Photocurable composition and use thereof

Abstract

Provided in the present application are a photocurable composition and the use thereof. The composition comprises the following components: (a) at least one benzoyl formate compound; and (b) at least one ethylenically unsaturated photopolymerizable compound; and the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) with the compound represented by general formula (II) or general formula (III), or is obtained by further reacting and terminating the compounds represented by formula (I), formula (II) and general formula (III) with a compound having an end-capping substituent. The benzoyl formate compound of the present application has good dissolving performance, the sensitivity of the obtained product is not reduced relative to that of existing micromolecules, and the hardness of the product is improved under the curing of an LED.

Description

A photocuring composition and application thereof TECHNICAL FIELD

[0001] The present application belongs to the field of photocuring, and particularly relates to a photocuring composition and application thereof. BACKGROUND

[0002] The benzoyl formate photoinitiator is a common free radical photoinitiator, which is very commonly used due to simple structure, easy synthesis and low price, but there are problems such as migration, odor, yellowing and solubility in the use process, which greatly limits its application. Chinese patent applications CN102442909A and CN101979373A macromolecularize the benzoyl formate photoinitiator, which to some extent solves the problems of odor and migration, but the initiation efficiency is reduced, and the cost factor is also a direction to be considered.

[0003] However, on the basis of improving the solubility and migration after curing of the initiator product, how to reduce the influence on the initiation efficiency is a goal that has been pursued, especially under LED curing, it is also a problem to be solved that the application performance of the product is not affected while the existing initiation efficiency is ensured. SUMMARY

[0004] The present application provides a photocuring composition and application thereof. The photocuring composition of the present application has good compatibility after application, no migration, less influence on initiation efficiency, low cost, and the hardness of the product is improved while the initiation efficiency is not affected under LED curing.

[0005] The present application adopts the following technical solutions:

[0006] In a first aspect, the present application provides a photocuring composition, which comprises the following components:

[0007] (a) at least one benzoyl formate compound;

[0008] (b) at least one ethylenically unsaturated photopolymerizable compound;

[0009] The benzoyl formate compound is a compound represented by general formula (I) and a compound represented by general formula (II) or general formula (III) in reaction:

[0010] A is a single bond, O, S or CR2R3, and R2 and R3 independently represent hydrogen, C1-C8 linear or branched alkyl;

[0011] Y represents hydrogen, halogen (such as fluorine, chlorine, bromine or iodine), nitro, C(=O)C(=O)-OR1, C1-C 10straight-chain or branched alkyl, C3-C 10 alkylcycloalkyl, C4-C 10 alkylcycloalkyl or C4-C 10 cycloalkylalkyl, or the -CH2- in said C1-C 10 straight-chain or branched alkyl, C3-C 10 alkylcycloalkyl, C4-C 10 alkylcycloalkyl or C4-C 10 cycloalkylalkyl, or the -CH2- in said C1-C

[0012] R1is hydroxy, halogen (e.g. fluorine, chlorine, bromine or iodine) or C1-C4alkoxy;

[0013] R4, R6, R5, R7independently of one another represent hydrogen, fluorine, hydroxy or C1-C 10 straight-chain or branched alkyl, the hydrogen on the alkyl group being further substitutable by fluorine;

[0014] R8, R9independently of one another represent hydrogen, C1-C8alkyl or C1-C8alkyl interrupted by an oxygen atom, an epoxy group, an oxacyclyl group, a phenyl ring;

[0015] Y1, Y2independently of one another represent a bond, C1-C 20 straight-chain or branched alkyl, C3-C 20 alkylcycloalkyl, C4-C 20 alkylcycloalkyl or C4-C 20 cycloalkylalkyl, or the -CH2- in said C1-C 20 straight-chain or branched alkyl, C3-C 20 alkylcycloalkyl, C4-C 20 alkylcycloalkyl or C4-C 20 cycloalkylalkyl, or the -CH2- in said C1-C

[0016] m and n are independently integers from 0 to 20 (e.g. 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19 or 20) and m and n are not simultaneously 0;

[0017] p is 0 or 1 ;

[0018] R a is C1-C 80 alkyl, or C1-C 80 alkyl interrupted by an oxygen atom, an epoxy group, an oxacyclyl group, a phenyl ring;

[0019] q is an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8).

[0020] Alternatively, the benzoyl formate compound is obtained by reacting a compound represented by the general formula (I) and a compound represented by the general formula (II) or (III), and further reacting with a compound having a capping substituent to cap.

[0021] In the present application, the range of the number of carbon atoms in the group definition indicates that the number of carbon atoms of the group defined can be any number within the defined range, for example, C1-C8 indicates that the number of carbon atoms can be 1, 2, 3, 4, 5, 6, 7, or 8, and the C1-C8 20 indicates that 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.

[0022] Preferably, the compound represented by the general formula (II) or the general formula (III) can be exemplified by ethylene glycol, polyethylene glycol, diethylene glycol, propylene glycol, polypropylene glycol, glycerol, pentaerythritol, pentatonic alcohol, cyclohexane hexanol, 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, 2,2-dimethyl-1,3-propanediol, 1,3-cyclohexanediol, 3,4-dihydroxyphenethyl alcohol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, tetramethyl ethylene glycol, 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 monomethyl ether, diethylene glycol dimethyl ether, 3,3'-oxybis(propane-1-ol), 2,2-dimethyl-3-hydroxypropanoic acid neopentyl glycol ester, triethylene glycol, 3,7-dioxa-1,9-nonanediol, 4,8-dioxadecane-1,11-diol, diethylene glycol, 4-oxaheptanediol, 1,4-dioxane-2,3-diol, 3-(2-hydroxyethoxy)propane-1,2-diol, 6H-benzofuro[3,2-C][1]benzopyran-3,9-diol, (3S,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6-diol, phenol diol, pentaglycol, (9Ci)-octahydro-4A,8A-(methyloxymethane)naphthalene-2,7-diol, 3,3'-[1,4-butanediylbis(oxy)]bis-1,2-propanediol, 3,3'-oxybis-1,2-propanediol, 2-ethyl-2-[(2-hydroxyethoxy)methyl]-1,3-propanediol, bis(2-hydroxypropyl) ether, drospirenone 5,5'-diol, 2-methyl-3,4-chromen- diol, 2,5-tetrahydrofuran diol, salicylic acid propylene glycol ester, octaethylene glycol, 5-methoxy-2-methoxy-tetrahydro-pyran-3,4-diol, 2,2-dimethyl-hexahydro-1,3,4,8-tetraoxacyclopenta(a)indene-5,7-diol, 6-methoxy-2-phenyl-hexahydro-pyran(3,2-D)(1,3)dioxane-7,8-diol, chrom-4,6-diol, R represents hydrogen, methyl or methyl further substituted by halogen, n1 is an integer from 1 to 10 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10); m1, n2 are independently an integer from 0 to 10 (e.g. 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10), and m1 + n2 = 10.

