TW200305780A - Novel MORPHOLINOKETONE derivatives, and preparation process and uses of the same - Google Patents

Abstract

Disclosed herein are novel morpholinoketone derivatives of formula (I): wherein each of the substituents is given the definition as set forth in the Specification and Claims. Also disclosed are the preparation process of the derivatives, and their uses as a photoinitiator in photopolymerizable compositions.

Description

200305780 发明 Description of the invention (The description of the invention should state: the technical field to which the invention belongs' previous technology, content, implementation, and drawings are briefly explained] [明 户户 属 ^^ member 3 Field of the invention The present invention relates to a kind of A novel morpholinoketone derivative of morpholinoketone with a photoinitiator, and a preparation method and application thereof.

L · U Background of the Invention Compared with the traditional lithographic printing technology, UV curing printing technology has a wider range of applications. It can not only be applied to the manufacture of traditional lithographic ink 10, offset ink. , Letter press ink, flexo ink, gravure ink, silk screen ink, etc., can also be applied to printed circuit boards (printed circuit board), photoresist, solder mask (solder masker, also known as green lacquer), dielectric substrate 15 (dielectric substrate), etc. Generally speaking, the UV hardening process requires a binder, a photopolymerizable monomer, and a photoinitiator. The photoinitiator can polymerize the monomer in a short time of UV irradiation. Form polymer. The photochemical polymerization of unsaturated monomers and prepolymers is a commonly known method with a wide range of industrial applicability. US 3,661,614 discloses a radiation-curable, solvent-free printing ink composition which is generally composed of: (1) a pentaerythritol acrylate, methyl propionic acid, of about 20 wt% to 98 wt% Ester or itaconic acid ester (itaconte), (2) a halogenated aromatic, alicyclic 6 200305780 (about 2wt% to 80wt ° / 0), a photoinitiator of an aliphatic or aliphatic hydrocarbon, in which the element i Directly connected to the ring structure of aromatic and alicyclic compounds and the carbon chain of aliphatic compounds, and a colorant. US 4,672, 〇79 discloses a poly-5 polymerizable or polymerizable aromatic-aliphatic ketone, preferably a 2-hydroxy-2-methyl (4-ethenylpropane), that can be used as a light initiator for polymerization. Benzene) [2-hydroxy-2-methyl (4-vinylpropiophenone)], 2-Cyclo-2-methylfluorene- (1-methylethynyl) propanylbenzene (2-11 > ^ 〇 义; / -2-11161:] 171-;?-(1-methylvinyl) propiophenone), p-vinylbenzoylcyclohexanol, p- (l-methylethylpyrrolyl) benzidine -10 cyclohexanol (p- (l-methylvinyl) benzoyl-cyclohexanol) and the polymerization and polymerization products thereof, suitable as ethylenically unsaturated monomers and prepolymers A photoinitiator for photopolymerization. US 4,943,516 discloses a photosensitive thermosetting resin composition, which 15 comprises: (a) a photosensitive prepolymer containing at least two ethylenically unsaturated bonds in its molecular unit; (b)-a photoinitiator (C) a photopolymerizable vinyl monomer and / or an organic solvent as a diluent; (d) a fine powdery epoxy compound containing at least two epoxy groups in its molecular unit, And exhibit a limited solubility in the solvent to be used; and (e) 20 kinds of selective curing agent for epoxy resin. The photosensitive thermosetting resin composition was revealed to exhibit good imaging properties and sensitivity and provide a long storage life. When introduced to coating, exposure, development, and post-curing treatments, the photosensitive thermosetting resin composition can be formed to exhibit properties such as adhesion, insulation resistance, electrolytic corrosion resistance, and the like. 7 200305780发明, the invention explains a good solder mask pattern. US 4,582,862 discloses a photocurable colored composition comprising: (a) an olefinically unsaturated photopolymerizable binder, (b) a pigment at 5-60% by weight, and (c) 0.1- 20% by weight of a light initiator having the chemical formula (I) disclosed in the fifth case. In particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropan-1-one (2-methyl-1-[4- ( methylthio) phenyl] -2-morpholino-propane- 1-one (MMMP) has become a widely used photoinitiator, especially in pigmented UV systems, such as solder resist (solder) 10 masker) and UV ink. It has been reported that MMMP can provide good photospeed and mechanical properties without harming its non-yellowing nature.

