WO2023190161A1 - Initiateur de polymérisation, composition polymérisable, produit durci et hydroperoxyde ayant un squelette de thioxanthone - Google Patents

Initiateur de polymérisation, composition polymérisable, produit durci et hydroperoxyde ayant un squelette de thioxanthone Download PDF

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WO2023190161A1
WO2023190161A1 PCT/JP2023/011824 JP2023011824W WO2023190161A1 WO 2023190161 A1 WO2023190161 A1 WO 2023190161A1 JP 2023011824 W JP2023011824 W JP 2023011824W WO 2023190161 A1 WO2023190161 A1 WO 2023190161A1
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meth
polymerization initiator
group
thioxanthone skeleton
hydroperoxide
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PCT/JP2023/011824
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English (en)
Japanese (ja)
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奈央 安岡
章世 矢野
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日油株式会社
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Priority to CN202380014102.6A priority Critical patent/CN118215691A/zh
Publication of WO2023190161A1 publication Critical patent/WO2023190161A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/16—Oxygen atoms, e.g. thioxanthones
    • 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
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

Definitions

  • the present invention relates to a polymerization initiator, a polymerizable composition, a cured product, and a hydroperoxide having a thioxanthone skeleton.
  • radical polymerization initiators that generate radicals by active energy rays such as light, heat, or oxidation-reduction are widely used.
  • examples of photopolymerization initiators that can generate radicals through bond cleavage and hydrogen abstraction reactions by absorbing active energy rays such as light include ⁇ -hydroxyacetophenone derivatives, ⁇ -aminoacetophenone derivatives, Acyl phosphine oxide derivatives, halomethyltriazine derivatives, benzyl ketal derivatives, thioxanthone derivatives, etc. are used.
  • the photopolymerizable composition composed of a photopolymerization initiator and a radically polymerizable compound as described above does not necessarily require dissolving the polymerizable composition in a solvent and curing by drying, which are widely performed during thermal curing. In addition to its quick curing properties upon light irradiation, it is also used in applications such as coating materials, paints, printing inks, photosensitive printing plates, adhesives, and various photoresists due to its low VOC properties.
  • Patent Document 1 discloses a polymerization initiator having a peroxide bond (-OO-) and a triazine skeleton in the molecule, and a polymerizable composition containing the compound.
  • Patent Document 2 discloses a polymerization initiator having a peroxide bond and a thioxanthone skeleton, and a polymerizable composition containing the compound.
  • radical polymerization initiators efficiently absorb light with a wavelength of 365 nm emitted from lamps such as high-pressure mercury lamps and LEDs, efficiently generate radicals, and have excellent curability. Since it has a peroxide bond in its molecule, it also has thermal polymerizability, so it has the property of dual curing with light and heat, making it possible to cure deep areas where light cannot reach or areas that contain a lot of pigment. It is.
  • the polymerizable compositions used for the above applications are subject to high temperatures in the environment inside shipping containers when transported overseas by sea or when stored at port facilities, and in the printing work environment when used as printing ink. , stability during storage is required in environments where temperature control is not performed.
  • the polymerizable compositions containing polymerization initiators described in Patent Document 1 and Patent Document 2 have good curability and ensure storage stability during transportation and storage. However, since the stability of the polymerizable composition deteriorates when a large amount of the polymerization initiator is included, further improvement in storage stability is required.
  • an object of the present invention is to provide a polymerization initiator that exhibits excellent curability to light having a wavelength of 365 nm, etc., and allows a polymerizable composition to be obtained that has excellent long-term storage stability at high temperatures.
  • Another object of the present invention is to provide the above polymerizable composition and a cured product thereof.
  • Another object of the present invention is to provide a hydroperoxide compound having a novel thioxanthone skeleton that is contained in the above polymerization initiator.
  • the present invention provides general formula (1): (In formula (1), R 1 , R 2 , R 3 and R 4 independently represent a methyl group or an ethyl group, R 5 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R 6 is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom, and n represents an integer from 0 to 2.)
  • n represents an integer from 0 to 2.
  • the present invention also relates to a polymerizable composition containing the polymerization initiator and the radically polymerizable compound (B), and a cured product formed from the polymerizable composition.
