TW201226422A - Crosslinkable liquid benzophenone (meth) acrylate - Google Patents

Abstract

The present invention relate to a crosslinkable liquid benzophenone (meth)acrylate, which can be used in photocurable coatings, not only acts a Norrish II type photoinitiator but also causes the (meth)acrylate ester subject to radical polymerization in the presence of tertiary amines, and can acts as a reactive monomer. Moreover, It will not migration when it is polymerized and can be used as packaging material for contacting food and as a bimedical materials.

Description

201226422 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a liquid crosslinkable diphenyl sulfonium (meth) acrylate, which itself has a photoinitiator And the number of oxime (eq) of the reactive monomer can make it

Diphenyl hydrazine _ is one of the most widely used low molecular weight photoinitiators in terms of good surface curing properties, solubility, and radical polymerization of fluorenyl acrylate. The monofunctional photoinitiator migrates from the cured product to the surface and volatilizes into the atmosphere μ due to its low molecular weight, photodegradation products produced during photocuring, and photocuring. The odour of this type of volatiles and its health hazards limit its use in biological materials: food and pharmaceutical packaging materials. One of the ways to effectively solve this problem is to use a photoinitiator having a functional benzophenone derivative. Compared with the conventional photoinitiator, the photoinitiator of the functional benzophenone derivative has the advantages of: having a large molecular weight and having crosslinkability, and being capable of reducing the initiator molecule and its photoproducts from the cured product. It migrates to the surface, thus solving the problem of harmful small molecule precipitation and taste. ~ North teeth, 2008 Master's thesis University of Chemical Technology (OF: Deming's) ,, benzophenone derivatives of synthesis and properties of the polymerization photoinitiator ,, a paper, the authors propose: (1) phenyl -2 Yue , 4-diisocyanate (TDI) and hydroquinone (HQ) as carriers to link 4-mercaptobenzophenone (HMBP) to synthesize a higher molecular weight difunctional benzophenone photoinitiator HMBP-TDI- HQ-TDI-HMBP (abbreviated as HTHTH); (2) 4-hydroxybenzophenone (HBP), toluene-2,4-diisocyanate (TDI), 4,4,-dihydroxybenzophenone ( DHBP) is used as a raw material to synthesize another high molecular weight benzophenone photoinitiator HBP-TDI-DHBP-TDI-HBP (abbreviated as HTDTH) through two-step reaction; (3) 4-hydroxydibenzophenone (HBP) , toluene-2,4-diisocyanate (TDI), didecylethanolamine (dmea) as a raw material, a two-step reaction to synthesize a benzophenone photoinitiator HBP with an amine-based co-initiator on the main chain -TDI-D MEA (referred to as HTD). The results show that the synthesized three large molecular weight diphenyl 201226422 ^ derivative photoinitiators compared with diphenyl hydrazine (Bp): (1) the light absorption efficiency is faster than the 'polymerization rate and the conversion rate is higher: (2) The structure of the amine-based co-initiator introduced into the main chain without amine initiator is different for light bursting; (3) the initiator with amine on the main chain, the UV suede length: benzene shell is significantly larger Red turn, extraction study age, same strip = lower: the amount of amine-based photoinitiator taken out of the stroke is much smaller than the benzophenone field). This approach provides a synthetic route for low mobility photoinitiators. In the Chinese Journal of Synthetic Chemistry (Chinese J〇umai of Synthetic Chemis = (= 3 = 36, Vn, 2003)), although it is proposed to prepare a benzoate material based on benzophenone The preparation method of the method is to dissolve and filter, and then to be washed and dried to obtain the mouth and mouth, which is solid, which is inconvenient to use and has been processed and complicated. U.S. Patent No. 5,900,472 discloses a polymer-copolymerized diphenyl hair-raising agent which has no precipitation problem in the UV-curing composition and contains 2 to 6 f ^ (meth)acrylic acid g group, which has solidification in the claw. Double efficacy, in which diphenyl sulfonate can be part of the network ^: to matrix, reducing migratory (migratiQn) and extracts (drinking the tactile structure may contain sulfur, nitrogen, phosphorus or dentate In the composition of the cyclization, the weather resistance is deteriorated, it is easy to yellow, and it is not easy to be correlated. In order to solve the above-mentioned shortcomings of the prior art, the same is true for the benzophenone (E0^^ research 'discovered by the diphenyl? After reacting with Ethylene B (IV) and then ((3) Acrylic acid is acetated with a methyl group), propylene is used to complete the liquid crosslinkable diphenyl phthalate of the present invention. Use, the lowest price ====味TM-based - coffee modified light f invention content] 201226422 The purpose of the invention is to provide a liquid crosslinkable benzophenone (f-based), which is not only itself It has the characteristics of refinement and functional groups of reactive monomers. The invention relates to liquid crosslinkable diphenyl (tetra) (meth) acrylate; when the photocurable coating is prepared, the cured product obtained has a refractive index of up to 157 to have a polymerizable functional group, and the lin is involved in fine The reaction can increase the crosslink density.

