Photocuring composition and application thereof

Abstract

The invention provides a photocuring composition and application thereof. The composition comprises the following components: (a) at least one benzoyl formate compound; (b) at least one ethylenically unsaturated photopolymerizable compound; the benzoyl formate compound is obtained by reacting a compound shown in a general formula (I) with a compound shown in a general formula (II), or is obtained by further reacting the compounds shown in the general formula (I) and the general formula (II) with a compound with an end-capped substituent group for end-capping. The sensitivity of the obtained product is not reduced compared with that of existing small molecules, and the hardness of the product is improved under LED curing.

Description

[0001] This application claims priority to patent application number 202410545313.9, which was filed on April 30, 2024, and is entitled "A Photoinitiator and Its Preparation Method and Application". Technical Field

[0002] This invention belongs to the field of photocuring, and specifically relates to a photocurable composition and its application. Background Technology

[0003] Benzoyl carbamate photoinitiators are common free radical photoinitiators. Due to their simple structure, ease of synthesis, and low price, they are widely used. However, problems such as migration, odor, yellowing, and solubility often exist during use, which greatly limits their application. Chinese patent applications CN102442909A and CN101979373A have macromolecularized benzoyl carbamate photoinitiators, which has solved the odor and migration problems to some extent. However, the initiation efficiency is reduced, and cost is also a factor to consider.

[0004] However, while improving the solubility and post-curing migration of initiator products, minimizing the impact on initiation efficiency has always been a goal, especially under LED curing. Ensuring the existing initiation efficiency while maintaining the product's application performance is also a problem that needs to be solved. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a photocurable composition and its applications. The photocurable composition of the present invention exhibits good compatibility after application, shows no migration, has minimal impact on initiation efficiency, and is low in cost. Under LED curing, the initiation efficiency remains unaffected while the product hardness is improved.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] On one hand, the present invention provides a photocurable composition comprising the following components:

[0008] (a) at least one benzoyl carbamate compound;

[0009] (b) at least one olefinically unsaturated photopolymerizable compound;

[0010] The benzoyl carbamate compound is obtained by reacting the compound of general formula (I) and the compound of general formula (II):

[0011]

[0012] Where A is a single bond, O, S or CR2R3, and R2 and R3 are independent of each other, representing hydrogen, C1-C8 straight-chain or branched alkyl groups;

[0013] Y represents hydrogen, halogen (e.g., fluorine, chlorine, bromine, or iodine), nitro, C(=O)C(=O)-OR1, C1-C 10 Straight-chain or branched alkyl groups, C3-C 10 alkyl cycloalkyl, C4-C 10 alkyl cycloalkyl or C4-C 10 cycloalkyl alkyl, or the C1-C 10 Straight-chain or branched alkyl groups, C3-C 10 alkyl cycloalkyl, C4-C 10 alkyl cycloalkyl or C4-C 10 The group formed when the -CH2- group in a cycloalkyl group is replaced by O, N, S, aryl, or C (=O);

[0014] R1 is a hydroxyl group, a halogen (e.g., fluorine, chlorine, bromine, or iodine), or a C1-C4 alkoxy group;

[0015] R4, R6, R5, and R7 independently represent hydrogen, fluorine, hydroxyl, or C1-C. 10 Straight-chain or branched alkyl groups, the hydrogen on the alkyl group can be further replaced by fluorine;

[0016] R8 and R9 represent hydrogen, C1-C4 alkyl, or C1-C4 alkyl carbonyl groups independently;

[0017] The independent representation of Y1 and Y2 is C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 alkyl cycloalkyl, C4-C 20 alkyl cycloalkyl or C4-C 20 cycloalkyl alkyl, or the C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 alkyl cycloalkyl, C4-C 20 alkyl cycloalkyl or C4-C 20 The group in a cycloalkyl group after the -CH2- is replaced by O, N, S, Si, aryl, bisphenol fluorene or C (=O);

[0018] m and n are independent integers from 0 to 20 (e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20), and m and n are not both 0;

[0019] Or the benzoyl carbamate compound is obtained by further reacting the compounds of formula (I) and (II) with a compound having a capping substituent to obtain a compound.

[0020] In this invention, the range of carbon atoms defined in the group definition indicates that the number of carbon atoms in the defined group can be any value within the defined range. For example, C1-C8 means that the number of carbon atoms can be 1, 2, 3, 4, 5, 6, 7 or 8. 20 The number of carbon atoms can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, and so on.

[0021] Preferably, the compounds described in formula (II) may include: ethylene glycol, polyethylene glycol, diethylene glycol, propylene glycol, polypropylene glycol, glycerol, pentaerythritol, pentapentanol, cyclohexanehexyl alcohol, 2,5-dimethyl-2,5-hexanediol, 1,4-butanediol, 1,5-pentanediol, dipropylene glycol, triethylene glycol, triethylene glycol methyl ether, 1,10-decanediol, tetraethylene glycol trioxide, 2,2-dimethyl-1,3-propanediol, 1,3-cyclohexanediol, 3,4-dihydroxyphenylethanol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, tetraethylene glycol, etc. Methyl ethylene glycol, sorbitol, pyridoxine, mannitol, 2,5-bis(1,1-dimethylpropyl)-1,4-phenylene glycol, xylitol, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, glycidyl ether, phenyl-1,2-ethylene glycol, 2-ethyl-1,3-hexanediol, propylene glycol monohydroxymethyl ether, diethylene glycol dimethyl ether, 3,3'-oxybis(propane-1-ol), neopentyl glycol 2,2-dimethyl-3-hydroxypropionate, triethylene glycol, 3,7-dioxa-1,9-nonanediol, 4,8-dioxa-undecane-1,11-diol, diethylene glycol, 4-hexaoxide Heptanediol, 1,4-dioxane-2,3-diol, 3-(2-hydroxyethoxy)propane-1,2-diol, 6H-benzofurano[3,2-C][1]benzopyran-3,9-diol, (3S,3aR,6S,6aR)-hexahydrofurano[3,2-b]furan-3,6-diol, phenoldiol, pentaethylene glycol, (9Ci)-octahydro-4A,8A-(methaneoxymethane)naphthalene-2,7-diol, 3,3'-[1,4-butadiylbis(oxy)]bis-1,2-propanediol, 3,3'-di-1,2-propanediol oxide, 2-Ethyl-2-[(2-hydroxyethoxy)methyl]-1,3-propanediol, di(2-hydroxypropyl) ether, drospirenone 5,5'-diol, 2-methyl-3,4-chromodiol, 2,5-tetrahydrofurandiol, propylene glycol salicylate, octaethylene glycol, 5-methoxy-2-methoxy-tetrahydro-pyran-3,4-diol, 2,2-dimethyl-hexahydro-1,3,4,8-tetraoxacyclopentane(a)indene-5,7-diol, 6-methoxy-2-phenyl-hexahydro-pyran(3,2-D)(1,3)dioxane-7,8-diol, chromo-4,6-diol,

[0022] R represents hydrogen, methyl, or further halogen-substituted methyl, n1 is an integer from 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10); m1 and n2 are independently integers from 0 to 10 (e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), and m1 + n2 = 10.

[0023] In this invention, initiators of compounds or mixtures with different structures are obtained according to the different ratios of compounds of formula (I) and formula (II) and the different raw materials.