[0023] In the present application, depending on the ratio of the compounds of formula (I) and formula (II) and the raw materials, different compounds or mixtures of initiators are obtained.

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

[0025] wherein R 10 is an R9group or group, the wavy line represents the connecting site of the group, R 11 is a Y group or group, R 12 is an R9group or group, the wavy line represents the connecting site of the group, R 13 is a Y group or group, the wavy line represents the connecting site of the group.

[0026] Preferably, the capping substituent is selected from a hydroxyl group, an ester group, a carboxylic acid, an acyl chloride, an isocyanate group (NCO) or a polyurethane group.

[0027] Preferably, the compound with a capping substituent is selected from an alcohol compound, an ester compound, an isocyanate, a carboxylic acid compound, an acyl chloride compound or a polyurethane.

[0028] Preferably, when the capping substituent is a hydroxyl group, the following compounds (i.e. alcohol compounds) can be listed:

[0029] Ethylene glycol, propylene glycol, 1,2-propylene glycol, 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-bishydroxymethylcyclohexane, 1,3-bishydroxymethylcyclohexane, 1,4-bishydroxymethylcyclohexane, 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-pentadecanediol, 1,16-hexadecanediol, and polyethylene glycol, glycerol, glycerol trimer, glycerol tetramer, glycerol pentamer, glycerol hexamer, glycerol heptamer, glycerol octamer, glycerol decamer, glycerol eicosamer, pentaerythritol, dipentaerythritol, trimethylol ethane, trimethylol propane, hexanetriol, butanetriol, decanetriol, pentanetriol, cyclohexanetriol, heptanetriol, nonanetriol, octanetriol, L-threitol, butanetetraol, or cyclohexanehexol.

[0030] Further, when the end-capping substituent is an ester group, the following compounds (i.e., ester compounds) can be listed:

[0031] dimethyl, diethyl, di-propyl, dihexyl, diheptyl, dioctyl, dinonyl, didecyl, di-n-butyl, di-t-butyl, di-isobutyl, di-n-octyl, di-isooctyl, di-2-ethylhexyl, di-n-nonyl, di-isnonyl, di-n-decyl, diisodecyl, dimethyl 2,6-naphthalene dicarboxylate, 2,7-naphthalene dicarboxylic acid, dimethyl 2,7-naphthalene dicarboxylate, 1,4'-naphthalene dicarboxylic acid, dimethyl 1,4'-naphthalene dicarboxylate, dimethyl 2,2-biphenyl dicarboxylate, dimethyl biphenyl dicarboxylate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl pentene dicarboxylate, monobutyl pentene dicarboxylate, dimethyl tetradecene dicarboxylate, dimethyl methyl maleate, dimethyl 3-methyl pentene dicarboxylate, diethyl pentene dicarboxylate, dibenzyl fumarate, diester maleate, monobutyl maleate, dioctyl maleate, monomethyl maleate, monoethyl maleate, triethyl trimellitate, triethyl ethane tricarboxylate, trimethyl propane tricarboxylate, triethyl propane tricarboxylate, triethyl methane tricarboxylate, tri-n-hexyl trimellitate, triisodecyl trimellitate, triethyl propane tricarboxylate, cyclohexane tricarboxylic acid, or triethyl benzene tricarboxylic acid.

[0032] (meth)acrylates: lauryl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, bicyclo-pentane (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glyceryl (meth)acrylate, modified butyl (meth)acrylate, epichlorohydrin-modified phenoxy (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, morpholino (meth)acrylate, or siliconic acid esters of various substituents.

[0033] 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, pentaerythritol di(meth)acrylate modified with stearic acid, bicyclo-pentene di(meth)acrylate, or di(meth)acryloyl isocyanurate, etc.

[0034] Tri- or higher functional (meth)acrylates include: di(trimethylolpropane) tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate.

[0035] Tri- or higher functional (meth)acrylates include: di(trimethylolpropane) tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate.

[0036] Further, when the end-capping substituent is a carboxylic acid group, the following compounds (i.e., carboxylic acid compounds) can be listed:

[0037] propionic acid, hexanoic acid, stearic acid, isostearic acid, and oleic acid; most preferably a monocarboxylic acid having 7 to 14 carbon atoms, such as one or more of heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, isononanoic acid, coconut oil fatty acid, decanoic acid, neodecanoic acid, dodecanoic acid, benzoic acid, o-benzoic acid, m-benzoic acid, p-benzoic acid, hexahydrobenzoic acid, t-butylbenzoic acid, maleic acid, maleic anhydride, fumaric acid, norbornene dicarboxylic anhydride, dodecene dicarboxylic acid, octene dicarboxylic acid, hexadiene dicarboxylic acid, trans-dodecene acid, octadecene dicarboxylic acid, 2,3-dimethyl maleic anhydride, pentene dicarboxylic acid, most preferably including maleic acid, maleic anhydride, dimethyl maleate, or octene dicarboxylic acid;

[0038] benzene tricarboxylic acid, triisopropyl benzene tricarboxylate, propanetricarboxylic acid, propenetricarboxylic acid, butane tricarboxylic acid, cyclohexane tricarboxylic acid, trimethyl cyclohexanetricarboxylate, pentane tricarboxylic acid, ethane tricarboxylic acid, trimellitic anhydride, trioctyl trimellitate, trinonyl trimellitate, 1,2,7-heptanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, butane tetracarboxylic acid, pyromellitic acid, biphenyl tetracarboxylic acid, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, benzene hexacarboxylic acid, or cyclohexane hexacarboxylic acid;

[0039] 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, and mixtures thereof; also including esters or anhydrides of these carboxylic acids, such as tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride, or methylhexahydrophthalic anhydride.