The liquid conjugated benzophenone (methyl) acetoacetate of the present invention has a functional ratio of methyl group to acid 〜 〜4, by adjusting its epoxy bake and propylene bromide The quantity ' can be adjusted to be hydrophilic or hydrophobic, so it can be synthesized according to the use, hydrophilic or hydrophobic, and can not only be used for the oil-based UV coating, but also the environmentally-friendly water-based coating which is paid more attention to. The cross-linked bis- 同 同 同 ? ? ? 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于When used*, there is a migration phenomenon which can be used for materials in contact with food or application of biomedical materials. The liquid crosslinkable benzophenone (meth) acrylate of the present invention is as follows The general formula (I) means:

〇

Wherein R1 to R4 represent Η or the base of the following formula (11): 0

X y but at least one of R1 to R4 is a group of the formula (Π); in the above formula (II), 'R represents Η or -CH3, and x20, yg〇, but the parent and the 乂 are not 0, and X+y =l~20, 201226422 or both, the same as %i:::""":|; urgent::, propyl vinegar or both. ~ text U methacrylic acid S or propylene system ^ Dimethyl) propylene axis, after the preparation reaction, and (methyl group = £ = ^ or propylene propylene) addition f bis-diphenyl benzene, benzamidine, oxybenzophenone, 4,4,_二Μ=基—本甲酉同,2-经基-4-辛酉等' but not limited to these. 兮工-同,2,2',4,4'-tetra-based Diphenyl species or a combination of two or more

0

The liquid crosslinkable ketone ketone (meth) acrylate of the present invention is made of 201226422 epoxy epoxide' firstly added with a hydroxybenzophenone derivative and ethylene oxide (E 〇 propylene (PO) In the reaction, an intermediate of the following formula (ΠΙ) is obtained: or

(III) wherein R1 to R4 represent fluorene or a group (IV) X y of the following formula (IV); but at least one of R1 to R4 is a group of the formula (jV); and xg 〇, yg 〇, but X and y are different It is 〇' and x+y=1~2〇. R' represents Η or 〇CnH2n+1 and η represents an integer of 1-20.