[0024] Preferably, the benzoyl carbamate compound has any one of the following structures:

[0025]

[0026] Among them, R 10 R9 group or Group, the wavy line represents the group's connection site, R 11 Y group or Groups, the wavy line represents the connection site of the group.

[0027] Preferably, the end-capping substituent is selected from hydroxyl, ester, carboxylic acid, acyl chloride, isocyanate (NCO) or polyurethane groups.

[0028] Preferably, the compound having end-capped substituents is selected from alcohols, esters, isocyanates, carboxylic acids, acyl chlorides, or polyurethanes.

[0029] Preferably, when the end-capping substituent is a hydroxyl group, the following compounds (i.e., alcohols) can be listed:

[0030] Ethylene glycol, propylene glycol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,4-dipentanol, 1,3-pentanediol, 1,2-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1, 2-Hexanediol, 2,5-Hexanediol, 2-Ethyl-1,3-Hexanediol, 2,5-Dimethyl-2,5-Hexanediol, Diethylene glycol, Triethylene glycol, Tetraethylene glycol, Dipropylene glycol, Tripropylene glycol, 1,2-Cyclopentanediol, 1,3-Cyclopentanediol, 1,2-Cyclohexanediol, 1,3-Cyclohexanediol, 1,4-Cyclohexanediol, 1,2-Dihydroxymethylcyclohexane, 1,3-Dihydroxymethylcyclohexane, 1,4 - Dimethylolcyclohexane, 3-methoxy-1,2-propanediol, 1,7-heptanediol, 1,2-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-decanediol, 1,11-undecanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanedanediol Alcohols, 1,16-hexadecanediol and polyethylene glycol, glycerol, glycerol trimer, glycerol tetramer, glycerol pentamer, glycerol hexamer, glycerol heptamer, glycerol octamer, glycerol decamer, glycerol eicosomer, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, hexanetriol, butanetriol, decatriol, pentaerythritol, cyclohexanetriol, heptatriol, nonanetriol, octatriol, L-threobutanol, butanetriol, cyclohexanehexaol.

[0031] Furthermore, when the terminating substituent is an ester group, the following compounds (i.e., ester compounds) can be listed:

[0032] Dimethyl ester, diethyl ester, di-propyl ester, dihexyl ester, diheptyl ester, di-octyl ester, di-nonyl ester and di-decyl ester, di-n-butyl ester, di-tert-butyl ester, di-isobutyl ester, di-n-octyl ester, di-isooctyl ester, di-2-ethylhexyl ester, di-n-nonyl ester, di-isononyl ester, di-n-decyl ester, diisodecyl ester, dimethyl 2,6-naphthalenedicarboxylate, 2,7-naphthalenedicarboxylic acid, dimethyl 2,7-naphthalenedicarboxylic acid, 1,4'-naphthalenedicarboxylic acid, dimethyl 1,4'-naphthalenedicarboxylic acid, dimethyl 2,2-biphenylenediate, dimethyl biphenylenediate, dimethyl maleate, diethyl maleate Dibutyl maleate, dimethyl pentene, monobutyl pentene, dimethyl tetradecenoate, dimethyl maleate, dimethyl methyl maleate, dimethyl 3-methylpentene, diethyl pentene, dibenzyl fumarate, dibutyl maleate, monobutyl maleate, dioctyl maleate, monomethyl maleate, monoethyl maleate, triethyl pyromellitic acid, triethyl ethane tricarboxylate, trimethyl propane tricarboxylate, triethyl propane tricarboxylate, triethyl methane tricarboxylate, trihexyl trimellitrate, triisodecyl trimellitrate, triethyl propane tricarboxylate, triethyl cyclohexane tricarboxylate, and triethyl pyromellitic acid.

[0033] (Meth)acrylates: lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, caprolactone-modified tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, isobornyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate, nonylphenoxyethyl methacrylate, butoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glyceryl methacrylate, modified butyl methacrylate, epichlorohydrin-modified phenoxy(meth)acrylate, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, morpholine methacrylate, or silicates with various substituents.

[0034] Difunctional (meth)acrylate monomers: neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, epichlorohydrin modified bisphenol A di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, di(meth)acryloyl isocyanurate, etc.

[0035] Trifunctional (meth)acrylates: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, epichlorohydrin modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified glycerol tri(meth)acrylate, etc.

[0036] Examples of tetrafunctional or higher (meth)acrylates include: di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0037] Furthermore, when the terminating substituent is a carboxylic acid group, the following compounds (i.e., carboxylic acid compounds) can be listed:

[0038] Propionic acid, hexanoic acid, stearic acid, isostearic acid, and oleic acid. Most preferably, monocarboxylic acids having 7-14 carbon atoms, such as heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, isononanoic acid, coconut oil fatty acids, decanoic acid, neodecanoic acid, dodecanoic acid, benzoic acid, o-benzoic acid, m-benzoic acid, terebenzoic acid, hexahydrobenzoic acid, tert-butylbenzoic acid, maleic acid, maleic anhydride, fumaric acid, norborneol anhydride, dodecenoic acid, octenedioic acid, hexadienoic acid, trans-dodecenoic acid, octadecenoic acid, 2,3-dimethylmaleic anhydride, pentenoic acid, and one or more thereof, most preferably including maleic acid, maleic anhydride, dimethyl maleate, and octenedioic acid;

[0039] Triphenyltricarboxylic acid, triisopropyl pyromellitic acid, propylene tricarboxylic acid, propylene tricarboxylic acid, butane tricarboxylic acid, cyclohexane tricarboxylic acid, trimethyl cyclohexane tricarboxylic acid, pentane tricarboxylic acid, ethane tricarboxylic acid, trimellitic anhydride, trioctyl trimellitic acid, trinonyl trimellitic acid, 1,2,7-heptanetriic acid, 1,3,5-cyclohexanetriic acid, butane tetracarboxylic acid, pyromellitic tetracarboxylic acid, biphenyl tetracarboxylic acid, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, benzene hexacarboxylic acid, and cyclohexane hexacarboxylic acid;

[0040] 1,2-Cyclohexanedicarboxylic acid, 1,3-Cyclohexanedicarboxylic acid, tetrahydrophthalic acid, bridged methylenetetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, and mixtures thereof. Also includes esters or anhydrides of these carboxylic acids such as tetrahydrophthalic anhydride, bridged methylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0041] Furthermore, when the end-capping substituent is an acyl chloride group, the following compounds (i.e., acyl chloride compounds) can be listed:

[0042] terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyldicarboxylate chloride, 3,3'-biphenyldicarboxylate chloride, 3,4'-biphenyldicarboxylate chloride, 4,4'-oxodi(benzoyl chloride), 3,3'-oxodi(benzoyl chloride), 3,4'-oxodi(benzoyl chloride), 4,4'-sulfonyldi(benzoyl chloride), 3,3'-sulfonyldi(benzoyl chloride), 3,4'-sulfonyldi(benzoyl chloride), naphthalene-2,6-dicarboxylate chloride, acryloyl chloride, methacryloyl chloride, ethylacryloyl chloride, propylacryloyl chloride, butylacryloyl chloride, butenoyl chloride, 10-undecenoyl chloride, 3-ethoxyacryloyl chloride, undecenoyl chloride, 3-N,N-dimethylaminomethacryloyl chloride, 2-methyl-3-phenyl- 2-Acryloyl chloride, 3-(4-trifluoromethoxy)phenylprop-2-enoyl chloride, trans-8-methyl-6-nonanoyl chloride, 3-(2-chloro-3,4-dimethoxyphenyl)-2-acryloyl chloride, arachidonicyl chloride, cinnamoyl chloride, 2-methyl-2-butenoyl chloride, piperine acetyl chloride, 3-(4-trifluoromethoxy)phenylprop-2-enoyl chloride, 1,4-phenylene diacetyl chloride, penenoyl chloride, undecenoyl chloride, 3-ethoxyacryloyl chloride, 3-methylcrotonyl chloride, α-bromopropionyl bromide, α-bromobutyryl bromide, α-bromoisobutyryl bromide, α-chloropropionyl chloride, α-chlorobutyryl chloride, α-chloroisobutyryl chloride, α-bromopropionyl chloride, α-bromobutyryl chloride or α-bromoisobutyryl chloride;