MMMP However, when MMMP is used, it will have a bad odor problem due to the inherent volatile sulfur residues in the post-curing processing, which limits its industrial application. In particular, when MMMP is applied to UV inks or solder resists, it produces problems with mild to objectionable bad odors, which are caused by the photofragmentation of MMMP ) 4-methylthiobenzaldehyde, which has a volatile odor of 20. 8 200305780 发明 Description of the invention Because of the limited choice of available photoinitiators, users often must endure the bad smell of MMMP or use MMMP derivatives ^ {Luigi Angiolini et al.} Journal of Applied. Ploymer Scinece (1995), 55: 1477-1488; US 4,582,862 ^ US 5,145,885 > US 5 5,506,279, US 5,837,746, WO 96/20795, US 6,048,667), especially 2-benzyl-2 as disclosed in US 5,145,885 -Dibenzyl-2- (4-morpholinophenyl) butan-1- (1-benzyl-2-dimethylamino-l- (4-morpholinophenyl) -butan-1 -one, BDMB) As a replacement for MMMP.

For some pigment systems (such as Cyan pigments) that use MMMP and BDMB as the main light initiators, an excessive grinding process may be required to incorporate all the light initiators, which may lead to premature curing and cause One of the viscosity of the ink is increased or even gelled, so it is necessary to add a polymer stabilizer such as paraben 15 (MEHQ). However, this stabilizer will eventually slow down the speed of light. Furthermore, MMMP and BDMB tend to increase the viscosity of the inks produced ', which is not desirable for applications that require low viscosity, such as elastic letterpress. Therefore, based on the shortcomings of the prior art, there is a need to develop new substances that can be used as photoinitiators for photopolymerizable compositions. [Summary of the Invention] 200305780 Summary of the Invention Summary of the Invention Therefore, in a first aspect, the present invention provides a compound having the following formula (I): 5 5

Where Xι represents: Η, S, alkyl group), (I)

〇, Ν or NR (where R is a Ci < X2 means: H, S, 0, N or NR (where R is a CIA alkyl group), but with the condition that when χι and neither is H, χ1 === χ2; R means: a Cl-Cl2 alkylene group (Ci-C12 alkylene

gr〇UP) or a group of the formula-(CH2〇CH2) p-, where p is an integer from 1 to 4; 15 and R2 are individually represented: H, phenyl, or optionally Cl_Cl2 alkyl, C2-C12 alkenyl, Cl-Cl2 ^ oxy substituted by phenyl; R3 and R4 each represent a C1_C6 alkyl group which is optionally substituted by a hydroxyl group, or I and R4 together with The nitrogen atoms together form a cyclic group selected from the group

10 200305780 发明, description of invention

R5 represents: Η, F, Cl, Br, I, nitro, phenyl, Ci_Ci2 alkyl or CVCu alkoxy; when X or X2 is Η, k is 〇; when X1 or & is S K, 1 for ◦, ◦, or NR; k for 2 when X, or χ2 is N; m is an integer from 2 to 5; and when k is 1, η is one An integer from 1 to 20, and when k is 2, each of η and n2 is an integer from i 10 to 10. In one aspect, the present invention provides a method for manufacturing a compound of formula (I) as described above, comprising the steps of: making a compound of formula (II) and a compound of formula (II) The lactone compound reacts to form the compound of formula ⑴: (H0-R) s-X2 (ho_r \ x

(Π) where the definitions of R !, R2, R3, R4 and Rs are the same as those defined by the compounds of the above formula ⑴, where χι represents Η, S, 0, N or NR (where R is a cvCi2 15 200305780 (regulatory group), X2 means: H, S, 0, N or NR (where r is a Ci-Ci2 alkyl group), and s is 0 or 1, 5 but with the condition that when When X〗 and X2 are not Η, Xi = χ2, and s is 1; and when Xi or χ2 is Η, s is 0;

-^) q (HI) where q is an integer from 1 to 4. The lactone compound 10 having the chemical formula (in), which can be used in the method of the present case, is selected from the group consisting of: / 3-propiolactone, γ-butolactone (Δ-valerolactone and ε-caprolactone. Preferably, the lactone compound having the chemical formula (in) is e-caprolactone.