[0040] Further, when the end-capping substituent is a carboxylic acid group, the following compounds (i.e., carboxylic acid compounds) can be listed:

[0041] terephthaloyl chloride, isophthaloyl chloride, 4,4'-biphenyldicarboxylic acid dichloride, 3,3'-biphenyldicarboxylic acid dichloride, 3,4'-biphenyldicarboxylic acid dichloride, 4,4'-oxybis(benzoyl chloride), 3,3'-oxybis(benzoyl chloride), 3,4'-oxybis(benzoyl chloride), 4,4'-sulfonylbis(benzoyl chloride), 3,3'-sulfonylbis(benzoyl chloride), 3,4'-sulfonylbis(benzoyl chloride), naphthalene-2,6-dicarboxylic acid dichloride, acryloyl chloride, methacryloyl chloride, ethyl acryloyl chloride, propyl acryloyl chloride, butyl acryloyl chloride, butenoyl chloride, 10-undecenoyl chloride, 3-ethoxyacryloyl chloride, undecenoyl chloride, 3-N,N-dimethylaminomethyl acryloyl chloride, 2-methyl-3-phenyl-2-propenoyl chloride, 3-(4-trifluoromethoxy)phenylprop-2-enoyl chloride, trans-8-methyl-6-nonanoyl chloride, 3-(2-chloro-3,4-dimethoxyphenyl)-2-propenoyl chloride, arachidonoyl chloride, cinnamoyl chloride, 2-methyl-2-butenoyl chloride, piperonyloyl chloride, 3-(4-trifluoromethoxy)phenylprop-2-enoyl chloride, 1,4-phenylenediacyl chloride, pentenoyl chloride, undecenoyl chloride, 3-ethoxyacryloyl chloride, 3-methylcrotonoyl 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;

[0042] Further, when the end-capping substituent is an NCO group, the following compounds (i.e., isocyanate compounds) can be exemplified:

[0043] methyl isocyanate, ethyl isocyanate, n-butyl isocyanate, o-tolyl isocyanate, 1,6-hexane diisocyanate, isopropyl isocyanate, t-butyl isocyanate, 2-thiophene isocyanate, benzyl isocyanate, amyl isocyanate, cyclopentyl isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, tetramethyl xylene diisocyanate, 4,4'-diphenyl methane diisocyanate, 2,4'-diphenyl methane diisocyanate, 4,4'-diphenyl methane diisocyanate, 2,4'-diphenyl methane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitro diphenyl ether-4,4'-diisocyanate, 2,2'-diphenyl propane-4,4'-diisocyanate, 3,3'-dimethyl diphenyl methane-4,4'-diisocyanate, 4,4'-diphenyl propane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxy diphenyl-4,4'-diisocyanate, and other aromatic diisocyanates, polymethylene polyisocyanates, aromatic polyisocyanates such as crude toluene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), decamethylene diisocyanate, lysine diisocyanate, and other aliphatic diisocyanates, isophorone diisocyanate (IPDI), hydrogenated toluene isocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenyl methane diisocyanate, and other alicyclic diisocyanates, and the like;

[0044] Further, when the end-capping substituent is a polyurethane group, the polyurethane compound can be obtained by reacting a polyisocyanate and a polyether polyol, or by reacting a polyisocyanate and an amino-containing organic compound, or by reacting a polyisocyanate, a polyether polyol I, and an amino-containing organic compound.

[0045] In the present application, the benzoyl formate compound can be a mixture of initiators or an oligomer of various initiators obtained by reacting the compound represented by general formula (I) and the compound represented by general formula (II) or general formula (III) as described above, or by reacting the compound represented by general formula (I) and the compound represented by general formula (II) or general formula (III) and further reacting with a compound having an end-capping substituent to cap the end.

[0046] Preferably, the number average molecular weight of the oligomer is preferably 500 to 50,000, for example, 500, 800, 1,000, 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 6,000, 8,000, 10,000, 13,000, 15,000, 18,000, 20,000, 23,000, 25,000, 30,000, 35,000, 40,000, 45,000, or 50,000.

[0047] Preferably, the compound of formula (I) and formula (II) is further reacted with a compound having a capping substituent to cap to obtain a compound of the following structure or a mixture thereof:

[0048] wherein R 14 is R1or a capping substituent; R 15 is R1or a capping substituent, R 14 and R 15 at least one of which is a capping substituent;

[0049] M represents a C2-C50 substituent, and the alkyl group in the above substituent can be further interrupted by a hydroxyl group, an oxygen atom, a carbonyl group, an epoxy group, an oxacycloalkyl group, or a benzene ring.

[0050] 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.).

[0051] In a preferred embodiment, the capping substituent is selected from * represents the connecting site of the group.

[0052] In a preferred embodiment, M is selected from wherein n1 is an integer from 1 to 20 (e.g., 1, 2, 3, 4, 5, 8, 10, 12, 14, 16, 18, 20, etc.), and * represents the connecting site of the group.

[0053] Preferably, the benzoyl formate compound is any one of the following compounds:

[0054] R in compound 8 is selected from methyl or

[0055] wherein n is an integer from 1 to 20.

[0056] The preparation method of the benzoyl formate compound as described above provided in the present application is not particularly limited, and different preparation methods can be selected according to different raw material compounds of general formula (II) or general formula (III). The benzoyl formate compound is obtained by reacting the compound of general formula (I) with the compound of general formula (II) or general formula (III).

[0057] Preferably, the molar ratio of the hydroxyl groups in the compound of formula (I) and the compound of formula (II) or (III) 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.

[0058] Preferably, the reaction of the compound of formula (I) and the compound of formula (II) or (III) is carried out under weakly basic conditions.

[0059] Preferably, the reaction of the compound of formula (I) and the compound of formula (II) or (III) is carried out at a temperature of 80-180°C (for example 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C) for a time period of 4-12h (for example 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h).

[0060] In the present application, the reaction of the compound of formula (I) and the compound of formula (II) or (III) can or can not be carried out in the presence of a solvent, and the type of solvent used is not particularly limited, provided that it is capable of dissolving the starting materials and does not adversely affect the reaction. Preferably, the solvent used in the reaction is selected from any one or a combination of at least two of xylene, m-dichlorobenzene or N,N-dimethylformamide.

[0061] Preferably, the ethylenically unsaturated photopolymerisable compound is selected from the group consisting of compounds having one or more ethylenic double bonds, esters of ethylenically unsaturated carboxylic acids with polyols or polyepoxides.

[0062] Preferably, the ethylenically unsaturated photopolymerisable compound is selected from the group consisting of alkyl acrylates, alkyl methacrylates, hydroxyalkyl esters, epoxyalkyl esters, (meth)acrylamides, N-substituted (meth)acrylamides, unsaturated carboxylic anhydrides, unsaturated esters, vinyl ethers, isocyanurates, N-vinyl heterocyclic compounds, acrylic acid, methacrylic acid, unsaturated fatty acids such as linolenic acid or oleic acid. Preferably, the unsaturated carboxylic acid is acrylic acid and methacrylic acid. The polyol can be an aromatic, aliphatic or cycloaliphatic polyol. Examples of aromatic polyols are hydroquinone, 4,4-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, a linear phenol-formaldehyde resin or a phenol-formaldehyde resin A. In another aspect of the present application, the ethylenically unsaturated photopolymerisable 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.

[0063] Preferably, the (a) component in the photocuring composition accounts for 0.5-10% by weight of the composition, for example 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0064] In the present application, the (b) component in the photocuring composition accounts for 2-99.5% by weight of the composition, for example 2%, 5%, 8%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90% or 95% and the like.