Pnvt describes the addition reaction of woven biphenyl brib organism with silk _Q) and/or propylene oxide (PO) to make hydroxybenzophenone derivatives in alkaline ring production = strong base in NaOH or KOH The compound is present in the presence of τ at a high pressure; the reaction is in the middle, and in the presence of a suitable solvent and a phase transfer catalyst, it is reacted with an ethylene bromide & === azide gas (Ρ0) gas. Epoxy Ethylene (4) and Ethylene Cepide = can be used alone or in combination, and ε〇 and ^) in the intermediate after addition can be randomly arranged or block arranged. Ηη. „!~ At room temperature to 2〇 (the optimum temperature is 80~ loo B at rC, the operating pressure can be up to 50~2000 psi, the most suitable solvent for the pressure is inert solvent, for example 曱Benzene, diterpene benzene, trimethyl ketone (D-foot), dimethyl-hard (DMSO) and quaternary, but not secret. Solution _ can be used for single thieves can also be mixed with two-diameter Μ. 201226422 The phase transfer catalyst which can be used is exemplified by a quaternary salt, a base (d), a base group, a diethyl group, a sulfonyl or a triethylbenzylammonium bromide, but not limited thereto, and the like can be used alone. It can also be mixed with two _. It is f廄bi = _~_, preferably _wt% or acetic acid, etc. The reaction can also add an appropriate amount of antioxidant to prevent = = _ agent ( -grade antioxidants) and the number of liquid crosslinkable benzophenone (meth) propylene's oxy-ethene (EO) and/or propylene-propylene (P) added to the scaly antioxidant J invention It can be controlled by the control of the addition of the epoxy bismuth oxime relative to the force; the relative amount of such reactants is controlled by the skilled person. The present invention will not be described in detail in the present invention. The intermediate represented by the above formula (ΠΙ) is reacted with (meth)acrylic acid to form a liquid crosslinkable diphenyl compound of the present invention. Fg^基). This--the reaction can be carried out under normal pressure or reduced pressure, and the organic solvent can be used for the dehydration of water. To prevent the occurrence of gelation reactions. ^ The reaction can be carried out under heterogeneous conditions, and __ should be selected at a low temperature (if the reaction can be carried out below 1 〇, for example, it can be carried out in, for example, methyl or para-acids. Examples of aromatic organic solvents are benzene and hydrazine. Benzene and diterpene benzene, etc.; I; for example, there are positively burned, cyclohexan and n-glybden, free ^ ί-tiQ) 'J&ASa(MEHQ ' O-Methyl-hydroquinone) > ^ Basic or Dibutyl permethyto (BHT). The liquid crosslinkable benzophenone (meth) acrylate vinegar of the present invention is not only simple in process, easy to obtain raw materials, but also has no problem of residual taste of the product: and due to both photoreactive functional groups and polymerization Reactive functional group, so it has the function as a monomer for the acrylic monomer in UV-curable coatings, and also has the function of as a photoinitiator at the same time. 'It can not only participate in the photocuring process to produce cross-linking reaction, but also apply. In photocurable coatings, 'the number of raw materials used in photocurable coatings can be simplified, and the surface of the polymer after photocuring has no odor and does not cause migration phenomenon. Therefore, it can be used for materials or biomedical materials that are in contact with food. ^ Application. Example 1 Synthesis of 2-(ethyleneoxy) 2_4-decyloxybenzophenone propionate Equipped with an air inlet, a mechanical stirrer, a water trap, a reflux condenser and a heating system Add 2_(ethylene oxide) 2_4_methoxybenzophenone to the liter reaction flask (the compound of the above formula (III) wherein R is a decyloxy group and is an integer of 2 and y is 0) 410.8 1.3 moles, 102.96 grams of acrylic acid (1.43 mole), 7.13 grams of hydrazino acid (0.052 mole), 280 grams of solvent benzene, 0.40 gram of 4-methoxyphenol (1000 ppm) and nitro alum Gram (5〇ppm). The resulting reaction mixture was heated to reflux for 9 hours, and the amount of water was collected and the acid value of the content was measured to judge whether or not the reaction was completed. After the reaction is completed, after cooling the reaction mixture to room temperature, the organic layer is neutralized with an appropriate amount of hydrazine aqueous sodium hydroxide solution and neutralized 'to remove the acid present in the reaction mixture' and then scrambled, and then left to stand. The aqueous layer and the organic layer were washed with an appropriate amount of 20% aqueous sodium chloride solution and allowed to stand to remove the aqueous layer. After the organic layer was finally taken out, it was concentrated under reduced pressure at 9 〇 to 92 to remove the solvent and residual water. Finally, after filtration, the product was obtained as a dark fading liquid. The product weight: 435.94 g, yield: 90 63%. The physicochemical properties of the obtained product were as follows: Refractive index (n25d): 1.56780 (tested by ATAGO refractometer, κχ_5000α instrument, tested at 25t). Viscosity (#4; 25 ° C; lOQrpm): llOOcps (tested by Brookfield DV-E viscometer, #4 rotor, at 25t). Example 2 Synthesis of 2_(Exetyloxy)2·4·octyloxybenzophenone j acrylate In one, an air inlet, a mechanical agitator, a water trap, a reflux condensation thief and a heating system were provided. 1 liter of reaction flask is added with ethoxylated) 2_4_octyloxy 201226422 bisbenzophenone _ (in the above formula (111), R is an octyloxy group, and χ is an integer of 2, and y is a compound of 0) 382.0 g (1.0 m〇ie), acrylic acid 79.2 g (li mole), methyllithic acid 5.49 g (〇.〇4 mole), solvent toluene 310 g, 4-methoxyphenol 0.389 g (500 ppm) and Nitrobenzene 0.0389 grams (50 ppm). The resulting reaction mixture was heated to reflux for 1 hour and 5 hours, and the amount of water was collected and the acid value of the content was measured to judge whether or not the reaction was completed. After the reaction is completed, after cooling the reaction mixture to room temperature, the organic layer is washed with an appropriate amount of hydrazine aqueous sodium hydroxide solution and neutralized to remove the acid present in the reaction mixture, then scrambled, and then left to stand. The aqueous layer and the organic layer were washed with an appropriate amount of 20% aqueous sodium chloride solution, and the aqueous layer was allowed to stand still. After the organic layer was finally taken out, it was concentrated under reduced pressure at 9 Torr to 92 ° C to remove the solvent and residual water, and finally, the title product was obtained as a dark brown liquid by filtration, product weight: 398.89 g, yield: 91.49 %. The physicochemical properties of the obtained product were as follows: Refractive index (n25d): 1.53610 (tested by ATAGO refractometer, RX-5〇〇〇a instrument, under 25 〇). Viscosity (#4; 25 ° C; lOOrpm): 128 cps (tested by a Brook field DV-E viscometer '#4 rotor' at 25 ° C). Example 3 Synthesis of 2,4-(Exoethoxy)4·diphenylfluorenone acrylates 1 liter equipped