  • the present invention also relates to a hydroperoxide (a-2) having a thioxanthone skeleton represented by the above general formula (2).
  • dialkyl peroxides having a thioxanthone skeleton are thermally stable compounds among polymerization initiators that have peroxide bonds in the molecule. Good storage stability. However, depending on transportation conditions and intended use, further improvement in storage stability is required.
  • a part of the generated active radical species abstracts hydrogen atoms from the hydroperoxide having a thioxanthone skeleton. While the hydroperoxide having a thioxanthone skeleton is inactivated by hydrogen atom, the hydrogen atom is extracted and the hydroperoxide is converted into a peroxy radical species.
  • active radical species that have not reacted with the hydroperoxide having a thioxanthone skeleton generate carbon radical species through an addition reaction to a radically polymerizable compound or a hydrogen abstraction reaction from a cured product, etc., but they do not combine with the peroxy radical species. By doing so, it becomes a thermally stable dialkyl peroxide compound, which is thought to suppress the increase in the molecular weight of the radically polymerizable compound.
  • Photocuring using a polymerization initiator containing a specific amount or more of a hydroperoxide having a thioxanthone skeleton will result in poor curing, so in order to obtain good curability, it is necessary to use dialkyl peroxides having a thioxanthone skeleton and hydroperoxides having a thioxanthone skeleton. It has been found that it is desirable to contain it in a specific ratio. As a result, it was found that the polymerizable composition containing the polymerization initiator of the present invention exhibits good curability and has excellent storage stability.
  • the polymerization initiator (A) of the present invention comprises a dialkyl peroxide (a-1) having a thioxanthone skeleton represented by the following general formula (1) and a hydroperoxide having a thioxanthone skeleton represented by the following general formula (2).
  • a-1 dialkyl peroxide having a thioxanthone skeleton represented by the following general formula (1)
  • a hydroperoxide having a thioxanthone skeleton represented by the following general formula (2).
  • the dialkyl peroxide (a-1) having a thioxanthone skeleton of the present invention can be represented by the following general formula (1).
  • R 1 , R 2 , R 3 and R 4 independently represent a methyl group or an ethyl group
  • R 5 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group
  • R 6 is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom
  • n represents an integer from 0 to 2.
  • R 1 , R 2 , R 3 and R 4 independently represent a methyl group or an ethyl group.
  • R 1 , R 2 , R 3 and R 4 are preferably methyl groups from the viewpoint of increasing the storage stability of the polymerizable composition since the decomposition temperature of the dialkyl peroxide having a thioxanthone skeleton is high.
  • R 5 is an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • the alkyl group may be linear or branched.
  • Specific examples of R 5 include methyl group, ethyl group, propyl group, 2,2-dimethylpropyl group, and phenyl group. Among these, methyl group, ethyl group, and propyl group are preferable from the viewpoint of easy synthesis of the dialkyl peroxide having the thioxanthone skeleton.
  • the decomposition temperature of the dialkyl peroxide having a thioxanthone skeleton is high, the storage stability of the polymerizable composition is high, and the sensitivity to lamp light is high, so methyl, ethyl, and propyl groups are preferred. preferable.
  • the substitution position of the dialkyl peroxide on the thioxanthone is not particularly limited, but from the viewpoint of high sensitivity to lamp light, it is substituted at the 2-position, 3-position, or 4-position of the thioxanthone skeleton. is preferable, and from the viewpoint of easy synthesis, substitution at the 2- or 3-position of the thioxanthone skeleton is more preferable.
  • R 6 is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom. Due to the push-pull effect on these substituents, the light absorption characteristics of the dialkyl peroxide having a thioxanthone skeleton can be adjusted with respect to the emission wavelength of the lamp used, and the light from the lamp can be efficiently absorbed. can.
  • n represents an integer from 0 to 2. From the viewpoint of easy synthesis of the dialkyl peroxide having the thioxanthone skeleton, n is preferably an integer from 0 to 1, and more preferably 0.
  • the substitution position of R 6 is not particularly limited, but from the viewpoint of high sensitivity to lamp light, it is substituted at the 6th or 7th position of the thioxanthone skeleton. Substitution is preferable, and from the viewpoint of easy synthesis of the dialkyl peroxide having a thioxanthone skeleton, substitution is more preferable at the 7-position of the thioxanthone skeleton.