[0065] The photocuring composition described in the present application can contain other photoinitiators (d) in addition to components (a) and (b). The photocuring composition of the present application can also be optionally added with organic and / or inorganic auxiliaries (c) commonly used in the art, including but not limited to pigments, leveling agents, dispersants, curing agents, surfactants or solvents and the like, which are obvious to those skilled in the art. In addition, sensitizers can also be added to the composition for compounding use without negatively affecting the application effect of the composition.

[0066] In a second aspect, the present application also provides the use of the photocuring composition as described above in paints, inks, adhesives or photoresists.

[0067] Compared with the prior art, the present application has the following beneficial effects:

[0068] The benzoyl formate compound of the present application has excellent solubility, the sensitivity of the photocuring composition containing the same is not reduced compared with the prior art small molecule, and the hardness of the product is improved under LED curing. DETAILED DESCRIPTION

[0069] The technical solutions of the present application are further illustrated by specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

[0070] Preparation Examples

[0071] Examples 1-3:

[0072] The present example provides a preparation method of compounds 1-3, and the reaction schematic flowchart of the preparation is shown as follows:

[0073] Preparation of compound 1:

[0074] (1) In a 1 L four-necked flask, add aluminum trichloride 109.8 g and dichloroethane 350 mL at room temperature, 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 oxalyl chloride (1b) dropwise. After the addition is completed, continue to stir at this temperature for 1 h. Then add 30 g of diphenyl sulfide (1a) dropwise. The addition is completed in 30 min. After the addition is completed, remove the ice bath, and stir naturally as the temperature rises. Track the reaction by HPLC. When the content of the intermediate (monosubstituted) is less than 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 it is neutral, and concentrate the organic phase to obtain the crude product. Recrystallize the crude product from methanol / dichloroethane to obtain the product 40 g of light yellow solid (HPLC 99.15%, yield 69.3%).

[0075] Use 1 The structure of the intermediate 1c is characterized by H-NMR, and the results are as follows:

[0076] 1 H-NMR (deuterated chloroform, 500 MHz): 7.99-8.01 (4H, d), 7.45-7.48 (4H, d), 3.98 (6H, s).

[0077] (2) In a 100 mL four-necked reaction flask, add 36 g of the above (1c), 5.3 g of compound (1d), and 1 g of potassium acetate. Vacuumize the system, and when the pressure drops to -0.095 MPa, start stirring and heat. Keep the internal temperature at 115 °C and stir for 6 h. Track the reaction by HPLC. When the reaction is completed, cool the system to room temperature. Pour the reaction solution into 250 mL of dichloromethane. Wash the organic layer with water until it is neutral. Collect the organic phase, and concentrate to obtain the crude product, which is a yellow liquid 37 g. Purify by column chromatography (n-hexane: ethyl acetate = 4:1 by volume) to obtain the product 16 g of light yellow liquid (compound 1) (HPLC 97.12%).

[0078] Use 1 The structure of the compound 1 is characterized by H-NMR, and the results are as follows:

[0079] 1 H-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).

[0080] Preparation of compound 2:

[0081] (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%).

[0082] use 1 The structure of intermediate 2c was characterized by H-NMR, and the results are as follows.

[0083] 1 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).

[0084] (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%).

[0085] use 1 The structure of compound 2 was characterized by H-NMR, and the results are as follows:

[0086] 1 ¹H-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).

[0087] Preparation of compound 3:

[0088] Into a 100 mL four-necked flask, 36 g of (1c), 27.2 g of (2c) and 10.6 g of compound (1d), 2 g of potassium acetate were added, the system was vacuumed, when the pressure dropped to -0.095 MPa, the stirring was started and the temperature was raised, the internal temperature was kept at 115°C for 6 h, the reaction was tracked by HPLC, after the reaction was completed, the system was cooled to room temperature, the reaction solution was poured into 250 mL of dichloromethane, the organic layer was washed with water until it was neutral, then the organic phase was collected, concentrated to obtain a yellow liquid 69 g of crude product, purified by column chromatography (n-hexane: ethyl acetate = 4:1) to obtain a yellow liquid (compound 3) 16.1 g (HPLC 97.02%).

[0089] The compound 3 was prepared by the following reaction process: 1 The structure of compound 3 was characterized by H-NMR, and the results were as follows.

[0090] 1 H-NMR (deuterated chloroform 500 MHz): 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).

[0091] It should be noted that different ratios of raw materials and different reaction conditions will result in mixtures containing different amounts of compound 1, compound 2 and compound 3 in actual reactions, but these compounds are effective photoinitiators. In addition, under certain reaction conditions, compound 1 and compound 3 can further react to obtain initiators with higher molecular weight.

[0092] Example 4-5

[0093] The present embodiment provides a method for preparing compounds 4-5, and the reaction process is as follows:

[0094] Preparation of compound 4:

[0095] (1) Into a 500 mL four-necked flask, 34 g of diphenyl ether (2a), 29.3 g of aluminum chloride and 150 mL of dichloroethane were added at room temperature, the stirring was started, the system was cooled in an ice water bath, when the internal temperature dropped to -5-0°C, 26.9 g of methyl oxalyl chloride (1b) was added dropwise, after the addition was completed, the temperature was kept at -5-0°C for 1 h. After the addition was completed, the ice bath was removed and the temperature was naturally raised, the reaction was tracked by HPLC, when the content of raw material (diphenyl ether) was less than 5%, the reaction was stopped, the reaction solution was poured into 150 mL of 1% hydrochloric acid solution, the organic layer was separated, the organic layer was washed with water until it was neutral, then the organic phase was concentrated to obtain a yellow solid product (4c) 44.7 g (HPLC 97.47%, yield 87.3%).

[0096] Using 1 The structure of intermediate 4c was characterized by H-NMR, and the results were as follows:

[0097] 1 H-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).

[0098] (2) 25.6 g of the above (4c), 160 g of compound 2d (weight average molecular weight 321), and 1 g of potassium acetate were added into a 250 mL four-necked reaction flask, the system was vacuumed, when the pressure dropped to -0.095 MPa, the stirring was started and the temperature was raised, the internal temperature was kept at 115°C for 6 h, the reaction was tracked by HPLC, after the reaction was completed, the system was cooled to room temperature, and the reaction solution was poured into 250 mL dichloromethane, the organic layer was washed with water until it was neutral, then the organic phase was collected and concentrated under reduced pressure to obtain the product, which was a yellow liquid (compound 4) 53.5 g (HPLC determination showed that the content was 95.12%), and the weight average molecular weight was 547.