with an air inlet, mechanical stirrer, moisture trap, reflux condenser and heating system 2,4-(Exetyloxy)4_dibenzophenone was added to the reaction flask (wherein R' in the above formula (III) is Η, X is an integer of 2, and y is a compound of ruthenium) 351.0 g (0.9 Mole), acrylic 136.08 g (1.89 mole), mercaptosulfonic acid 7.41 g (0.054 mole), solvent benzene 270 g, 4-decyloxyphenol 0.38 g (500 pm) and nitrobenzene 0.038 g (50 ppm) . The resulting reaction mixture was heated to reflux for 10 hours, and the amount of water was collected and the acid value of the contents was measured to judge whether or not the reaction was completed. After the reaction is completed, after cooling the reaction mixture to room temperature, the organic layer is washed with an appropriate amount of an aqueous solution of 1% by weight of sodium hydroxide and neutralized to remove the acid present in the reaction mixture, and then mixed, and then allowed to stand for 10 201226422 The aqueous layer was removed. The organic layer was washed with an appropriate amount of 20% aqueous sodium chloride solution, and the aqueous layer was allowed to stand. After the organic layer was finally taken out, it was concentrated under reduced pressure at 90-92 t: to remove solvent and residual water, and finally, after filtration, the title product was obtained as a dark brown liquid, product weight: 384.19 g, yield: 85.72 %. The physicochemical properties of the obtained product were as follows: Refractive index (n25d): 1.55320 (by ATAGO refractometer, RX_5〇〇〇a instrument 'at 25: (under test). Viscosity (#4; 25 C; lOOrpm): 2766 cps (Tested by Brookfield DV-E viscometer, #4 rotor, at 25 ° C.) # Example 4 2,2,4,4 -(Exetyloxy)8-diphenylformamide Acrylic Synthesis 2, 2, 4, 4, - (Extended ethoxy V benzophenone) in a 1 liter reaction flask equipped with an air inlet, mechanical stirrer, moisture trap, reflux condenser and heating system Ketone (in the above formula (111), R is Η 'X is an integer of 2, and y is a compound of ruthenium) 299.0 g (0.5 mole), acrylic acid 155.52 g (2.16 mole), methyl acid acid 8.229 g (0.06) Mole), solvent 300 g of toluene, 0.57 g (750 ppm) of 4-decyloxyphenol and 0.038 g (50 ppm) of nitrobenzene. The resulting reaction mixture was heated under reflux for 1 hour, and the amount of water was collected. The acid value is used to judge whether the reaction is completed. After the reaction is completed, the reaction mixture is cooled to room temperature, and the organic layer is 10% in an appropriate amount. The sodium solution is washed and neutralized to remove the acid present in the reaction mixture, and then stirred, and then the aqueous layer is removed. The organic layer is washed with an appropriate amount of 20% aqueous sodium chloride solution to remove the aqueous layer. After the layer, it was added under the condition of 90-92 〇C, and concentrated to remove the solvent and residual water. Finally, the title product of the dark-labeled liquid was obtained by filtration, the product weight: 331.07 g, and the yield: 81.34%. The physicochemical properties of the obtained product were as follows: Refractive index (n25d): 1.53909 (tested by ATAG0 refractometer, RX-5000a instrument, tested at 25 ° C.) Viscosity (#4; 25. (: ; i〇〇rpm): 2502 cps 11 201226422 (tested by Brookfield DV-E viscometer, #4 rotor, tested at 25 ° C.) Example 5 Synthesis of 4-(extended ethoxy) 2 - dibenzophenone acrylate Add 4-(extended ethoxy)r dibenzophenone to the 1 liter reaction flask of the air inlet, mechanical stirrer, moisture trap, reflux condenser and heating system (in the above formula (III), R' is Η, X is an integer of 2, and y is a compound of bismuth) 286.0 g (1.0 mole), Acrylic acid 79.2 g (1.1 mole), mercaptosulfonic acid 5.486 g (0.04 mole), solvent toluene 330 g, 4-methoxyphenol 0.525 g (750 ppm) and nitrobenzoquinone. 35 g (5 〇 ppm) . The resulting reaction mixture was heated to reflux for 11.0 hours, and the amount of water was collected and the acid value of the contents was measured to judge whether or not the reaction was completed. After the completion of the reaction, after cooling the reaction mixture to room temperature, the organic layer was washed with an appropriate amount of 10% aqueous sodium hydroxide solution and neutralized to remove the acid present in the reaction mixture, and then stirred to remove the aqueous layer. The organic layer was washed with an appropriate amount of 20% aqueous sodium chloride solution, and the aqueous layer was allowed to stand still. After the organic layer was finally taken out, it was concentrated under reduced pressure at 90 to 92 °C to remove solvent and residual water. The title product of the yellow liquid was obtained by filtration, and product weight: 300.06 g. Yield: 88.25%. The physicochemical properties of the obtained product were as follows: Refractive index (n25d): 1.57627 (tested by ATAGO refractometer, RX-5000a instrument, at 25 Torr). Viscosity (#4; 25 ° C; lOOrpm): 930 cps (tested by Brook field DV-E viscometer, #4 rotor, under 25. 〇). Example 6 Synthesis of 4-(propenyloxy)r diphenylhydrazine acrylate in a 1 liter reaction flask equipped with an air inlet, mechanical stirrer, moisture trap, reflux condenser and heating system Add 4_f acetamidine (in the above formula (10), R is Η, X is an integer of 0, and y is an object) 200 g (0.78 m〇le), acrylic acid 62 g (0 86 m〇le), 曱^ 12 201226422 12 grams of sulfonic acid (0.126 mole), 200 grams of solvent, 0.3 gram of 4-decyloxybenzene (630 ppm) and 0.03 grams of nitrobenzene (63 ppm). The resulting reaction mixture was heated to reflux for 7.0 hours' and the amount of water was collected and the content acid value was measured to judge whether or not the reaction was completed. After the reaction was completed, after cooling the reaction mixture to room temperature, the organic layer was washed with an appropriate amount of 10% aqueous sodium hydroxide solution and neutralized to remove the acid present in the reaction mixture, and then stirred to remove the aqueous layer. The organic layer was washed with an appropriate amount of 20% aqueous sodium chloride solution, and the aqueous layer was allowed to stand still. After finally removing the organic layer, it is at 90 to 92. (: Concentration under reduced pressure, solvent and residual water were removed, and finally the title product of the yellow liquid was obtained by filtration, product weight: 213.4 g. Yield: 88.18%. The physicochemical properties of the obtained product were as follows: (n25d): 1.57869 (tested by ATAGO refractometer, rx_5000cx instrument at 25 ° C.) Viscosity (#4; 25 ° C; lOOrpm): 3246 cps (by Brook field DV-E viscometer ' #4 rotor, Tested at 25 ° C.) Test Example 1 The liquid crosslinkable diphenyl fluorenone (mercapto) acrylate of the present invention was mixed with benzophenone (BP 丨 as a composition as shown in the following table). Thereafter, it was applied to a substrate, and a comparison of drying properties was carried out at a drying speed shown in Table 1. Equipment: UV irradiation machine (4) 5.2.3; light source instrument company) Operating conditions: coating with a wire rod After being placed on the ABS board, it is passed through a UV irradiator. 13 201226422表1