[0043] Furthermore, when the terminating substituent is an NCO group, the following compounds (i.e., isocyanate compounds) can be listed:

[0044] Methyl isocyanate, ethyl isocyanate, n-butyl isocyanate, o-toluene isocyanate, 1,6-hexanediisocyanate, isopropyl isocyanate, tert-butyl isocyanate, 2-thiophene isocyanate, benzyl isocyanate, pentyl isocyanate, cyclopentyl isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, tetramethylxylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl ether-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diphenylmethane diisocyanate Isocyanates, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate and other aromatic diisocyanates, polymethylene polyisocyanates, crude toluene diisocyanate and other aromatic polyisocyanates, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), decamethylene diisocyanate, lysine diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate (IPDI), hydrogenated toluene isocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate and other alicyclic diisocyanates, etc.

[0045] Furthermore, when the end-capping substituent is a polyurethane group, the polyurethane compound can be obtained by reacting polyisocyanate and polyether polyol, or by reacting polyisocyanate and amino-containing organic compound; it can also be obtained by reacting polyisocyanate, polyether polyol I and amino-containing organic compound.

[0046] In this invention, the benzoyl carbamate compound may be a mixture of initiators or oligomers of multiple initiators obtained by reacting the compound of general formula (I) and the compound of general formula (II) as described above, or by further reacting the compound of formula (I) and formula (II) with a compound having end-capping substituents to obtain end-capping.

[0047] Preferably, the number average molecular weight of the oligomer is 500-50000, for example 500, 800, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 6000, 8000, 10000, 13000, 15000, 18000, 20000, 23000, 25000, 30000, 35000, 40000, 45000, or 50000.

[0048] Preferably, the compounds of formulas (I) and (II) further reacted with compounds having end-capping substituents to obtain compounds with the following structures or mixtures thereof:

[0049]

[0050] Where R 14 R1 or end-capping substituent; R 15 R1 or end-capping substituent, R 14 and R 15 At least one of them is a capping substituent;

[0051] M represents a C2-C50 substituent, and the alkyl group in the above substituent can be further interrupted by hydroxyl, oxygen atom, carbonyl, epoxy group, oxo group, or benzene ring.

[0052] y is an integer from 1 to 6 (e.g., 1, 2, 3, 4, 5 or 6), and z is an integer from 1 to 50 (e.g., 1, 3, 5, 8, 10, 12, 15, 18, 20, 23, 25, 28, 30, 33, 35, 38, 40, 43, 45, 48 or 50, etc.).

[0053] In a preferred embodiment, the end-capping substituent is selected from...

[0054] In a preferred embodiment, M is selected from... Where n1 is an integer from 1 to 20 (e.g., 1, 2, 3, 4, 5, 8, 10, 12, 14, 16, 18, 20, etc.).

[0055] Preferably, the benzoyl carbamate compound is any one of the following compounds:

[0056]

[0057] In compound 8, R is selected from methyl or

[0058]

[0059]

[0060]

[0061] Where n is an integer from 1 to 20.

[0062] The method for preparing the benzoyl carbamate compound provided by the present invention is not particularly limited. Different suitable preparation methods can be selected according to different raw materials (II). The benzoyl carbamate compound is obtained by reacting the compound described in general formula (I) and the compound described in general formula (II).

[0063] Preferably, the molar ratio of hydroxyl groups in the compound of general formula (I) and the compound of general formula (II) is 1:1.05-6:1, for example 1:1.05, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1 or 6:1.

[0064] Preferably, the reaction of the compound of general formula (I) and the compound of general formula (II) is carried out under weakly alkaline conditions.

[0065] Preferably, the reaction temperature of the compound of general formula (I) and the compound of general formula (II) is 80-180°C (e.g., 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C), and the reaction time is 4-12h (e.g., 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h).

[0066] In this invention, the reaction of the compound of general formula (I) and the compound of general formula (II) may or may not involve the addition of a solvent. There is no particular limitation on the type of solvent used, as long as it can dissolve the reaction raw materials and has no adverse effect on the reaction. Preferably, the solvent for the reaction is selected from any one or a combination of at least two of xylene, m-dichlorobenzene or N,N-dimethylformamide.

[0067] Preferably, the olefinically unsaturated photopolymerizable compound is selected from compounds having one or more olefinic double bonds, esters of olefinically unsaturated carboxylic acids and polyols or polyepoxides.

[0068] Preferably, the olefinically unsaturated photopolymerizable compound is selected from alkyl acrylates, alkyl methacrylates, hydroxyalkyl acrylates, alkyl epoxy esters, (meth)acrylamide, N-substituted (meth)acrylamide, unsaturated carboxylic anhydrides, unsaturated esters, vinyl ethers, isocyanurates, N-vinyl heterocyclic compounds, acrylic acid, methacrylic acid, and unsaturated fatty acids such as linolenic acid or oleic acid. Preferably, the unsaturated carboxylic acid is acrylic acid and methacrylic acid. The polyol may be aromatic, aliphatic, or cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, and linear phenolic resins and phenolic resin A. In another aspect of the invention, the olefinically unsaturated photopolymerizable compound is an acrylated epoxy resin, an alkyl acrylate, an alkoxy acrylate, or a mixture thereof, most preferably an epoxy acrylate, trimethylolpropane triacrylate, or a mixture thereof.

[0069] Preferably, component (a) in the photocurable composition accounts for 0.5-10% of the weight of the composition, for example, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0070] In this invention, component (b) of the photocurable composition accounts for 2-99.5% of the weight of the composition, for example, 2%, 5%, 8%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, etc.

[0071] In addition to components (a) and (b), the photocurable composition of this invention may also contain other photoinitiators (d). The photocurable composition of this invention may also selectively contain commonly used organic and / or inorganic additives (c) in the art, including but not limited to pigments, leveling agents, dispersants, curing agents, surfactants, solvents, etc., which will be obvious to those skilled in the art. Furthermore, sensitizers may also be added to the composition for compound use, provided that they do not negatively affect the application effect of the composition.

[0072] On the other hand, the present invention also provides the use of the photocurable composition as described above in coatings, inks, adhesives or photoresists.