[0099] Preparation of compound 5:

[0100] (1) 109.8 g of aluminum chloride and 350 mL of dichloroethane were added into a 1 L four-necked flask at room temperature, the stirring was started, the system was cooled in an ice water bath, when the internal temperature dropped to -5-0°C, 80.7 g of methyl oxalyl chloride (1b) was added dropwise, after the addition was completed, the temperature was kept at -5-0°C for 1 h. Then 27.4 g of diphenyl ether (2a) was added dropwise, and the addition was completed in 30 min, after the addition was completed, the ice bath was removed, and the natural temperature was raised for stirring, the reaction was tracked by HPLC, when the content of intermediate (monosubstituted) was less than 2%, the reaction was stopped, the reaction solution was poured into 300 mL of 1% hydrochloric acid solution, the organic layer was separated, the organic layer was washed with water until it was neutral, and the organic phase was concentrated to obtain a crude product, which was recrystallized from methanol / dichloroethane to obtain a yellowish solid product (5c) 39.2 g (HPLC determination showed that the content was 98.27%, and the yield was 71.2%), and the weight average molecular weight was 921.

[0101] Using 1 The structure of intermediate 5c was characterized by H-NMR, and the results were as follows:

[0102] 1 H-NMR (deuterated chloroform, 500 MHz): 8.09-8.11 (4H, d), 7.14-7.16 (4H, d), 3.99 (6H, s).

[0103] (2) In a 250 mL four-necked flask, 34 g of the above (5c), 160 g of compound 2d (weight average molecular weight 321), 1 g of potassium acetate were added, the system was vacuumed, when the pressure dropped to -0.095 MPa, the stirring was started and the temperature was raised, the internal temperature was kept at 115°C for 6 h, the reaction was tracked by HPLC, after the reaction was completed, the system was cooled to room temperature, the reaction solution was poured into 250 mL dichloromethane, the organic layer was washed with water until it was neutral, then the organic phase was collected and concentrated under reduced pressure to obtain the product, which was a yellow liquid (compound 5), 90.0 g (HPLC determination showed that the content was 94.36%).

[0104] Example 6

[0105] Preparation of compound 6:

[0106] In a 1 L four-necked flask, 36.7 g of the above acyl chloride and 350 mL of dichloroethane were added at room temperature, the stirring was started, the system was cooled in an ice-salt bath, when the internal temperature dropped to -5-0°C, 20 g of anhydrous ethanol was added dropwise, the early exothermic gas emission was obvious, the dropping speed and tail gas absorption were controlled well. After the addition was completed, the system was stirred at room temperature for 1 h, the reaction was tracked by HPLC, when the content of the raw material was less than 1%, the reaction was stopped, the organic phase was concentrated to obtain the crude product, which was recrystallized from methanol / dichloroethane to obtain the product (compound 6) as a yellow solid, 36.1 g (HPLC determination showed that the content was 98.77%, the yield was 93.5%).

[0107] The compound 6 was prepared by the method of Example 6. 1 The structure of compound 6 was characterized by H-NMR, and the results were as follows:

[0108] 1 H-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).

[0109] Example 7

[0110] Preparation of compound 7:

[0111] In a 250 mL single-necked flask, 34.0 g of the above carboxylic acid and 148 g of tert-butyl alcohol were added at room temperature, the stirring was started, after the mixture was uniformly mixed, 2 ml of concentrated sulfuric acid was added, the temperature was raised to 90°C, the reaction was kept for 4 h, the reaction was tracked by HPLC, when the content of the raw material was less than 1%, the reaction was stopped, the organic phase was concentrated to obtain the crude product, which was recrystallized from methanol / dichloroethane to obtain the product (compound 7) as a white solid, 40.5 g (HPLC determination showed that the content was 99.17%, the yield was 89.5%).

[0112] The compound 7 was prepared by the method of Example 7. 1H-NMR was used to characterize the structure of compound 7, and the results were as follows:

[0113] 1 H-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).

[0114] Example 8

[0115] Preparation of compound 8:

[0116] In a 100 mL single-neck flask, 35 g of the above (1c), 23.2 g of TCM101, and 1 g of potassium acetate were added and uniformly mixed. The system began to warm up, and when the external temperature rose to 110°C, the stirring was started. The system was vacuumized, and when the pressure dropped to -0.095 MPa, the external temperature was maintained at 110°C and stirring was carried out for 4 h. HPLC was used to track the reaction, and when the raw material (1c) was less than 1%, the reaction was stopped. The system was cooled to room temperature, and the reaction liquid was poured into water. Dichloromethane was used for extraction, and the organic phase was combined. 1 g of activated carbon was added to the organic phase, and stirring was carried out for 2 h. Filtration and concentration were carried out to obtain 40.0 g of yellow liquid (compound 8). The weight average molecular weight was measured to be 502.

[0117] Examples 9-40

[0118] Referring to the methods of Examples 1-8, by selecting raw materials and controlling the amount of reaction raw materials, initiators with different structures can be obtained, as shown in Table 1. Some of the nuclear magnetic characterization data of the compounds are shown in Table 2.

[0119] Table 1

[0120] Table 2

[0121] Further, the compounds of formula (I) and formula (II) are further reacted with compounds with different substituents to cap and obtain compounds, and specific implementations are as follows: Example 41

[0122] R 14 , R 15 is methoxy or group, the asterisk represents the connection site of the 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.

[0123] In 100 mL single neck flask, add above (5c) 34 g, 20 g polypropylene glycol-400, 11.6 g TCM101, potassium acetate 1 g, mix well, then the system starts to warm up, when the external temperature rises to 110°C, open the stirring, the system is vacuumized, when the pressure drops to -0.095 MPa, keep the external temperature 110°C for 2 h, after the incubation, further improve the vacuum degree of the system to 200-300 Pa, GPC tracking reaction, when the product weight average molecular weight > 1000, stop the reaction, the system is reduced to room temperature, add 1 g activated carbon to the reaction liquid and stir for 2 h, filter to get sticky yellow liquid 59.0 g (compound 41), the weight average molecular weight is measured to be 1822.

[0124] Example 42

[0125] In 100 mL single neck flask, add above (5c) 34 g, 20 g polypropylene glycol-400, 11.6 g TCM101, potassium acetate 1 g, mix well, then the system starts to warm up, when the external temperature rises to 110°C, open the stirring, the system is vacuumized, when the pressure drops to -0.095 MPa, keep the external temperature 110°C for 2 h, after the incubation, further improve the vacuum degree of the system to 200-300 Pa, GPC tracking reaction, when the product weight average molecular weight > 1000, stop the reaction, the system is reduced to room temperature, add 1 g activated carbon to the reaction liquid and stir for 2 h, filter to get sticky yellow liquid 59.0 g (compound 41), the weight average molecular weight is measured to be 1822.

