
  • HLC-8220GPC manufactured by Tosoh Corporation
  • TSKgelHZM-M manufactured by Tosoh Corporation
  • tetrahydrofuran is used as a developing solvent
  • column temperature is 40 ° C.
  • flow rate is 0.3 ml / min.
  • the chromatography can be performed under the conditions of RI detector, sample injection concentration 0.5 mass%, injection amount 10 microliters, and the weight average molecular weight in terms of polystyrene can be obtained.
  • the ratio of (c) alkali-soluble resin is preferably 10 to 70% by mass, and more preferably 15 to 60% by mass in the total solid content of the polymerizable composition.
  • the ratio is less than 10% by mass, the developability is poor, which is not preferable.
  • the ratio is more than 70% by mass, the pattern shape reproducibility and heat resistance are lowered, which is not preferable.
  • the (c) alkali-soluble resin may be a product obtained by isolating and purifying an alkali-soluble resin which is an active ingredient after the synthesis reaction, or a reaction solution obtained by the synthesis reaction, a dried product thereof, or the like. You can also.
  • the polymerizable composition can be cured by heating at a low temperature.
  • a curing accelerator for example, an amine compound, a thiourea compound, a 2-mercaptobenzimidazole compound, an orthobenzoixsulfimide, a fourth-period transition metal compound compound, or the like can be used.
  • a hardening accelerator may be used independently and may use 2 or more types together.
  • the amine compound is preferably a tertiary amine, for example, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-diethylaniline, N, N-bis (2-hydroxyethyl) -p- Toluidine, ethyl 4- (dimethylamino) benzoate, (2-methacryloyloxy) ethyl 4-dimethylaminobenzoate and the like.
  • a tertiary amine for example, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-diethylaniline, N, N-bis (2-hydroxyethyl) -p- Toluidine, ethyl 4- (dimethylamino) benzoate, (2-methacryloyloxy) ethyl 4-dimethylaminobenzoate and the like.
  • thiourea examples include acetylthiourea and N, N′dibutylthiourea.
  • Examples of the 2-mercaptobenzimidazole compound include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 2-mercaptomethoxybenzimidazole, and the like.
  • the compound of the fourth period transition metal compound can be selected from organic acid salts such as vanadium, cobalt, copper, or metal chelate compounds, for example, cobalt octylate, cobalt naphthenate, copper naphthenate, vanadium naphthenate. , Copper acetylacetonate, manganese acetylacetonate, vanadyl acetylacetonate and the like.
  • organic acid salts such as vanadium, cobalt, copper, or metal chelate compounds, for example, cobalt octylate, cobalt naphthenate, copper naphthenate, vanadium naphthenate.
  • the curing accelerator is preferably blended immediately before using the polymerizable composition.
  • the content of the curing accelerator is preferably 0.1 to 20 parts by mass and more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the (b) radical polymerizable compound.
  • the polymerizable composition is generally used in applications such as coating agents, paints, printing inks, photosensitive printing plates, adhesives, various photoresists such as color resists and black resists.
  • Additives can be blended. Examples of the additives include sensitizers (isopropylthioxanthone, 9,10-dibutoxyanthracene, coumarin, ketocoumarin, acridine orange, camphorquinone, etc.), polymerization inhibitors (p-methoxyphenol, hydroquinone, 2,6-dithiol).
  • the content of the additive is appropriately selected according to the purpose of use and is not particularly limited, but is usually 500 parts by mass or less with respect to 100 parts by mass of the (b) radical polymerizable compound.
  • the amount is preferably 100 parts by mass or less.
  • the solvent may be further added to the polymerizable composition in order to improve the viscosity, paintability, and smoothness of the cured film.
  • the solvent is capable of dissolving or dispersing the (a) polymerization initiator, the (b) radical polymerizable compound, the (c) alkali-soluble resin, and the other components, and volatilizes at a drying temperature. If it is a solvent, it will not restrict
  • Examples of the solvent include water, alcohol solvents, carbitol solvents, ester solvents, ketone solvents, ether solvents, lactone solvents, unsaturated hydrocarbon solvents, cellosolve acetate solvents, carbitol acetate solvents.