  • R 6 examples include alkyl groups such as methyl group, ethyl group, isopropyl group, n-butyl group; methoxy group, ethoxy group, n-propyloxy group, sec-butyloxy group, tert-butyloxy group.
  • alkoxy groups such as; chlorine atoms, etc. From the viewpoint of high sensitivity to lamp light, methoxy and ethoxy groups are more preferred.
  • dialkyl peroxide (a-1) having a thioxanthone skeleton of the present invention are shown below, but the present invention is not limited thereto.
  • the dialkyl peroxide (a-1) having a thioxanthone skeleton preferably includes Compounds 1 to 9, more preferably Compound 1, Compound 2, Compound 3, Compound 7, and Compound 8.
  • the method for producing the dialkyl peroxide (a-1) having a thioxanthone skeleton represented by the general formula (1) is not particularly limited, and for example, WO 2020/067118 may be referred to.
  • the hydroperoxide (a-2) having a thioxanthone skeleton of the present invention can be represented by the following general formula (2).
  • R 1 and R 2 independently represent a methyl group or an ethyl group
  • R 3 is an independent substituent, such as an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. represents an alkoxy group or a chlorine atom, and n represents an integer from 0 to 2.
  • R 1 and R 2 independently represent a methyl group or an ethyl group.
  • R 1 and R 2 are preferably methyl groups from the viewpoint of increasing the storage stability of the polymerizable composition since the hydroperoxide having the thioxanthone skeleton has a high decomposition temperature.
  • R 3 is an independent substituent and represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a chlorine atom. Due to the push-pull effect of these substituents, the light absorption characteristics of the hydroperoxide having a thioxanthone skeleton can be adjusted according to the emission wavelength of the lamp used, and the light from the lamp can be efficiently absorbed. can.
  • n represents an integer from 0 to 2. From the viewpoint of easy synthesis of the hydroperoxide having a thioxanthone skeleton, n is preferably an integer from 0 to 1, and more preferably 0.
  • the substitution position of R3 is not particularly limited, but from the viewpoint of high sensitivity to lamp light, it is substituted at the 6th or 7th position of the thioxanthone skeleton. Substitution is preferable, and from the viewpoint of easy synthesis of the hydroperoxide having the thioxanthone skeleton, substitution is more preferable at the 7-position of the thioxanthone skeleton.
  • R 3 examples include alkyl groups such as methyl group, ethyl group, isopropyl group, n-butyl group; methoxy group, ethoxy group, n-propyloxy group, sec-butyloxy group, tert-butyloxy group.
  • alkoxy groups such as; chlorine atoms, etc. From the viewpoint of high sensitivity to lamp light, methoxy and ethoxy groups are more preferred.
  • hydroperoxide (a-2) having a thioxanthone skeleton of the present invention are shown below, but the present invention is not limited thereto.
  • the hydroperoxide (a-2) having a thioxanthone skeleton preferably includes compounds 10 to 18, more preferably compounds 10 and 11.
  • the method for producing the hydroperoxide (a-2) having a thioxanthone skeleton represented by the general formula (2) is, for example, as shown in the reaction formula below, in which an isoalkyl group-substituted thioxanthone derivative is reacted with a hydroperoxide in the presence of a metal complex.
  • Examples include a method including a step of reacting (hereinafter also referred to as step (A)). Note that, after the reaction, a step of distilling off (removing) excess raw materials and the like under reduced pressure, and a purification step may be included.
  • R 1 , R 2 , R 3 and n are the same as in the above general formula (2), R 4 and R 5 independently represent a methyl group or an ethyl group, and R 6 is the number of carbon atoms Represents an alkyl group of 1 to 6 or a phenyl group.
  • a commercially available product can be used as the isoalkyl group-substituted thioxanthone derivative.
  • a commercially available product for example, J. Chem. Soc. 99,645 (1911), it can be synthesized by reacting 2,2'-dithiodibenzoic acid with an aromatic compound in sulfuric acid.
  • step (A) it is preferable that 0.8 mol or more of the hydroperoxide be reacted with 1.0 mol of the isoalkyl group-substituted thioxanthone derivative, and 1.0 mol or more, from the viewpoint of increasing the yield of the target product. It is more preferable to react at least 10.0 mol or less, and more preferably to react at 6.0 mol or less.