[0126] Example 43

[0127] R 14 , R 15 is methoxy or group, the asterisk represents the connection site of the 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.

[0128] In 100 mL single neck flask, add above (5c) 34 g, 20 g polypropylene glycol-400, 11.6 g TCM101, potassium acetate 1 g, mix well, then the system starts to warm up, when the external temperature rises to 110°C, open the stirring, the system is vacuumized, when the pressure drops to -0.095 MPa, keep the external temperature 110°C for 2 h, after the incubation, further improve the vacuum degree of the system to 200-300 Pa, GPC tracking reaction, when the product weight average molecular weight > 1000, stop the reaction, the system is reduced to room temperature, add 1 g activated carbon to the reaction liquid and stir for 2 h, filter to get sticky yellow liquid 59.0 g (compound 41), the weight average molecular weight is measured to be 1822.

[0129] Example 44

[0130] In a 250ml single-neck flask, 35g of the above (1c), 14g of polyethylene glycol-200, 9.3g of TCM101, 1g of potassium acetate were added, and after mixing, the system began to warm up. When the external temperature rose to 110°C, the stirring was started, the system was vacuumized, and when the pressure dropped to -0.095MPa, the external temperature was kept at 110°C for 2h. After the incubation was over, the vacuum degree of the system was further increased to 200-300Pa, and the reaction was tracked by GPC. When the weight average molecular weight of the product reached the predetermined value, the reaction was stopped, the system was cooled to room temperature, 1g of activated carbon was added to the reaction liquid, and stirred for 2h. Then, the product was obtained by filtration, which was a yellow viscous liquid 60.0g (compound 44), and the weight average molecular weight was measured to be 10306.

[0131] Example 45

[0132] In a 250ml single-neck flask, 35g of the above (1c), 14g of polyethylene glycol-200, 9.3g of TCM101, 1g of potassium acetate were added, and after mixing, the system began to warm up. When the external temperature rose to 110°C, the stirring was started, the system was vacuumized, and when the pressure dropped to -0.095MPa, the external temperature was kept at 110°C for 2h. After the incubation was over, the vacuum degree of the system was further increased to 200-300Pa, and the reaction was tracked by GPC. When the weight average molecular weight of the product reached the predetermined value, the reaction was stopped, the system was cooled to room temperature, 1g of activated carbon was added to the reaction liquid, and stirred for 2h. Then, the product was obtained by filtration, which was a yellow viscous liquid 60.0g (compound 44), and the weight average molecular weight was measured to be 10306.

[0133] Example 46

[0134] In a 250ml single-neck flask, 35g of the above (1c), 14g of polyethylene glycol-200, 9.3g of TCM101, 1g of potassium acetate were added, and after mixing, the system began to warm up. When the external temperature rose to 110°C, the stirring was started, the system was vacuumized, and when the pressure dropped to -0.095MPa, the external temperature was kept at 110°C for 2h. After the incubation was over, the vacuum degree of the system was further increased to 200-300Pa, and the reaction was tracked by GPC. When the weight average molecular weight of the product reached the predetermined value, the reaction was stopped, the system was cooled to room temperature, 1g of activated carbon was added to the reaction liquid, and stirred for 2h. Then, the product was obtained by filtration, which was a yellow viscous liquid 60.0g (compound 44), and the weight average molecular weight was measured to be 10306.

[0135] Example 47

[0136] R 14 、R 15 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.

[0137] In a 250 mL single neck flask, 34 g of (5c) above, 60 g of polyethylene glycol-300, 1 g of potassium acetate were added, mixed well, and the system started to warm up. When the outside temperature reached 110°C, the stirring was started, the system was vacuumed, and when the pressure dropped to -0.095 MPa, the outside temperature was kept at 110°C for 2 h. After the temperature holding was finished, the vacuum degree of the system was further increased to 200-300 Pa, and the reaction was tracked by GPC. When the weight average molecular weight of the product was > 1000, the reaction was stopped, the system was cooled to room temperature, the reaction solution was poured into water, dichloromethane was used for extraction, the organic phases were combined, dried and filtered, 22 g of triethylamine was added to the system, and the temperature was lowered to 0°C. Then 20 g of acryloyl chloride was added dropwise, and after the dropwise addition was finished, the system was naturally warmed up. The reaction was carried out at room temperature for 6 h. After the reaction was finished, the reaction solution was poured into water, dichloromethane was used for extraction, the organic phases were combined, 1 g of activated carbon was added to the organic phase, stirred for 2 h, filtered and concentrated to obtain 45.0 g of a viscous yellow liquid (compound 47), and the weight average molecular weight was measured to be 1900.

[0138] Example 48

[0139] R 14 , R 15 is methoxy or group, y is an integer of 1-10, n is an integer of 1-20, and z is an integer of 1-10.

[0140] The difference between Example 48 and Example 47 is that the mother nucleus raw material of Example 48 is (1c), and the weight average molecular weight of compound 48 is 2138.

[0141] Example 49

[0142] R 14 , R 15 is methoxy or group, y is an integer of 1-10, n is an integer of 1-20, and z is an integer of 1-10.

[0143] In a 250 mL single neck flask, 35 g of the above (1c), 60 g of polyethylene glycol-300, 1 g of potassium acetate were added, and the system was heated to 110°C. When the temperature reached 110°C, the stirring was started, and the system was vacuumized. When the pressure dropped to -0.095 MPa, the temperature was kept at 110°C and the stirring was continued for 2 hours. The vacuum was further increased to 200-300 Pa, and the reaction was tracked by GPC. When the weight average molecular weight of the product was greater than 1000, the reaction was stopped. The system was cooled to room temperature, and the reaction solution was poured into water. The dichloromethane was used to extract the product. The organic phase was combined, dried, filtered, and then desolventized. The residue was transferred to a 500 mL four-neck flask, 15 g of acrylic acid and 150 g of toluene were added to the system, and 1 g of tetraethyl titanate was added dropwise after stirring. The reaction was continued at reflux for 4 hours. After the reaction was completed, the reaction solution was poured into water, and dichloromethane was used to extract the product. The organic phase was washed with water once and with acid once. 1 g of activated carbon was added to the organic phase, and the stirring was continued for 2 hours. The product was filtered and concentrated to obtain 47.0 g of a viscous yellow liquid (compound 49), and the weight average molecular weight was measured to be 2156.

[0144] Example 50

[0145] R 15 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.

[0146] The difference between Example 50 and Example 49 is that the chain extender of Example 50 is polypropylene glycol-300, and the molar addition amount is 2.0 eq. Compound 50 is obtained, and the weight average molecular weight is 2068.