Control group (g) The present invention (g) AgiSyn 28842) (PETIA) 70 70 AgiSyn 28333) (DPGDA) 18 12 Product of Example 3 -9 Diphenyl fluorenone (BP) 3 AgiSyn 0014) (tertiary amine) 9 9 Drying speed (m/min) 40 40 Drying energy (mJ/cm2) 140 140 Test results Dry once and dry once 1) Compare the molar number such as benzophenone (BP) and fix the amount of AgiSyn〇〇1 . 2) AgiSyn2884 is a product of Xinlimei Technology Co., Ltd., which is a mixture of quaternary tetraol triacrylate and pentaerythritol tetraacrylate. 3) AgiSyn2833 is a product of Xinlimei Technology Co., Ltd., which is dipropyiene glycoacrylate (dipropyiene glyc〇1). Diacrylate) 4) AgiSyn 001 is a product of Xinlimei Technology Co., Ltd., an amine synergist

It is known from the experimental results that the liquid crosslinkable benzophenone (mercapto) acrylate of Example 3 can be used not only as a photoinitiator but also as a polymerizable monomer, and can replace the 4-injected double-g energy base. The raw material component is AgiSyn 2833 (DPGDA). Test Example 2 Liquid crosslinkable benzophenone (meth) acrylate and diphenyl ketone of the present invention