  • the hydroperoxide can be commercially available, and if there is no commercially available product, it can be synthesized according to the known synthesis method described in JP-A-58-72557 and the like.
  • a metal complex of a metal selected from the fourth and fifth period transition metals can be used as the metal complex.
  • metals in metal complexes include copper, cobalt, manganese, iron, chromium, and zinc
  • examples of ligands include halogens such as bromine and chlorine, and minerals such as sulfuric acid, phosphoric acid, nitric acid, and carbonic acid.
  • examples include organic acids such as acids, formic acid, acetic acid, naphthenic acid, octenoic acid, and gluconic acid, cyanide, acetylacetonate, and the like.
  • the metal complex is preferably used in an amount of 0.0001 mol or more, more preferably 0.001 mol or more, and, It is preferable to use 1.0 mol or less, more preferably 0.1 mol or less.
  • the reaction temperature is preferably 0°C or higher, more preferably 20°C or higher, and preferably 100°C or lower, from the viewpoint of increasing the yield of the target product.
  • the temperature is preferably 80°C or lower, and more preferably 80°C or lower.
  • water is preferably used as the medium, and water and an organic solvent may be used in combination.
  • the organic solvent for example, benzene, toluene, chlorobenzene, o-dichlorobenzene, nitrobenzene, etc. can be used.
  • the amount of the organic solvent and water used is usually about 50 to 1000 parts by weight based on 100 parts by weight of the total amount of raw materials.
  • the hydroperoxide having a thioxanthone skeleton may be taken out by distilling off or separating the organic solvent and water after step (A).
  • the step (A) can be carried out under normal pressure, increased pressure, or reduced pressure, but it is preferably carried out in an inert gas atmosphere such as nitrogen or in the atmosphere, and more preferably in the atmosphere. preferable.
  • organic solvents for example, organic solvents, ion exchange water, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sulfuric acid are used.
  • examples include a step of purifying the target product by washing with a basic aqueous solution such as a sodium or sodium sulfite aqueous solution, or an acidic aqueous solution such as hydrochloric acid or sulfuric acid.
  • a basic aqueous solution such as a sodium or sodium sulfite aqueous solution
  • an acidic aqueous solution such as hydrochloric acid or sulfuric acid.
  • the organic solvent for example, benzene, toluene, heptane, methanol, chlorobenzene, o-dichlorobenzene, nitrobenzene, etc. can be used.
  • washing with an organic solvent is preferable, and washing with heptane or methanol is more preferable.
  • the organic solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent used is usually about 50 to 1000 parts by weight based on 100 parts by weight of the total amount of raw materials.
  • the polymerization initiator (A) of the present invention comprises a dialkyl peroxide (a-1) having a thioxanthone skeleton represented by the general formula (1) and a hydroperoxide (a-1) having a thioxanthone skeleton represented by the general formula (2). Contains a-2).
  • the polymerization initiator (A) is decomposed by active energy rays or heat, and the generated radicals have the function of initiating polymerization (curing) of the radically polymerizable compound (B).
  • the amount of the hydroperoxide (a-2) having a thioxanthone skeleton is 30 parts by mass or less from the viewpoint of suppressing the increase in the molecular weight of the radically polymerizable compound, and 15 parts by mass or less is Preferably, from the viewpoint of storage stability, the amount is preferably 0.1 part by mass or more, and more preferably 0.5 part by mass or more.
  • the dialkyl peroxide (a-1) having a thioxanthone skeleton is preferably 30 parts by mass or more, and preferably 50 parts by mass or more, from the viewpoint of curability. From the viewpoint of storage stability, the amount is preferably 98 parts by mass or less, and preferably 95 parts by mass or less.
  • the polymerization initiator (A) can contain a polymerization initiator other than dialkyl peroxide having a thioxanthone skeleton or hydroperoxide having a thioxanthone skeleton (hereinafter also referred to as other polymerization initiator).
  • Lamps that emit light of multiple wavelengths such as high-pressure mercury lamps, by using two or more types of dialkyl peroxides having a thioxanthone skeleton, hydroperoxides having a thioxanthone skeleton, and other polymerization initiators with different absorption bands. In contrast, it is possible to increase the sensitivity of the polymerizable composition.