[0073] Compared with the prior art, the present invention has the following beneficial effects:

[0074] The benzoyl carbamate compounds of the present invention have excellent solubility, and the sensitivity of the photocurable compositions containing them is not reduced compared to existing small molecule compositions. Furthermore, the hardness of the products is improved under LED curing. Detailed Implementation

[0075] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0076] Preparation Examples

[0077] Examples 1-3:

[0078] This embodiment provides a method for preparing compounds 1-3, and the reaction process for their preparation is shown below:

[0079]

[0080] Preparation of compound 1:

[0081] (1) At room temperature, add 109.8 g of aluminum trichloride and 350 mL of dichloroethane to a 1 L four-necked flask, start stirring, and cool the system in an ice-water bath. When the internal temperature drops to 0-5 °C, add 80.7 g of methyl oxaloyl chloride (1b). After the addition is complete, continue stirring at this temperature for 1 h. Then add 30 g of diphenyl sulfide (1a) dropwise over 30 min. After the addition is complete, remove the ice bath, allow the temperature to rise naturally and stir. Monitor the reaction with HPLC. When the content of the intermediate (monosubstituted) is <2%, stop the reaction. Pour the reaction solution into 300 mL of 1% hydrochloric acid solution, separate the organic layer, wash the organic layer with water until neutral, concentrate the organic phase to obtain the crude product, and recrystallize the crude product from methanol / dichloroethane to obtain 40 g of pale yellow solid product (HPLC 99.15%, yield 69.3%).

[0082] The structure of intermediate 1c was characterized by 1H-NMR, and the results are as follows:

[0083] 1H-NMR (deuterated chloroform, 500MHz): 7.99-8.01 (4H, d), 7.45-7.48 (4H, d), 3.98 (6H, s).

[0084] (2) Add 36g of (1c), 5.3g of compound (1d), and 1g of potassium acetate to a 100mL four-necked reaction flask. Vacuum the system and, when the pressure drops to -0.095MPa, start the stirrer and heat the mixture, maintaining an internal temperature of 115℃ for 6 hours. Monitor the reaction using HPLC. After the reaction is complete, cool the system to room temperature and pour the reaction solution into 250mL of dichloromethane. Wash the organic layer with water until neutral. Collect the organic phase and concentrate to obtain 37g of crude product, a yellow liquid. Purify by column chromatography (hexane:ethyl acetate volume ratio).

[0085] =4:1), yielding 16g of a pale yellow liquid (compound 1) (HPLC 97.12%).

[0086] The structure of compound 1 was characterized by 1H-NMR, and the results are as follows:

[0087] 1 ¹H-NMR (deuterated chloroform, 500 MHz): 7.65–7.66 (8H, d), 7.56–7.57 (8H, d), 4.26–4.30 (4H, m), 3.59–3.63 (4H, m), 3.61 (6H, s).

[0088] Preparation of compound 2:

[0089] (1) At room temperature, add 30g of diphenyl sulfide (1a), 45g of aluminum trichloride, and 150mL of dichloroethane to a 500mL four-necked flask, start stirring, and cool the system in an ice-water bath. When the internal temperature drops to -5 to 0℃, add 23.7g of methyl oxaloyl chloride (1b) dropwise. After the dropwise addition is completed, continue stirring at this temperature for 1h. After the dropwise addition is completed, the ice bath can be removed, and the system can be heated and stirred naturally. The reaction is monitored by HPLC. When the content of the raw material (diphenyl sulfide) is <5%, the reaction is stopped. Pour the reaction solution into 150mL of 1% hydrochloric acid solution, separate the organic layer, wash the organic layer with water until neutral, concentrate the organic phase to obtain the crude product, and recrystallize the crude product from methanol / dichloroethane to obtain a pale yellow solid product 2c 33.4g (HPLC 97.75%, yield 76.1%).

[0090] use 1 The structure of intermediate 2c was characterized by H-NMR, and the results are as follows.

[0091] 1H-NMR (deuterated chloroform 500MHz): 7.64-7.65 (2H, d), 7.55-7.56 (2H, d), 7.40-7.45 (5H, m), 3.61 (3H, s).

[0092] (2) Add 27.2g of (2c), 5.3g of compound (1d), and 1g of potassium acetate to a 100mL four-necked reaction flask. Vacuum the system and when the pressure drops to -0.095MPa, turn on the stirrer and heat it. Maintain the internal temperature at 115℃ and stir for 6h. Monitor the reaction with HPLC. After the reaction is completed, cool the system to room temperature and pour the reaction solution into 250mL of dichloromethane. Wash the organic layer with water until neutral. Collect the organic phase and concentrate it to obtain a crude product, which is a yellow liquid of 29g. Purify by column chromatography (n-hexane: ethyl acetate = 4:1) to obtain a pale yellow liquid (compound 2) of 23.0g (HPLC 98.34%, yield 78.6%).

[0093] use 1 The structure of compound 2 was characterized by H-NMR, and the results are as follows:

[0094] 1¹H-NMR (deuterated chloroform 500MHz): 7.61-7.62 (4H, d), 7.51-7.52 (4H, d), 7.39-7.43 (¹⁰H, m), 4.25-4.29 (4H, m), 3.58-3.63 (4H, m).

[0095] Preparation of compound 3: 36 g of (1c), 27.2 g of (2c), and 10.6 g of compound (1d) were added to a 100 mL four-necked reaction flask, along with 2 g of potassium acetate. The system was evacuated, and when the pressure dropped to -0.095 MPa, the stirrer was turned on and the temperature was increased. The internal temperature was maintained at 115 °C and stirred for 6 h. The reaction was monitored by HPLC. After the reaction was completed, the system was cooled to room temperature, and the reaction solution was poured into 250 mL of dichloromethane. The organic layer was washed with water until neutral. The organic phase was collected and concentrated to obtain a crude product, which was a yellow liquid of 69 g. The crude product was purified by column chromatography (n-hexane: ethyl acetate = 4:1) to obtain a pale yellow liquid (compound 3) of 16.1 g (HPLC 97.02%).

[0096] The structure of compound 3 was characterized by 1H-NMR, and the results are as follows.

[0097] 1H-NMR (deuterated chloroform 500MHz): 7.63-7.67 (6H, m), 7.53-7.57 (6H, m), 7.39-7.44 (5H, m), 4.26-4.30 (4H, m), 3.58-3.64 (4H, m), 3.62 (3H, s).

[0098] It should be noted that different proportions of the reactants and varying reaction conditions will result in mixtures containing varying amounts of compounds 1, 2, and 3 in actual reactions, but all of these compounds are effective photoinitiators. Furthermore, under certain reaction conditions, compounds 1 and 3 can react further to yield initiators with higher molecular weights.

[0099] Examples 4-5

[0100] This embodiment provides a method for preparing compounds 4-6, and the reaction process for their preparation is shown below:

[0101]

[0102] Preparation of compound 4:

[0103] (1) At room temperature, add 34g of diphenyl ether (2a), 29.3g of aluminum trichloride, and 150mL of dichloroethane to a 500mL four-necked flask, start stirring, and cool the system in an ice-water bath. When the internal temperature drops to -5 to 0℃, add 26.9g of methyl oxaloyl chloride (1b) dropwise. After the dropwise addition is completed, continue stirring at this temperature for 1h. After the dropwise addition is completed, the ice bath can be removed, and the system can be heated and stirred naturally. The reaction is monitored by HPLC. When the content of the raw material (diphenyl ether) is <5%, the reaction is stopped. Pour the reaction solution into 150mL of 1% hydrochloric acid solution, separate the organic layer, wash the organic layer with water until neutral, concentrate the organic phase to obtain the crude product, and recrystallize the crude product from methanol / dichloroethane to obtain 44.7g of a pale yellow solid product (4c) (HPLC 97.47%, yield 87.3%).