  • Examples include solvents, propylene glycol monomethyl ether acetate, and diethylene glycol dimethyl ether.
  • a solvent may be used independently and may use 2 or more types together.
  • the amount of the solvent used is preferably 10 to 1000 parts by mass and more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable composition.
  • ⁇ Method for Preparing Polymerizable Composition When adjusting the polymerizable composition, the (a) polymerization initiator, the (b) radical polymerizable compound, and, if necessary, the (c) alkali-soluble resin and the other components in a storage container. And then dissolved or dispersed in accordance with a conventional method using a paint shaker, bead mill, sand grind mill, ball mill, attritor mill, 2-roll mill, 3-roll mill, or the like. Moreover, you may filter through a mesh or a membrane filter etc. as needed.
  • the (a) polymerization initiator may be added to the polymerizable composition from the beginning, but when the polymerizable composition is stored for a relatively long time.
  • the (a) polymerization initiator is preferably dissolved or dispersed in the composition containing (b) radical polymerizability immediately before use.
  • the cured product of the present invention is formed from the polymerizable composition.
  • cured material is a manufacturing which includes any process of the process of irradiating the said polymeric composition with an active energy ray, and heating the said polymeric composition after apply
  • Examples of the coating method include spin coating, bar coating, spray coating, dip coating, flow coating, slit coating, doctor blade coating, gravure coating, screen printing, offset printing, and inkjet.
  • Various methods, such as a printing method and a dispenser printing method, are mentioned.
  • Examples of the substrate include glass, silicon wafer, metal and plastic films and sheets, and three-dimensional molded products, and the shape of the substrate is not limited.
  • the step of irradiating the polymerizable composition with active energy rays comprises (a) decomposing a polymerization initiator by irradiating active energy rays such as electron beam, ultraviolet ray, visible light, and radiation, and (b) radical polymerization.
  • active energy rays such as electron beam, ultraviolet ray, visible light, and radiation
  • radical polymerization irradiating active energy rays such as electron beam, ultraviolet ray, visible light, and radiation.
  • a cured product can be obtained by polymerizing the active compound.
  • the active energy ray is preferably light having an active energy ray wavelength of 250 to 450 nm, and more preferably light having a wavelength of 350 to 410 nm from the viewpoint of allowing rapid curing.
  • a low pressure mercury lamp As the light source for the light irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, a light emitting diode (LED), a xenon arc lamp, a carbon arc lamp, sunlight, a YAG laser, etc.
  • a gas laser such as a solid-state laser, a semiconductor laser, or an argon laser can be used.
  • curing can be performed by using a sensitizer that absorbs the light as the additive. .
  • the exposure amount of the active energy ray should be appropriately set according to the wavelength and intensity of the active energy ray and the composition of the polymerizable composition.
  • the exposure dose in the UV-A region is preferably 10 to 5,000 mJ / cm 2 , and more preferably 30 to 1,000 mJ / cm 2 .
  • (a) polymerization initiator is completely by an active energy ray.
  • the exposure amount should be set as appropriate so that it is not decomposed.
  • a cured product in the step of heating the polymerizable composition, can be obtained by (a) decomposing the polymerization initiator with heat and (b) polymerizing the radical polymerizable compound.
  • examples of the heating method include heating and ventilation heating.
  • the heating method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, electromagnetic wave irradiation, and the like.
  • a ventilation drying oven etc. are mentioned, for example.
  • the higher the heating temperature the faster the decomposition rate of (a) the polymerization initiator.
  • the decomposition rate is too high, the decomposition residue of the (b) radical polymerizable compound tends to increase.
  • the lower the heating temperature the slower the decomposition rate of (a) the polymerization initiator, and thus a longer time is required for curing. Therefore, the heating temperature and the heating time should be appropriately set depending on the composition of the polymerizable composition.
  • the heating temperature is preferably 50 to 230 ° C, and more preferably 100 to 160 ° C.
  • heating temperature can be arbitrarily adjusted at 160 degreeC from room temperature with the kind and compounding quantity.
  • the heating time is preferably 1 to 180 minutes, and more preferably 5 to 120 minutes.