[0147] Example 51

[0148] The difference between Example 51 and Example 50 is that the mother nucleus raw material of Example 51 is ethyl diphenyl ether ketone acid, and the weight average molecular weight of compound 51 is 1960.

[0149] Example 52

[0150] R 15 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.

[0151] In a 250 mL single neck flask, 35 g of the above (1c), 60 g of polyethylene glycol-300, 1 g of potassium acetate were added, and the system was heated after being mixed uniformly. When the external temperature reached 110°C, the stirring was started, and the system was vacuumized. When the pressure dropped to -0.095 MPa, the external temperature was maintained at 110°C and the stirring was continued for 2 h. After the temperature maintenance, the vacuum degree of the system was further increased to 200-300 Pa, and the reaction was tracked by GPC. When the weight average molecular weight of the product was greater than 1000, the reaction was stopped, and the system was cooled to room temperature. The reaction liquid was poured into water, extracted with dichloromethane, and the combined organic phase was dried and filtered. Then the system was cooled to 0°C, and 16 g of ethyl isocyanate was added dropwise. After the dropwise addition was completed, the system was naturally warmed, and the reaction was continued at room temperature for 4 h. After the reaction was completed, the reaction liquid was poured into water, extracted with dichloromethane, and the combined organic phase was stirred with 1 g of activated carbon for 2 h, filtered and concentrated to obtain 55.0 g of a viscous yellow liquid (compound 52) with a weight average molecular weight of 1890.

[0152] Example 53

[0153] R 15 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.

[0154] The difference between Example 53 and Example 52 is that the mother nucleus raw material of Example 53 is methyl biphenyl ketone acid, and the weight average molecular weight of compound 53 is 1820.

[0155] Example 54

[0156] R 15 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.

[0157] The difference between Example 54 and Example 53 is that the mother nucleus raw material of Example 54 is methyl diphenyl ketone acid, and the weight average molecular weight of compound 54 is 1850.

[0158] Performance evaluation

[0159] 1. The application performance of the initiator was evaluated by preparing an exemplary photocuring composition (i.e., photosensitive resin composition, mass parts).

[0160] Table 3 Photocuring composition

[0161] E201: Bisphenol A epoxy acrylate (Changzhou Qiangli Electronic New Material Co., Ltd.) ACMO: Acryloyl morpholine (Runao Chemical Industry)

[0162] TMPTA: trimethylolpropane triacrylate

[0163] PEGDA: polyethylene glycol diacrylate

[0164] BYK307: leveling agent (BYK, Germany)

[0165] Initiator A: [4-(4-methoxyoxalyl-phenylsulfanyl)-phenyl]-oxo-acetic acid methyl ester

[0166] Initiator B: 2-(9,9-dimethoxyxanthene-2-yl)-2-oxo-acetic acid ethyl ester

[0167] Initiator C: Initiator MBF

[0168] Initiator D: Initiator 754.

[0169] 2. Performance evaluation method

[0170] (1) Solubility evaluation

[0171] The solubility of initiator A: [4-(4-methoxyoxalyl-phenylsulfanyl)-phenyl]-oxo-acetic acid methyl ester (IGM), initiator B: 2-(9,9-dimethoxyxanthene-2-yl)-2-oxo-acetic acid ethyl ester (IGM) and the photoinitiator provided by the example in propylene glycol methyl ether acetate was tested respectively, and the results are shown in Table 4 below.

[0172] Among them, the test method of solubility is: under the condition of room temperature 20±0.5℃, add appropriate amount of 6110: TMPTA=1:1(mass ratio) photocuring monomer as solvent in a 250mL glass beaker, take 0.5g of test sample and add it into the solvent, stir and mix for 20min, observe with naked eye whether there is undissolved sample. If the solution is clear, continue to add 0.5g of the sample to be tested, stir and mix for 20min, until there is undissolved substance, stop adding the sample, record the data and calculate the solubility of the sample according to the following formula:

[0173] Table 4

[0174] (2) Curing performance evaluation

[0175] The photocuring composition was stirred and mixed under LED (light source 405nm) lamp, and the material was taken on PET template and rolled to form a film with a film thickness of about 50μm. The film was exposed under mercury lamp (100%, 1m / min, 1140mJ / cm 2 ) and the curing condition of the composition was observed. The photosensitivity was evaluated according to the following standard:

[0176] 1, oil, not solid

[0177] 2, surface oil, primer cured

[0178] 3, surface tack, heavy fingerprints after hand touch

[0179] 4, nearly dry to the touch, slightly tacky, light fingerprints after hand touch

[0180] 5, fully cured, smooth surface, no fingerprints after hand touch

[0181] The hardness of the cured film after curing was evaluated according to the B method of GB T 6739-1996 standard:

[0182] The test results are shown in Table 5:

[0183] Table 5 Test Results

[0184] The absorption wavelength of the compositions of Comparative Examples 3 and 4 did not meet the light source requirements, did not cure, and could not be evaluated.

[0185] (3) Migration Test

[0186] The initiator was respectively prepared into a 1 x 10 -5 mol / L solution with ethanol as the solvent, the maximum absorption wavelength and the absorbance A1 were determined by a UV 3010 ultraviolet spectrophotometer, and the molar extinction coefficient was calculated by formula (1): c = A / ε x b (1) R = 100 x c / c1 (2)

[0187] The formulations of Table 1-2 Evaluation Examples and Comparative Example 1 were fully cured, 0.05 g of the cured film of the above photocuring composition cured under a high-pressure mercury lamp was weighed, and was respectively immersed in 30 g of ethanol, and after being placed at room temperature for 24 h, the same volume of the immersion liquid was taken and the absorbance A2 at the maximum absorption wavelength was measured by an ultraviolet spectrophotometer. The concentration of the photoinitiator migrated out of the three cured films was calculated by formula (1), and the concentration value of the photoinitiator (1) was taken as the reference benchmark, and the relative migration rate of various photoinitiators was calculated by formula (2).

[0188] In the above formula, c is the relative concentration (mol / L), c1 is the relative concentration of the photoinitiator (1), A is the absorbance, ε is the molar absorption coefficient (L / mol-cm); b is the sample cell thickness (cm); R is the relative migration rate. The test results are shown in Table 6.

[0189] Table 6

[0190] Experiments show that the initiator of the present application has no migration and high initiation efficiency, especially in the case of molecular weight improvement, the initiation efficiency is basically not affected, the hardness of the product after curing is obviously improved compared with the existing initiator, and it has the characteristics of low migration.