  • the polymerizability of the radically polymerizable compound (B) contained in the polymerizable composition considering the polymerizability of the radically polymerizable compound (B) contained in the polymerizable composition, the type of pigment that absorbs or scatters light contained in the polymerizable composition, the film thickness of the cured product, etc.
  • the polymerization initiator By using the polymerization initiator, the surface curability, deep curability, transparency, etc. of the polymerizable composition can be improved.
  • polymerization initiators known ones can be used, such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-propiophenone, 4'-(2-hydroxyethoxy)-2-hydroxy -2-Methylpropiophenone, ⁇ -hydroxyacetophenone derivatives such as 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, etc.
  • Examples include peroxides; azo compounds such as azobisisobutyronitrile; and camphorquinone.
  • peroxides azo compounds such as azobisisobutyronitrile
  • camphorquinone one type selected from acylphosphine oxide derivatives and thioxanthone derivatives 2-isopropyl-9H-thioxanthene-9-one and 2-(2-hydroxypropan-2-yl)-9H-thioxanthene-9-one.
  • acylphosphine oxide derivatives and thioxanthone derivatives 2-isopropyl-9H-thioxanthene-9-one and 2-(2-hydroxypropan-2-yl)-9H-thioxanthene-9-one.
  • Other polymerization initiators may be used alone or in combination of two or more types.
  • the proportion of the other polymerization initiator can be appropriately set depending on the wavelength emitted from a lamp, etc.; In agent (A), 80% by mass or less and 50% by mass or less can be exemplified.
  • the polymerizable composition of the present invention contains the polymerization initiator (A) and the radically polymerizable compound (B).
  • radically polymerizable compound (B) of the present invention a compound having an ethylenically unsaturated group can be preferably used.
  • the radically polymerizable compound (B) include (meth)acrylic esters, styrenes, maleic esters, fumaric esters, itaconic esters, cinnamic esters, crotonic 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 include highly reactive (meth)acrylic esters.
  • the radically polymerizable compound (B) may be used alone or in combination of two or more types.
  • monofunctional compounds and polyfunctional compounds can be used as the (meth)acrylic esters.
  • Monofunctional compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate.
  • 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 alcohol such as acrylate and 2-ethyl-2-adamantyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate ; 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, polyethylene glycol mono(meth)acrylate Monomers with hydroxy groups such as acrylate, polypropylene glycol mono(meth)acrylate, etc.
  • Monomers having an isocyanate group such as 2-(meth)acryloyloxyethyl isocyanate; Monomers having an epoxy group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether; Phosphoric acid 2-( Monomers having a phosphorus atom such as (meth)acryloyloxy)ethyl; monomers having a silicon atom such as 3-(meth)acryloxypropyltrimethoxysilane; 2,2,2-trifluoroethyl (meth)acrylate, 2, Monomers containing fluorine atoms such as 2,3,3,3-pentafluoropropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate; (meth)acrylic acid, succinic acid mono(2-(meth)acrylate); ) acryloyloxyethyl), mono(2-(meth)acryloyloxy
  • the polyfunctional compounds 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, 1,9-nonanediol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, glycerin propoxytri(meth)acrylate, trimethylolethane triacrylate (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, dipentaerythritol penta(
  • ester compounds of the polyhydric alcohol and (meth)acrylic acid are preferable, and in particular, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, Pentaerythritol hexaacrylate is preferred.
  • the content of the polymerization initiator (A) is preferably 0.1 parts by mass or more, and more preferably 1.0 parts by mass or more, based on 100 parts by mass of the radically polymerizable compound (B) from the viewpoint of curability. Further, the content of the polymerization initiator (A) is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, from the viewpoint of storage stability and solubility in radically polymerizable compounds.
  • the polymerizable composition can be cured by heating at a low temperature.
  • a curing accelerator for example, amine compounds, thiourea compounds, 2-mercaptobenzimidazole compounds, orthobenzoic sulfimide, fourth period transition metal compounds, etc. can be used.
  • the curing accelerator may be used alone or in combination of two or more types.