[0104] use 1 The structure of intermediate 4c was characterized by H-NMR, and the results are as follows.

[0105] 1 ¹H-NMR (deuterated chloroform, 500 MHz): 7.63–7.64 (2H, d), 7.52–7.56 (2H, m), 7.18–7.25 (5H, m), 3.60 (3H, s).

[0106] (2) Add 25.6 g of (4c), 160 g of compound 2d (weight average molecular weight 321), and 1 g of potassium acetate to a 250 mL four-necked reaction flask. Vacuum the system and when the pressure drops to -0.095 MPa, turn on the stirrer and heat it. Maintain the internal temperature at 115 °C and stir for 6 h. Monitor the reaction with HPLC. After the reaction is complete, cool the system to room temperature and pour the reaction solution into 250 mL of dichloromethane. Wash the organic layer with water until neutral. After collecting the organic phase, concentrate it under reduced pressure to obtain the product, which is a yellow liquid (compound 4) 53.5 g (HPLC determination of content is 95.12%) with a weight average molecular weight of 547.

[0107] Preparation of compound 5:

[0108] 109.8 g of aluminum trichloride and 350 mL of dichloroethane were added to a 1 L four-necked flask at room temperature. The mixture was stirred and cooled in an ice-water bath. When the internal temperature dropped to -5 to 0 °C, 80.7 g of methyl oxaloyl chloride (1b) was added dropwise. After the addition was completed, the mixture was kept at this temperature and stirred for 1 h. Then, 27.4 g of diphenyl ether (2a) was added dropwise over 30 min. After the addition was completed, the ice bath was removed, and the mixture was allowed to heat naturally with stirring. The reaction was monitored by HPLC. When the content of the intermediate (monosubstituted) was <2%, the reaction was stopped. The reaction solution was poured into 300 mL of 1% hydrochloric acid solution, and the organic layer was separated. The organic layer was washed with water until neutral, and the organic phase was concentrated to obtain the crude product. The crude product was recrystallized from methanol / dichloroethane to obtain a pale yellow solid product (5c) of 39.2 g (HPLC determination showed a content of 98.27%, yield of 71.2%) with a weight average molecular weight of 921.

[0109] use 1 The structure of intermediate 5c was characterized by H-NMR, and the results are as follows:

[0110] 1 ¹H-NMR (deuterated chloroform, 500 MHz): 8.09–8.11 (4H, d), 7.14–7.16 (4H, d), 3.99 (6H, s).

[0111] (2) Add 34g of (5c), 160g of compound 2d (weight average molecular weight 321), and 1g of potassium acetate to a 250mL four-necked reaction flask. Vacuum the system and when the pressure drops to -0.095MPa, turn on the stirrer and heat it. Maintain the internal temperature at 115℃ and stir for 6h. Monitor the reaction with HPLC. After the reaction is completed, cool the system to room temperature and pour the reaction solution into 250mL of dichloromethane. Wash the organic layer with water until neutral. After collecting the organic phase, concentrate it under reduced pressure to obtain the product, which is a yellow liquid (compound 5) 90.0g (HPLC determination of content is 94.36%).

[0112] Example 6

[0113] Preparation of compound 6

[0114]

[0115] Preparation of compound 6:

[0116] At room temperature, 36.7 g of the above-mentioned acyl chloride and 350 mL of dichloroethane were added to a 1 L four-necked flask. The mixture was stirred and cooled in an ice-salt bath. When the internal temperature dropped to -5 to 0 °C, 20 g of anhydrous ethanol was added dropwise. Exothermic and gas release was significant in the early stages; the dropping rate and tail gas absorption were carefully controlled. After the addition was complete, the mixture was returned to room temperature and stirred for 1 h. The reaction was monitored by HPLC. When the starting material content was <1%, the reaction was stopped, and the organic phase was concentrated to obtain the crude product. The crude product was recrystallized from methanol / dichloroethane to obtain 36.1 g of a yellow solid product (compound 6) (HPLC determination showed a content of 98.77%, yield 93.5%).

[0117] use 1 The structure of compound 6 was characterized by H-NMR, and the results are as follows:

[0118] 1 ¹H-NMR (deuterated chloroform, 500 MHz): 7.98–7.99 (4H, d), 7.43–7.46 (4H, d), 4.35–4.38 (4H, q), 1.39–1.41 (6H, t).

[0119] Example 7

[0120]

[0121] Preparation of compound 7:

[0122] At room temperature, 34.0 g of the above-mentioned carboxylic acid and 148 g of tert-butanol were added to a 250 mL single-necked flask. The mixture was stirred and stirred until homogeneous. Then, 2 mL of concentrated sulfuric acid was added, and the temperature was raised to 90 °C and maintained for 4 h. The reaction was monitored by HPLC. When the content of the starting material was <1%, the reaction was stopped, and the organic phase was concentrated to obtain the crude product. The crude product was recrystallized from methanol / dichloroethane to obtain a white solid product (compound 7).

[0123] 40.5g (HPLC determination showed a content of 99.17% and a yield of 89.5%).

[0124] use 1 The structure of compound 7 was characterized by H-NMR, and the results are as follows:

[0125] 1 ¹H-NMR (deuterated chloroform, 500 MHz): 7.99–8.01 (4H, d), 7.59–7.60 (4H, d), 1.72 (6H, s), 1.41 (18H, s).

[0126] Example 8

[0127] Preparation of compound 8

[0128]

[0129] Add 35g of (1c), 23.2g of TCM101, and 1g of potassium acetate to a 100mL single-necked flask. After mixing thoroughly, the system is heated. When the external temperature reaches 110℃, stirring is started, and the system is evacuated. When the pressure drops to -0.095MPa, the external temperature is maintained at 110℃ and stirred for 4h. The reaction is monitored by HPLC. When the starting material (1c) is less than 1%, the reaction is stopped. The system is cooled to room temperature, the reaction solution is poured into water, and extracted with dichloromethane. The organic phases are combined, and 1g of activated carbon is added to the organic phase and stirred for 2h. The mixture is filtered and concentrated to obtain 40.0g of yellow liquid (compound 8), and the weight-average molecular weight is measured to be 502.

[0130] Examples 9-40

[0131] Following the methods of Examples 1-8, initiators with different structures can be obtained by selecting raw materials and controlling the amount of reactants, as shown in Table 1. The NMR characterization data of some of these compounds are shown in Table 2.

[0132] Table 1

[0133]

[0134]

[0135]

[0136]

[0137] Table 2

[0138]

[0139]

[0140]

[0141] Furthermore, the compounds described in formulas (I) and (II) are further reacted with compounds of different substituents to obtain end-capped compounds, as shown in the following specific examples:

[0142] Example 41

[0143]

[0144] R 14 R 15 It is methoxy or Groups, asterisks represent group linkage sites, y is an integer from 1 to 10, n is an integer from 1 to 20, and z is an integer from 1 to 10.