  • a colored pigment that absorbs or scatters light by performing a heating process after a process of irradiating the polymerizable composition with active energy rays. This is preferable because it can efficiently cure the deep part of the coating film of the polymerization composition containing a high concentration of light and a portion where light is blocked and light does not reach.
  • the method for producing the cured product may include a drying step.
  • a drying step when applying the step of irradiating with the active energy ray after applying the polymerizable composition on the substrate, it is preferable to provide a drying step before the step of irradiating with the active energy ray.
  • examples of the method for drying the solvent include heat drying, ventilation heat drying, and reduced pressure drying.
  • the method of heat drying is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, electromagnetic wave irradiation, and the like.
  • a ventilation drying oven etc. are mentioned, for example.
  • the temperature of the polymerizable composition is lower than the preset drying temperature due to the latent heat of vaporization of the solvent, so that it is possible to ensure a long time until the polymerizable composition is gelled. Since the time until gelation is affected by the drying method, film thickness, and the like, the drying temperature and time should be appropriately set including the selection of the solvent. As an example, the drying temperature is preferably 20 to 120 ° C., and more preferably 40 to 100 ° C. The drying time is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes. Further, by using the polymerization inhibitor, it is possible to ensure a long time until gelation. Although the peroxycinnamate derivative is decomposed by heat, the decomposition rate of the compound when heated at 80 ° C. for 5 minutes is about 0.1%. There is not much thickening or gelation.
  • the dry film thickness (cured material film thickness) of the polymerizable composition is appropriately set depending on the application, but is preferably 0.05 to 300 ⁇ m, more preferably 0.1 to 100 ⁇ m.
  • a pattern can be formed by a photolithography method.
  • the polymerizable composition is applied to a substrate and dried as necessary to form a dry film. Then, by irradiating the dry film with active energy rays through a mask, the radical polymerizable compound (b) is polymerized in the exposed portion to form a cured film.
  • a highly accurate pattern shape can be produced without using a mask by direct writing using a laser.
  • the unexposed portion is developed and removed with an alkaline developer such as an aqueous solution of 0.3 to 3% by mass of sodium carbonate to obtain a patterned cured film.
  • an alkaline developer such as an aqueous solution of 0.3 to 3% by mass of sodium carbonate
  • post-baking is performed as post-drying at 180 to 250 ° C. for 20 to 90 minutes for the purpose of improving the adhesion between the cured film and the substrate. In this way, a desired pattern based on the cured film is formed.
  • the polymerizable composition of the present invention includes a hard coating agent, a coating agent for optical disks, a coating agent for optical fibers, a coating material for mobile terminals, a coating material for home appliances, a coating material for woodwork, a coating material for cosmetic containers, an inner surface antireflection coating material for optical elements, a high coating material.
  • Paints and coating agents such as low refractive index coating agent, thermal barrier coating agent, heat radiation coating agent, anti-fogging agent; offset printing ink, gravure printing ink, screen printing ink, inkjet printing ink, conductive ink, insulating ink, Printing ink such as ink for light guide plate; photosensitive printing plate; nanoimprint material; resin for 3D printer; holographic recording material; dental material; waveguide material; black stripe for lens sheet; green sheet and electrode material for capacitor; Adhesive, HDD adhesive, optical pickup adhesive, image sensor Adhesives, sealants for organic EL, OCA for touch panel, OCR for touch panel, etc
  • Synthesis was performed according to the method described in Synthesis Example 1 except that the hydroperoxide aqueous solution was changed to 90% by mass tert-hexyl hydroperoxide and 80% by mass cumene hydroperoxide, respectively.
  • Tables 1 and 2 show properties of Compound 6, Compound 10, Compound 14, Compound 16, and Compound 19, and analysis results by EI-MS and 1 H-NMR.
  • Table 3 shows the results of Compound R1, Compound R2, and Compound R3.
  • Compound R1 was synthesized according to the method described in Synthesis Example 1 except that 4-methoxycinnamic acid described in Synthesis Example 1 was changed to cinnamic acid, and identified by EI-MS and 1 H-NMR. did.