ϋΡ) The composition shown in the following Table 2 was blended with the composition 'and dried in the same manner as in Experimental Example 1 above. 4 thief 1 J 14 201226422 Table 2 A (g) B (g) AgiSyn2815υ (TPGDA) 70 70 AgiSyn 28302) (DPHA) 18 18 Product of Example 5 - 5.6 Dibenzophenone (BP) 3 AgiSyn 0013) ( Tertiary Amine) 7.2 7.2 AgiSyn2832 (2-PEA) 10 7.4 Drying Energy (mJ/cm2) 400 400 Test Results Dry once and dry once 1) Compare the molars such as benzophenone (BP) and fix AgiSyn 001 Dosage. 2) AgiSyn2815 is a product of Xinlimei Technology Co., Ltd., which is a tripropylene glycol dipropylene acid

3) AgiSyn 283 is a product of Xinlimei Technology Co., Ltd., which is dipentaerythritol hexaacrylate. 4) AgiSyn001 is a product of Xinlimei Technology Co., Ltd., which is known from the results of the test for amine synergists-;,^ " --only milk column" Wenshoukou J-crossed dibenzophenone (a can be used as a light-based acrylic acid, can be substituted. The raw material component of the early functional base Agi 8 = As described above, compared with the conventional photoinitiator II, the cross-linking of the diphenyl benzoate is the same as the (meth) propionate. The invention belongs to the acrylic monomer and can be cross-linked. Door <Special Health. (1) As Noci (10), Π type light = agent = contains, the structure and the number of bases can make it water-soluble; (4) ' (wrong is more convenient by increasing the oxygen Use; (5) _ ^ ^ ^ this A _ comparison, for liquid, UV hardening accounting money consumption ^ ^ can participate in cross-linking reaction, t, it can be used ^ food contact with the attack material or it, with Β ρ The odor ring structure is also a high refractive index acrylic/medical material; (6) contains benzene advantages.

Claims (1)

201226422 VII. Scope of application for patents: 1. Two kinds, the second kind of cross-linking _(曱基)_acid §, which is expressed by the following formula and formula Ci). (1) wherein R1 to R1 represent Η or the group of the following formula (H): -(-ο^Κ X but at least one of R1 to R1 is a group of formula (II); in the above formula ¢0, R represents Η or -CH3, and X20, yg〇, but χ盥 is not 0 at the same time, and x+y=l~20, /, y R' represents Η or 0CnH2n+1 and η represents an integer of 1 to 20. 2. Liquid crosslinkable benzophenone (methyl) as claimed in claim 1 Cyanate ester, which is used as a Norrish Type II photoinitiator. 3. Liquid crosslinkable diphenyl sulfonium (meth) acrylate as in claim 1 The ester is used as a polymerization-reactive monomer. 1 16 1 . The liquid crosslinkable benzophenone (meth) acrylate according to claim 1 of the patent application, which is obtained by the following intermediates (III) ) esterified with (meth)acrylic acid, 201226422 〇 R3 r2 (III) wherein R1 to R4 represent H or a group of the following formula (IV): x y (iv) However, at least one of R1 to R4 is a group of the formula (IV); and xgo, y$〇, but X and y are not 0 at the same time, and X+y=l~20. 17 201226422 IV. Designated representative map: (1) The representative representative of the case is: ( ). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 2