[0145] Add 34g of (5c), 20g of polypropylene glycol-400, 11.6g of TCM101, and 1g of potassium acetate to a 100mL single-necked flask. After mixing evenly, start heating the system. When the external temperature reaches 110℃, start stirring and evacuate the system. When the pressure drops to -0.095MPa, maintain the external temperature at 110℃ and stir for 2h. After the heat preservation is completed, further increase the vacuum degree of the system to 200-300Pa. GPC monitors the reaction. Stop the reaction when the weight average molecular weight of the product is >1000. Cool the system to room temperature, add 1g of activated carbon to the reaction solution and stir for 2h. Filter to obtain 59.0g of viscous yellow liquid (compound 41), and the weight average molecular weight is measured to be 1822.

[0146] Example 42

[0147] Add 34g of (5c), 10g of polyethylene glycol-200, 11.6g of TCM101, and 1g of potassium acetate to a 100mL single-necked flask. After mixing evenly, start heating the system. When the external temperature reaches 110℃, start stirring and evacuate the system. When the pressure drops to -0.095MPa, maintain the external temperature at 110℃ and stir for 2h. After the heat preservation is completed, further increase the vacuum degree of the system to 200-300Pa. GPC monitors the reaction. Stop the reaction when the weight average molecular weight of the product is >1000. Cool the system to room temperature, add 1g of activated carbon to the reaction solution and stir for 2h. Filter to obtain 56.0g of viscous yellow liquid (compound 42), and the weight average molecular weight is measured to be 2116.

[0148] Example 43

[0149]

[0150] R 14 R 15 It is methoxy or Groups, asterisks represent group linkage sites, y is an integer from 1 to 10, n is an integer from 1 to 20, and z is an integer from 1 to 10.

[0151] Add 35g of (1c), 12g of polyethylene glycol-200, 10.5g of TCM101, and 1g of potassium acetate to a 250mL single-necked flask. After mixing evenly, start heating the system. When the external temperature reaches 110℃, start stirring and evacuate the system. When the pressure drops to -0.095MPa, maintain the external temperature at 110℃ and stir for 2h. After the heat preservation is completed, further increase the vacuum degree of the system to 200-300Pa. GPC monitors the reaction. Stop the reaction when the weight-average molecular weight of the product reaches the predetermined value. Cool the system to room temperature, add 1g of activated carbon to the reaction solution and stir for 2h. Filter to obtain 61.0g of viscous yellow liquid (compound 43), and the weight-average molecular weight is measured to be 5104.

[0152] Example 44

[0153] Add 35g of (1c), 14g of polyethylene glycol-200, 9.3g of TCM101, and 1g of potassium acetate to a 250mL single-necked flask. After mixing thoroughly, the system is heated. When the external temperature reaches 110℃, stirring is started, and the system is evacuated. When the pressure drops to -0.095MPa, the external temperature is maintained at 110℃ and stirred for 2h. After the heat preservation is completed, the vacuum degree of the system is further increased to 200-300Pa. GPC is used to monitor the reaction. When the weight-average molecular weight of the product reaches the predetermined value, the reaction is stopped. The system is cooled to room temperature, and 1g of activated carbon is added to the reaction solution and stirred for 2h. After filtration, 60.0g of viscous yellow liquid (compound 44) ​​is obtained, and the weight-average molecular weight is measured to be 10306.

[0154] Example 45

[0155] Add 35g of (1c), 16g of polyethylene glycol-200, 8.2g of TCM101, and 1g of potassium acetate to a 250mL single-necked flask. After mixing thoroughly, the system is heated. When the external temperature reaches 110℃, stirring is started, and the system is evacuated. When the pressure drops to -0.095MPa, the external temperature is maintained at 110℃ and stirred for 2h. After the heat preservation is completed, the vacuum degree of the system is further increased to 200-300Pa. GPC is used to monitor the reaction. When the weight-average molecular weight of the product reaches the predetermined value, the reaction is stopped. The system is cooled to room temperature, and 1g of activated carbon is added to the reaction solution and stirred for 2h. After filtration, 57.0g of viscous yellow liquid (compound 45) is obtained, and the weight-average molecular weight is measured to be 22196.

[0156] Example 46

[0157] Add 35g of (1c), 18g of polyethylene glycol-200, 7.0g of TCM101, and 1g of potassium acetate to a 250mL single-necked flask. After mixing thoroughly, the system is heated. When the external temperature reaches 110℃, stirring is started, and the system is evacuated. When the pressure drops to -0.095MPa, the external temperature is maintained at 110℃ and stirred for 2h. After the heat preservation is completed, the vacuum degree of the system is further increased to 200-300Pa. GPC is used to monitor the reaction. When the weight-average molecular weight of the product reaches the predetermined value, the reaction is stopped. The system is cooled to room temperature, and 1g of activated carbon is added to the reaction solution and stirred for 2h. After filtration, 51.0g of viscous yellow liquid (compound 46) is obtained, and the weight-average molecular weight is measured to be 49104.

[0158] Example 47

[0159]

[0160] R 14 R 15 It is methoxy or Group, y is an integer from 1 to 10, n is an integer from 1 to 20, and z is an integer from 1 to 10.

[0161] Add 34g of (5c), 60g of polyethylene glycol-300, and 1g of potassium acetate to a 250mL single-necked flask. After mixing evenly, start heating the system. When the external temperature reaches 110℃, start stirring and evacuate the system. When the pressure drops to -0.095MPa, maintain the external temperature at 110℃ and stir for 2 hours. After the heat preservation is completed, further increase the vacuum degree of the system to 200-300Pa. Monitor the reaction with GPC. Stop the reaction when the weight average molecular weight of the product is >1000. Cool the system to room temperature, pour the reaction solution into water, extract with dichloromethane, combine the organic phases, dry and filter. Add 22g of triethylamine to the system and cool to 0℃. Start adding 20g of acryloyl chloride dropwise. After the dropwise addition is completed, naturally heat up and keep the reaction at room temperature for 6 hours. After the reaction was completed, the reaction solution was poured into water, extracted with dichloromethane, and the organic phases were combined. 1g of activated carbon was added to the organic phase and stirred for 2 hours. The mixture was then filtered and concentrated to obtain 45.0g of a viscous yellow liquid (compound 44), and the weight-average molecular weight was measured to be 1900.

[0162] Example 48

[0163]

[0164] R 14 R 15 It is methoxy or Group, y is an integer from 1 to 10, n is an integer from 1 to 20, and z is an integer from 1 to 10.

[0165] The difference from Example 47 is that the parent material of Example 48 is (1c), and the weight-average molecular weight of compound 48 is 2138.

[0166] Example 49

[0167]

[0168] R 14 R 15 It is methoxy or Group, y is an integer from 1 to 10, n is an integer from 1 to 20, and z is an integer from 1 to 10.

[0169] Add 35g of (1c), 60g of polyethylene glycol-300, and 1g of potassium acetate to a 250mL single-necked flask. After mixing evenly, start heating the system. When the external temperature reaches 110℃, start stirring and evacuate the system. When the pressure drops to -0.095MPa, maintain the external temperature at 110℃ and stir for 2 hours. After the heat preservation is completed, further increase the vacuum degree of the system to 200-300Pa. Monitor the reaction with GPC. Stop the reaction when the weight average molecular weight of the product is >1000. Cool the system to room temperature, pour the reaction solution into water, extract with dichloromethane, combine the organic phases, dry and filter, and remove solvent. Transfer the residue to a 500mL four-necked flask. Add 15g of acrylic acid and 150g of toluene to the system, stir evenly, and then add 1g of tetraethyl titanate dropwise. Reflux and keep the reaction at the temperature for 4 hours. After the reaction was completed, the reaction solution was poured into water, extracted with dichloromethane, and the organic phases were combined. The organic phases were washed once with water and once with acid. 1g of activated carbon was added to the organic phase and stirred for 2h. After filtration and concentration, 47.0g of viscous yellow liquid (compound 49) was obtained, and the weight-average molecular weight was measured to be 2156.