  • Compound R2 was synthesized according to the production method described in JP-A-59-197401.
  • Compound 3 was Irgacure 184 (manufactured by BASF).
  • ⁇ max is the maximum absorption wavelength (nm)
  • ⁇ max is the molar extinction coefficient at the maximum absorption wavelength (L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 )
  • ⁇ 365 is the molar extinction coefficient at the wavelength 365 nm (L ⁇ mol). ⁇ 1 ⁇ cm ⁇ 1 ).
  • Table 3 the absorption band of Compound 1, Compound 6, Compound 10, Compound 14, Compound 16, and Compound 19 of the present invention is shifted to the long wavelength region with respect to Compound R1 having no substituent on the benzene ring. It can be seen that the molar extinction coefficient at a wavelength of 365 nm, which is one of the emission wavelengths of the high-pressure mercury lamp, is large.
  • DPHA is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: Aronix M-402, manufactured by Toagosei Co., Ltd.);
  • RD200 is a methyl methacrylate / methacrylic acid / cyclohexyl maleimide (mass%: 61/14/25) copolymer, weight average molecular weight: 17,000, acid value: 90 (synthetic product);
  • F-477 is a fluorine-based leveling agent (trade name: Megafax F-477, manufactured by DIC Corporation);
  • PGMEA indicates propylene glycol monomethyl ether acetate.
  • UV-3700B is urethane acrylate (trade name: Purple light UV-3700B, manufactured by Nippon Synthetic Chemical Industry); IBOA is isobornyl acrylate; THFA is tetrahydrofurfuryl acrylate; TMPTA is trimethylolpropane triacrylate; DMT stands for N, N-dimethyltoluidine.
  • the polymerizable composition (B) prepared as described above was applied to a PET film (trade name: Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 100 ⁇ m using an applicator.
  • a PET film (having a wavelength of 365 nm having a transmittance of less than 0.1%) applied to 50 ⁇ m and having a black coating on the surface was placed in a half region of the coating.
  • irradiation of 100 mJ / cm ⁇ 2 > was performed using the conveyor type
  • the black film-coated PET film was removed to expose the cured film, and the cured film portion was measured for degree of cure (%) by attenuated total reflection infrared spectroscopy (ATR-IR). .
  • ATR-IR attenuated total reflection infrared spectroscopy
  • the peroxycinnamate derivative of the present invention and the polymerizable composition containing the compound have excellent sensitivity to light, and are characterized by having photocurability and thermosetting properties. Is clear.

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Abstract

La présente invention concerne un dérivé de peroxycinnamate représenté par la formule générale (1) (dans la formule (1), n représente un nombre entier de 1 à 3 ; chaque R1 représente indépendamment un substituant représenté par la formule générale (2) : R–X–, un groupe nitro, ou un groupe cyano ; X représente un atome d'oxygène ou un atome de soufre ; et R représente un groupe hydrocarboné ayant 1 à 6 atomes de carbone, qui peut avoir, dans le squelette carboné, au moins l'une quelconque d'une liaison éther, d'une liaison thioéther et d'un groupe hydroxyle au niveau de l'extrémité, ou, R1 représente un groupe hydrocarboné qui forme un cycle à 5 ou 6 chaînons tel que fourni par deux substituants R–X– adjacents représentés par la formule générale (2). R2 représente un atome d'hydrogène ou un groupe méthyle ; R3 et R4 représentent chacun indépendamment un groupe méthyle ou un groupe éthyle ; et R5 représente un groupe hydrocarboné aliphatique ayant 1 à 5 atomes de carbone, ou représente un groupe hydrocarboné aromatique ayant de 6 à 9 atomes de carbone, qui peut avoir un groupe alkyle.) Le dérivé de peroxycinnamate présente à la fois une polymérisabilité thermique et une photo-polymérisabilité, ce par quoi des radicaux peuvent être générés par l'absorption efficace de la lumière à une longueur d'onde, par exemple, de 365 nm, émise à partir d'une lampe.
PCT/JP2017/040778 2016-12-13 2017-11-13 Dérivé de peroxycinnamate et composition polymérisable le contenant Ceased WO2018110179A1 (fr)

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