[0191] The applicant declares that the photocuring composition and its application of the present application are illustrated by the above examples, but the present application is not limited to the above examples, that is, it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific mode, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A photocurable composition comprising the following components: (a) at least one benzoyl formate compound; (b) at least one ethylenically unsaturated photopolymerizable compound; (c) at least one photoinitiator; (d) optionally, at least one further additive; wherein the benzoyl formate compound is represented by the following general formula (I) or (II) or (III): ###0001### (I) (II) (III) A is a single bond, O, S or CR2R3, R2, R3 independently of one another represent hydrogen, C1-C8 straight-chain or branched alkyl; R1 is hydroxyl, halogen or C1-C4 alkoxy; R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent. R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent. R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent. wherein the benzoyl formate compound is a compound represented by general formula (I) and a compound represented by general formula (II) or general formula (III) is reacted: wherein R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent. Y represents hydrogen, halogen, nitro, C(=O)C(=O)-OR1, C1-C 10 straight-chain or branched alkyl, C3-C 10 alkylcycloalkyl, C4-C 10 alkylcycloalkyl or C4-C 10 cycloalkylalkyl, or the group -CH2- in said C1-C 10 straight-chain or branched alkyl, C3-C 10 alkylcycloalkyl, C4-C 10 alkylcycloalkyl or C4-C 10 cycloalkylalkyl is replaced by O, N, S, aryl or C(=O); R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent. R4, R6, R5, R7 independently of one another represent hydrogen, fluorine, hydroxyl or a linear or branched alkyl group having 1 to 6 carbon atoms, the hydrogens of which can be further replaced by fluorine; 10 R4, R6, R5, R7 independently of one another represent hydrogen, fluorine, hydroxyl or a linear or branched alkyl group having 1 to 6 carbon atoms, the hydrogens of which can be further replaced by fluorine; R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent. Y1, Y2independently of one another denote a bond, C1-C 20 straight-chain or branched alkyl, C3-C 20 alkylcycloalkyl, C4-C 20 alkylcycloalkyl or C4-C 20 cycloalkylalkyl, or the -CH2- in said C1-C 20 straight-chain or branched alkyl, C3-C 20 alkylcycloalkyl, C4-C 20 alkylcycloalkyl or C4-C 20 cycloalkylalkyl is replaced by O, N, S, Si, aryl, bisphenolfluorene or C(=O); R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent. R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent. R a C1-C4alkyl, or C1-C4alkyl interrupted by an oxygen atom, an oxiranyl group, an oxetanyl group, a phenyl ring; 80 C1-C4alkyl, or C1-C4alkyl interrupted by an oxygen atom, an oxiranyl group, an oxetanyl group, a phenyl ring; 80 C1-C4alkyl, or C1-C4alkyl interrupted by an oxygen atom, an oxir R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent. R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent.

2. The photocurable composition according to claim 1, wherein, The compound of general formula (II) or general formula (III) is selected from the group consisting of ethylene glycol, polyethylene glycol, diethylene glycol, propylene glycol, polypropylene glycol, glycerol, pentaerythritol, pentatonic alcohol, cyclohexanehexol, 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, 2,2-dimethyl-1,3-propanediol, 1,3-cyclohexanediol, 3,4-dihydroxyphenethyl alcohol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, tetramethylethylene glycol, 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-ethanediol, 2-ethyl-1,3-hexanediol, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, 3,3'-oxybis(propane-1-ol), 2,2-dimethyl-3-hydroxypropanoic acid neopentyl glycol ester, triethylene glycol, 3,7-dioxa-1,9-nonanediol, 4,8-dioxadecan-1,11-diol, diethylene glycol, 4-oxaheptanediol, 1,4-dioxane-2,3-diol, 3-(2-hydroxyethoxy)propane-1,2-diol, 6H-benzofuro[3,2-C][1]benzopyran-3,9-diol, (3S,3aR,6S,6aR)-hexahydrofuro[3,2-b]furan-3,6-diol, phenol diol, pentaethylene glycol, (9Ci)-octahydro-4A,8A-(methyloxymethane)naphthalene-2,7-diol, 3,3'-[1,4-butanediylbis(oxy)]bis-1,2-propanediol, 3,3'-oxybis-1,2-propanediol, 2-ethyl-2-[(2-hydroxyethoxy)methyl]-1,3-propanediol, bis(2-hydroxypropyl) ether, drospirenone 5,5'-diol, 2-methyl-3,4-chromen- diol, 2,5-tetrahydrofuran diol, propylene glycol salicylate, octaethylene glycol, 5-methoxy-2-methoxy-tetrahydro-pyran-3,4-diol, 2,2-dimethyl-hexahydro-1,3,4,8-tetraoxacyclopenta(a)indene-5,7-diol, 6-methoxy-2-phenyl-hexahydro-pyran(3,2-D)(1,3)dioxane-7,8-diol, chrom-4,6-diol, R represents hydrogen, methyl or methyl further substituted by halogen, n1 is an integer from 1 to 10; m1, n2 are independently an integer from 0 to 10 and m1 + n2 = 10.

3. The photocurable composition according to claim 1 or 2, wherein, The benzoyl formate compound has any one of the following structures: wherein R is a R9group or 10 is a R9group or group, the wavy line represents the point of attachment of the group, R 11 Y is a group of formula (Y1) or (Y2) group, R 12 R9is a group or group, the wavy line represents the point of attachment of the group, R 13 Y is a group of the formula R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent.

4. The photocurable composition according to any one of claims 1 to 3, wherein, The benzoyl formate compound is any one of the following compounds: R in compound 8 is selected from methyl or R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent.

5. The photocurable composition according to any one of claims 1 to 3, wherein, R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula (I) and a compound represented by general formula (II) or (III) and further capping with a compound having a capping substituent. R8, R9 independently of one another represent hydrogen, C1-C8 alkyl or C1-C8 alkyl interrupted by an oxygen atom, an epoxy group, an oxiranyl group, a phenyl ring; m and n independently are integers from 0 to 20, and m and n are not simultaneously 0; p is 0 or 1 ; q is an integer from 1 to 8; or the benzoyl formate compound is obtained by reacting a compound represented by general formula ( ​ ​ 6. The photocurable composition according to any one of claims 1-3, wherein, The compound of general formula (I) is reacted with a compound of general formula (II) or (III) and further reacted with a compound having a capping substituent to obtain a compound of the following structure or a mixture thereof: wherein R 14 is R1or an endcapping substituent; R 15 is R1or an endcapping substituent, R 14 and R 15 at least one of which is an endcapping substituent; ​ ​ 7. The photocurable composition according to claim 6, wherein, the end-capping substituent is selected from * represents the point of attachment of the group; Preferably, M is selected from ​ 8. The photocurable composition according to any one of claims 1 to 7, wherein, ​ 9. The photocurable composition according to any one of claims 1-8, wherein, ​ ​

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