[0170] Example 50

[0171]

[0172] R 15 It is methoxy or Group, y is an integer from 1 to 10, n is an integer from 1 to 20, and z is an integer from 1 to 10.

[0173] The difference from Example 49 is that the chain extender in Example 50 is polypropylene glycol-300, with a molar addition of 2.0 eq, resulting in a weight-average molecular weight of 2068 for compound 50.

[0174] Example 51

[0175]

[0176] The difference from Example 50 is that the parent material of Example 48 was ethyl diphenyl ether ketone acid, and the weight-average molecular weight of compound 51 was 1960.

[0177] Example 52

[0178]

[0179] R 15 It is methoxy or Group, y is an integer from 1 to 10, n is an integer from 1 to 20, z is an integer from 1 to 10, and m is 0.

[0180] Add 35g of (1c), 60g of polyethylene glycol-300, and 1g of potassium acetate to a 250mL single-necked flask. After mixing thoroughly, start heating the system. When the external temperature reaches 110℃, start stirring and evacuate the system. When the pressure drops to -0.095MPa, maintain the external temperature at 110℃ and stir for 2 hours. After the heat preservation is completed, further increase the vacuum degree of the system to 200-300Pa. Monitor the reaction with GPC. Stop the reaction when the weight average molecular weight of the product is >1000. Cool the system to room temperature, pour the reaction solution into water, extract with dichloromethane, combine the organic phases, dry and filter, and cool the system to 0℃. Start adding 16g of ethyl isocyanate dropwise. After the dropwise addition is completed, allow the temperature to rise naturally and keep the reaction at room temperature for 4 hours. After the reaction was completed, the reaction solution was poured into water, extracted with dichloromethane, and the organic phases were combined. 1g of activated carbon was added to the organic phase and stirred for 2 hours. The mixture was then filtered and concentrated to obtain 55.0g of a viscous yellow liquid (compound 52), and the weight-average molecular weight was measured to be 1890.

[0181] Example 53

[0182]

[0183] R 15 It is methoxy or Group, y is an integer from 1 to 10, n is an integer from 1 to 20, z is an integer from 1 to 10, and m is 0.

[0184] The difference from Example 52 is that the parent material of Example 50 was methyl benzyl ketone, and the weight-average molecular weight of compound 53 was 1820.

[0185] Example 54

[0186]

[0187] R 15 It is methoxy or Group, y is an integer from 1 to 10, n is an integer from 1 to 20, z is an integer from 1 to 10, and m is 0.

[0188] The difference from Example 53 is that the parent material of Example 51 was methyl diphenylmethane ketone, and the weight-average molecular weight of compound 54 was 1850.

[0189] Performance Evaluation

[0190] The application performance of the initiator of the present invention was evaluated by formulating exemplary photocurable compositions (i.e., photosensitive resin compositions, parts by weight).

[0191] Table 3 Photocurable Compositions

[0192]

[0193]

[0194] E201: Bisphenol A epoxy acrylate (Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0195] ACMO: Acryloylmorpholine (Runao Chemical)

[0196] TMPTA: Trimethylolpropane triacrylate

[0197] PEGDA: Polyethylene glycol diacrylate

[0198] BYK307: Leveling agent (BYK Chemicals, Germany)

[0199] Initiator A: [4-(4-methoxyoxaloyl-phenylthioalkyl)-phenyl]-oxo-acetic acid methyl ester

[0200] Initiator B: 2-(9,9-dimethoxyxanthone-2-yl)-2-oxo-ethyl acetate

[0201] Initiator C: Initiator MBF

[0202] Initiator D: Initiator 754.

[0203] 2. Performance Evaluation Methods

[0204] (1) Solubility evaluation

[0205] The solubility of initiator A: [4-(4-methoxyoxalyl-phenylthioalkyl)-phenyl]-oxo-acetic acid methyl ester (IGM), initiator B: 2-(9,9-dimethoxyxanthan-2-yl)-2-oxo-ethyl acetate (IGM), and the photoinitiator provided in the examples in propylene glycol methyl ether acetate were tested respectively, and the results are shown in Table 4 below.

[0206] The solubility test method is as follows: At room temperature (20±0.5℃), add an appropriate amount of 6110:TMPTA = 1:1 (mass ratio) photocurable monomer as a solvent to a 250mL glass beaker. Add 0.5g of the test sample to the solvent and stir for 20min. Visually observe whether there is any undissolved sample. If it dissolves completely, continue to add 0.5g of the test sample and stir for 20min until there is insoluble matter. Stop adding the sample, record the data, and calculate the sample solubility according to the following formula:

[0207]

[0208] Table 4

[0209]

[0210]

[0211] (2) Evaluation of curing performance

[0212] The photocurable composition was stirred and mixed under an LED (405nm light source) lamp, and then rolled onto a PET template to form a film with a thickness of approximately 50μm. A mercury lamp (100%, 1m / min, 1140mJ / cm²) was used. 2 Expose the sample under light and observe the curing process. Evaluate the photosensitivity according to the following standards:

[0213] 1. Oil, not solid

[0214] 2. Surface oil, base layer cured.

[0215] 3. The surface is sticky, and fingerprints are easily left on the skin after touching it.

[0216] 4. Basically dry, slightly rough to the touch, faint fingerprints.

[0217] 5. Fully cured, smooth surface, no fingerprints after touching.

[0218] The hardness of the cured film after curing was evaluated according to Method B of GB / T 6739-1996 standard:

[0219] The test results are shown in Table 5:

[0220] Table 5 Test Results

[0221]

[0222] The compositions of Comparative Examples 3 and 4 did not meet the absorption wavelength requirements of the light source, did not cure, and could not be evaluated.

[0223] (3) Transferability Testing

[0224] Using ethanol as a solvent, the initiator was prepared into 1×10⁻⁶ solutions. -5 The maximum absorption wavelength and absorbance A1 of the mol / L solution were measured using a UV3010 ultraviolet spectrophotometer, and the molar extinction coefficient was calculated using formula (1):

[0225] c = A / ε × b (1)

[0226] R = 100 × c / c1 (2)

[0227] Using the formulations of the evaluation examples and comparative example 1 in Table 1-2, after thorough curing, 0.05 g of the above photocurable composition was weighed and fully cured under a high-pressure mercury lamp to obtain a cured film. Each film was immersed in 30 g of ethanol and left at room temperature for 24 h. The absorbance A2 at the maximum absorption wavelength was measured using an ultraviolet spectrophotometer with the same volume of the immersion solution. The concentration of the photoinitiator migrating from the three cured films was calculated using formula (1). Using the concentration value of photoinitiator (1) as a reference, the relative migration rate of each photoinitiator was calculated using formula (2).

[0228] In the above formula, c is the relative concentration (mol / L), c1 is the relative concentration of photoinitiator (1), A is the absorbance, ε is the molar absorptivity (L / mol·cm), b is the sample cell thickness (cm), and R is the relative mobility. The test results are shown in Table 6.