  • the amine compound is preferably a tertiary amine, such as N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-diethylaniline, N,N-bis(2-hydroxyethyl)-p- Examples include toluidine, ethyl 4-(dimethylamino)benzoate, and ethyl 4-dimethylaminobenzoate (2-methacryloyloxy).
  • a tertiary amine such as N,N-dimethylaniline, N,N-dimethyltoluidine, N,N-diethylaniline, N,N-bis(2-hydroxyethyl)-p- Examples include toluidine, ethyl 4-(dimethylamino)benzoate, and ethyl 4-dimethylaminobenzoate (2-methacryloyloxy).
  • thiourea examples include acetylthiourea, N,N'dibutylthiourea, and the like.
  • 2-mercaptobenzimidazole compounds examples include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 2-mercaptomethoxybenzimidazole, and the like.
  • the fourth period transition metal compound can be selected from organic acid salts or metal chelate compounds such as vanadium, cobalt, and copper, such as cobalt octylate, cobalt naphthenate, copper naphthenate, vanadium naphthenate, and copper.
  • organic acid salts or metal chelate compounds such as vanadium, cobalt, and copper, such as cobalt octylate, cobalt naphthenate, copper naphthenate, vanadium naphthenate, and copper.
  • metal chelate compounds such as vanadium, cobalt, and copper, such as cobalt octylate, cobalt naphthenate, copper naphthenate, vanadium naphthenate, and copper.
  • cobalt octylate cobalt naphthenate
  • copper naphthenate copper naphthenate
  • vanadium naphthenate vanadium naphthenate
  • copper such as
  • the curing accelerator is preferably added immediately before using the polymerizable composition.
  • the content of the curing accelerator is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the radically polymerizable compound (B).
  • the polymerizable composition includes coating agents, paints, printing inks, photosensitive printing plates, adhesives, and those commonly used in various photoresists such as color resists and black resists.
  • Additives can be added. Examples of additives include sensitizers (isopropylthioxanthone, diethylthioxanthone, 4,4'-bis(diethylamino)benzophenone, 9,10-dibutoxyanthracene, coumarin, ketocoumarin, acridine orange, camphorquinone, etc.), polymerization inhibitors, etc.
  • UV absorbers p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc.
  • ultraviolet absorbers infrared absorbers
  • chain transfer agents light stabilizers, antioxidants, leveling agents , surface conditioners, surfactants, thickeners, antifoaming agents, adhesion promoters, plasticizers, epoxy compounds, thiol compounds, resins with ethylenically unsaturated bonds, saturated resins, colored dyes, fluorescent dyes, pigments ( organic pigments, inorganic pigments), carbon-based materials (carbon fiber, carbon black, graphite, graphitized carbon black, activated carbon, carbon nanotubes, fullerene, graphene, carbon microcoils, carbon nanohorns, carbon aerogels, etc.), metal oxides (oxidized titanium, iridium oxide, zinc oxide, alumina, silica, etc.), metals (silver, copper, etc.), inorganic compounds (glass powder
  • the content of the additive is appropriately selected depending on the purpose of use and is not particularly limited, but it is usually 500 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound (B).
  • the amount is preferably 100 parts by mass or less, and more preferably 100 parts by mass or less.
  • a solvent can also be added to the polymerizable composition in order to improve the viscosity, paintability, and smoothness of the cured film.
  • the solvent is one that can dissolve or disperse the polymerization initiator (A), the radically polymerizable compound (B), and the other components, and is not particularly limited as long as it evaporates at the drying temperature. It's not something you can do.
  • the solvent examples include water, alcohol solvents, carbitol solvents, ester solvents, ketone solvents, ether solvents, lactone solvents, unsaturated hydrocarbon solvents, cellosolve acetate solvents, and carbitol acetate solvents.
  • examples include solvents, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and the like.
  • the solvent may be used alone or in combination of two or more.
  • the amount of the solvent used is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, based on 100 parts by mass of the solid content of the polymerizable composition.
  • ⁇ Method for preparing polymerizable composition When preparing the polymerizable composition, the polymerization initiator (A), the radically polymerizable compound (B), and, if necessary, the other components are placed in a storage container, and the mixture is heated in a paint shaker or bead mill. , a sand grind mill, a ball mill, an attritor mill, a two-roll mill, a three-roll mill, etc., and may be dissolved or dispersed according to a conventional method. Furthermore, if necessary, it may be filtered through a mesh or membrane filter.