[0229] Table 6

[0230]

[0231]

[0232] Experiments show that the initiator of the present invention does not migrate and has high initiation efficiency. In particular, the initiation efficiency is basically unaffected when the molecular weight is increased. The hardness of the cured product is significantly improved compared with existing initiators, and it has the characteristics of low migration.

[0233] The applicant declares that the present invention is illustrated by the above embodiments to demonstrate the photocurable composition and its application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A photocurable composition, characterized in that, The composition comprises the following components: (a) at least one benzoyl carbamate compound; (b) at least one olefinically unsaturated photopolymerizable compound; The benzoyl carbamate compound is formed by reacting the compound of general formula (I) and the compound of general formula (II): Where A is a single bond, O, S or CR2R3, and R2 and R3 are independent of each other, representing hydrogen, C1-C8 straight-chain or branched alkyl groups; Y represents hydrogen, halogen, nitro, C(=O)C(=O)-OR1, C1-C 10 Straight-chain or branched alkyl groups, C3-C 10 alkyl cycloalkyl, C4-C 10 alkyl cycloalkyl or C4-C 10 cycloalkyl alkyl, or the C1-C 10 Straight-chain or branched alkyl groups, C3-C 10 alkyl cycloalkyl, C4-C 10 alkyl cycloalkyl or C4-C 10 The group formed when the -CH2- group in a cycloalkyl group is replaced by O, N, S, aryl, or C (=O); R1 is a hydroxyl, halogen, or C1-C4 alkoxy group; R4, R6, R5, and R7 independently represent hydrogen, fluorine, hydroxyl, or C1-C. 10 Straight-chain or branched alkyl groups, the hydrogen on the alkyl group can be further replaced by fluorine; R8 and R9 represent hydrogen, C1-C4 alkyl, or C1-C4 alkyl carbonyl groups independently; The independent representation of Y1 and Y2 is C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 alkyl cycloalkyl, C4-C 20 alkyl cycloalkyl or C4-C 20 cycloalkyl alkyl, or the C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 alkyl cycloalkyl, C4-C 20 alkyl cycloalkyl or C4-C 20 The group in a cycloalkyl group after the -CH2- is replaced by O, N, S, Si, aryl, bisphenol fluorene or C (=O); m and n are independent integers from 0 to 20, and m and n are not both 0 at the same time; Or the benzoyl carbamate compound is obtained by further reacting the compounds of formula (I) and (II) with a compound having a capping substituent to obtain a compound.

2. The photocurable composition according to claim 1, characterized in that, The compounds described in formula (II) are selected from: ethylene glycol, polyethylene glycol, diethylene glycol, propylene glycol, polypropylene glycol, glycerol, pentaerythritol, pentapentanol, cyclohexanehexanedol, 2,5-dimethyl-2,5-hexanediol, 1,4-butanediol, 1,5-pentanediol, dipropylene glycol, triethylene glycol, triethylene glycol methyl ether, 1,10-decanediol, tetraethylene glycol trioxide, 2,2-dimethyl-1,3-propanediol, 1,3-cyclohexanediol, 3,4-dihydroxyphenylethanol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, tetramethylethanol Diols, sorbitol, pyridoxine, mannitol, 2,5-bis(1,1-dimethylpropyl)-1,4-benzenediol, xylitol, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, glycidyl ether, phenyl-1,2-ethylene glycol, 2-ethyl-1,3-hexanediol, propylene glycol monohydroxymethyl ether, diethylene glycol dimethyl ether, 3,3'-oxybis(propane-1-ol), neopentyl glycol 2,2-dimethyl-3-hydroxypropionate, triethylene glycol, 3,7-dioxa-1,9-nonanediol, 4,8-dioxaundecane-1,11-diol, diethylene glycol, 4-heptaoxyheptane Diol, 1,4-dioxane-2,3-diol, 3-(2-hydroxyethoxy)propane-1,2-diol, 6H-benzofurano[3,2-C][1]benzopyran-3,9-diol, (3S,3aR,6S,6aR)-hexahydrofurano[3,2-b]furan-3,6-diol, phenol glycol, pentaethylene glycol, (9Ci)-octahydro-4A,8A-(methaneoxymethane)naphthalene-2,7-diol, 3,3'-[1,4-butadiylbis(oxy)]bis-1,2-propanediol, 3,3'-di-1,2-propanediol oxide, 2 -Ethyl-2-[(2-hydroxyethoxy)methyl]-1,3-propanediol, di(2-hydroxypropyl) ether, drospirenone 5,5'-diol, 2-methyl-3,4-chromodiol, 2,5-tetrahydrofurandiol, propylene glycol salicylate, octaethylene glycol, 5-methoxy-2-methoxy-tetrahydro-pyran-3,4-diol, 2,2-dimethyl-hexahydro-1,3,4,8-tetraoxacyclopentane(a)inden-5,7-diol, 6-methoxy-2-phenyl-hexahydro-pyran(3,2-D)(1,3)dioxane-7,8-diol, chromo-4,6-diol, R represents hydrogen, methyl, or further halogen-substituted methyl, n1 is an integer from 1 to 10; m1 and n2 are independently integers from 0 to 10, and m1 + n2 = 10.

3. The photocurable composition according to claim 1 or 2, characterized in that, The benzoyl carbamate compound has any one of the following structures: Among them, R 10 R9 group or Group, the wavy line represents the group's connection site, R 11 Y group or Groups, the wavy line represents the connection site of the group.

4. The photocurable composition according to any one of claims 1-3, characterized in that, The benzoyl carbamate compound is any one of the following compounds: In compound 8, R is selected from methyl or Where n is an integer from 1 to 20.

5. The photocurable composition according to any one of claims 1-3, characterized in that, The terminating substituent is selected from hydroxyl, ester, carboxylic acid, acyl chloride, isocyanate, or polyurethane groups; Preferably, the compound having end-capped substituents is selected from alcohols, esters, isocyanates, carboxylic acids, acyl chlorides, or polyurethanes; Preferably, the benzoyl carbamate compound may be a mixture of initiators or oligomers of multiple initiators obtained by reacting the compound of general formula (I) and the compound of general formula (II) as described above, or by further reacting the compound of formula (I) and formula (II) with a compound having end-capping substituents to obtain end-capping. Preferably, the number-average molecular weight of the oligomer is 500-50000.

6. The photocurable composition according to any one of claims 1-3, characterized in that, The compounds of formulas (I) and (II) further reacted with compounds having end-capping substituents to obtain compounds with the following structures or mixtures thereof: Where R 14 R1 or end-capping substituent; R 15 R1 or end-capping substituent, R 14 and R 15 At least one of them is a capping substituent; M represents a C2-C50 alkyl group, which may be further interrupted by hydroxyl, oxygen atom, carbonyl, epoxy group, oxo group, or benzene ring; y is an integer from 1 to 6, and z is an integer from 1 to 50.

7. The photocurable composition according to claim 6, characterized in that, The terminating substituent is selected from... Preferably, M is selected from Where n1 is an integer from 1 to 20.

8. The photocurable composition according to any one of claims 1-7, characterized in that, In the photocurable composition, component (a) accounts for 0.5-10% of the weight of the composition.

9. The photocurable composition according to any one of claims 1-8, characterized in that, The photocurable composition also includes other additives (c) and / or other photoinitiators (d).

10. The use of the photocurable composition according to any one of claims 1-9 in coatings, inks, adhesives or photoresists.

Images