  • the polymerization initiator (A) may be added to the polymerizable composition from the beginning, but when storing the polymerizable composition for a relatively long time, It is preferable to dissolve or disperse the polymerization initiator (A) in the composition containing the radically polymerizable compound (B) immediately before use.
  • the cured product of the present invention is formed from the polymerizable composition.
  • the method for producing a cured product includes applying the polymerizable composition onto a substrate, then irradiating the polymerizable composition with active energy rays, heating the polymerizable composition, or both steps. This is a manufacturing method including. Further, a process including both the step of irradiating with active energy rays and the step of heating is also referred to as a dual cure step.
  • 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 coating.
  • Various methods such as a printing method and a dispenser printing method can be used.
  • examples of the substrate include films and sheets made of glass, silicon wafers, metals, plastics, etc., and three-dimensional molded products, and the shape of the substrate is not limited.
  • the step of irradiating the above polymerizable composition with active energy rays includes decomposing the polymerization initiator (A) by irradiating the active energy rays such as electron beams, ultraviolet rays, visible light, and radiation, and converting the radically polymerizable compound ( A cured product can be obtained by polymerizing B).
  • active energy rays such as electron beams, ultraviolet rays, visible light, and radiation
  • the active energy ray is preferably light with a wavelength of 250 to 450 nm, and more preferably 350 to 410 nm from the viewpoint of rapid curing.
  • the light source for the light irradiation includes a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, an LED lamp, a xenon arc lamp, a carbon arc lamp, sunlight, and a solid laser such as a YAG laser. , a semiconductor laser, a gas laser such as an argon laser, etc. can be used.
  • curing can be carried out by using a sensitizer that absorbs the light as the additive. .
  • the exposure amount of the active energy rays should be appropriately set depending on the wavelength and intensity of the active energy rays and the composition of the polymerizable composition.
  • the exposure amount in the UV-A region is preferably from 10 to 5,000 mJ/cm 2 , more preferably from 30 to 1,000 mJ/cm 2 .
  • the polymerization initiator (A) is completely cured by the active energy rays.
  • the exposure amount should be set appropriately to avoid decomposition.
  • a cured product can be obtained by decomposing the polymerization initiator (A) with heat and polymerizing the radically polymerizable compound (B).
  • heating methods include heating, ventilation heating, and the like.
  • the heating method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, electromagnetic wave irradiation, and the like.
  • examples of the ventilation heating method include a ventilation drying oven.
  • the heating temperature and heating time should be appropriately set depending on the composition of the polymerizable composition.
  • the heating temperature is preferably 50 to 230°C, more preferably 100 to 200°C.
  • the heating temperature can be arbitrarily adjusted from room temperature to 160° C. depending on the type and amount of the curing accelerator.
  • the heating time is preferably 1 to 180 minutes, more preferably 5 to 120 minutes.
  • the method for producing the cured product can include a drying step.
  • a drying step when applying the step of irradiating with the active energy rays after coating the polymerizable composition on the substrate, it is preferable to provide a drying step before the step of irradiating with the active energy rays.
  • methods for drying the solvent include, for example, heating drying, ventilation heating drying, reduced pressure drying, and the like.
  • the heating drying method is not particularly limited, and examples thereof include an oven, a hot plate, infrared irradiation, electromagnetic wave irradiation, and the like.
  • examples of the ventilation heating drying method include a ventilation drying oven.
  • the temperature of the polymerizable composition is lower than the drying set temperature due to the latent heat of vaporization of the solvent, so it is possible to secure a long time until the polymerizable composition gels. Since the time required for this gelation to occur is affected by the drying method, film thickness, etc., the drying temperature and time should be set appropriately, including the selection of the solvent. As an example, the drying temperature is preferably from 20 to 120°C, more preferably from 40 to 100°C. The drying time is preferably 1 to 60 minutes, more preferably 1 to 30 minutes. Furthermore, by using the polymerization inhibitor, it is possible to secure a longer period of time until gelation occurs.
  • dialkyl peroxide having a thioxanthone skeleton is decomposed by heat, but the decomposition rate of the compound when heated at 90°C for 5 minutes is less than 0.1%, so under these conditions, polymerization is not possible.
  • the composition does not thicken or gel.
  • the dry film thickness (thickness of the cured product) of the polymerizable composition is appropriately set depending on the application, but is preferably from 0.05 to 500 ⁇ m, more preferably from 0.1 to 100 ⁇ m. .
  • the polymerizable composition of the present invention is a hard coating agent, a coating agent for optical discs, a coating agent for optical fibers, a coating agent for mobile terminals, a coating for home appliances, a coating for cosmetic containers, an internal antireflection coating for optical elements, and a high/low refractive index coating.
  • Paints and coating agents such as coating agents, thermal barrier coating agents, heat dissipation coating agents, antifogging agents; offset printing inks, gravure printing inks, screen printing inks, inkjet printing inks, conductive inks, insulating inks, inks for light guide plates
  • Printing inks such as; photosensitive printing plates; nanoimprint materials; resins for 3D printers; holographic recording materials; dental materials; materials for waveguides; black stripes for lens sheets; green sheets and electrode materials for capacitors; adhesives for FPD; Adhesives and sealants for HDDs, optical pickups, image sensors, organic EL sealants, OCA for touch panels, OCR for touch panels, etc.
  • the polymerizable composition prepared above was coated onto a PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) that had been subjected to easy-adhesion treatment using a bar coater (#6), and was coated uniformly to a thickness of about 10 ⁇ m.
  • a membrane was prepared.
  • light irradiation was performed using an LED lamp (UniJet E110III, manufactured by Ushio Inc.) with a wavelength of 385 nm at an illuminance of 3.5 W/cm 2 and a line speed of 6 m/min.
  • the surface of the printed matter was palpated, and the number of irradiations until the photocurable ink no longer stuck to the hand was evaluated as curing property.
  • the results are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)

Abstract

La présente invention concerne un initiateur de polymérisation (A) qui contient un peroxyde de dialkyle (a-1) qui a un squelette de thioxanthone représenté par la formule générale (1) et un hydroperoxyde (a-2) qui a un squelette de thioxanthone représenté par la formule générale (2), la teneur de l'hydroperoxyde (a-2) qui a un squelette de thioxanthone étant inférieure ou égale à 30 parties en masse pour 100 parties en masse de l'initiateur de polymérisation (A). Cet initiateur de polymérisation présente une excellente aptitude au durcissement en ce qui concerne de la lumière ayant une longueur d'onde de 365 nm ou similaire, tout en ayant une excellente stabilité au stockage à long terme à des températures élevées.
PCT/JP2023/011824 2022-03-28 2023-03-24 Initiateur de polymérisation, composition polymérisable, produit durci et hydroperoxyde ayant un squelette de thioxanthone WO2023190161A1 (fr)

Priority Applications (1)

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CN202380014102.6A CN118215691A (zh) 2022-03-28 2023-03-24 聚合引发剂、聚合性组合物及固化物、以及具有噻吨酮骨架的氢过氧化物

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JP2022-052213 2022-03-28

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4956982A (fr) * 1972-10-05 1974-06-03
JPS63146903A (ja) * 1986-12-10 1988-06-18 Hitachi Chem Co Ltd 光開始剤およびこれを用いた光重合性組成物
JPH0352856A (ja) * 1989-07-19 1991-03-07 Nippon Oil & Fats Co Ltd ジアルキルペルオキシドおよびその用途
JP2021147516A (ja) * 2020-03-19 2021-09-27 日油株式会社 重合開始剤混合物、重合性組成物、硬化物、および硬化物の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4956982A (fr) * 1972-10-05 1974-06-03
JPS63146903A (ja) * 1986-12-10 1988-06-18 Hitachi Chem Co Ltd 光開始剤およびこれを用いた光重合性組成物
JPH0352856A (ja) * 1989-07-19 1991-03-07 Nippon Oil & Fats Co Ltd ジアルキルペルオキシドおよびその用途
JP2021147516A (ja) * 2020-03-19 2021-09-27 日油株式会社 重合開始剤混合物、重合性組成物、硬化物、および硬化物の製造方法

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