In a preferred embodiment, the method is performed in the presence of a tin-containing catalytic agent. Preferably, the method in this case is performed in the presence of n-butyl-tin tris (alkanoate) (SCAT-24). In a preferred embodiment, the compound of formula (π) used in the method of the present case is obtained by reacting a compound of formula (n,) 20 with a compound of formula (IV) Generated: 12 200305780 玖, description of the invention

(II,) means only, {7, 匸 1, ^, 1 or cyano, 2 indicates that Η, F, a, Br, I, or cyano, but only when Υι and Y2 are different Ηι, Υι R ,, xr, oh above

Where (IV) 10 X is an s group),

NH or NR (where R is a ^ 12 alkyl R 'definition is the same as that defined by the above chemical formula and formula ⑴; 15 when X is S, 0 or NR, R, and when H is R, R "Is r, 0H.

And when X is NH

The invention also encompasses the use of the compound of formula VII. For example, the inventor of the present case found that the compound of formula (I) can be used as a photoinitiator. Therefore, the compound of formula VII and the photopolymerizable monomer compound of the present invention can be formulated into a 20 photopolymerizable composition 'such as a printing oil black. Other objects, features and advantages of the present invention will be described in detail with reference to the following 13 200305780 玖, description of the invention

It will become apparent after the illustration and the illustration of the preferred embodiment. [Detailed description of the invention of the square package method H. 5 In order to overcome the bad odor problem of MMMP, the present invention attempts to modify the structure of the MMMP rafter by linking a polymerizable link to the methyl sulfur part of the MMMP, and has developed a The following chemical two compounds:

Where 10 (I) X! Means: Η, S, Ο, N or NR (where R is a Ci_c alkyl group),

X2 means: Η, S, Ο, N or NR (where R is an alkyl group), but with the condition that when χι and the heart are not Η, x1 = x2; R represents a C 丨 < 12 CKCi2 alkylene group or a group having a chemical formula of-(CH20CH2V, where p is an integer from 1 to 4;

Ri and R2 respectively represent: H, phenyl, or CVCi2 alkyl, c2-Ci2 alkenyl, optionally substituted with phenyl, 01-(: 12 alkoxy; 14 200305780 Kan, Zheng Yue The alkene 4 individually represents a Ci-C6 optionally substituted with a group " Human 4 together with the nitrogen atom attached thereto forms a cyclic group selected from the group: 'Ν Ν-ι. And Han 5 means: η, p, 0, ~, 1, nitro, benzyl, (:, -0, 2 alkyl or c ^ c, 2 alkoxy;

When χι or X2 is Η, k is 0; tXjX2 is S 10 15. When bribing or bribery, k is 1; when XistX2 is 2; m is an integer from 2 to 5; and ^ k is 1 k and 11 is an integer from 1 to 2G. When k is 2, η == ηι + η < 20, where a and z are each an integer from 1 to 10. In a preferred embodiment, m is 5. In a preferred specific example, R is a CA elongation group, a terbine ethyl group, or a chemical formula _ (cH2〇ch + or _CH2〇CH2CH2〇CH2 -The group represented by the formula. "R! And R2 are each a group selected from the group consisting of methyl, ethyl, propyl, phenyl-substituted methyl, and Phenyl-substituted propyl. In one preferred embodiment, U & are all 15 20 200305780 玖, invention illustrative group. In another preferred embodiment, Ri is phenyl-substituted methyl, and R2 is an ethyl group. In the specific example of the vehicle, R3 and R4 are each a group selected from the group consisting of methyl, ethyl, propyl, and methyl and ethyl. — A more specific example A, both feet 3 and R4 are fluorenyl. In another—a better specific example, R3 # & together with the nitrogen-Γ-

The atoms together form a \ _ / 0 group. In the specific example of early tuning, R5 is r Α, 10 " Cl.C6. In a more specific embodiment, R5 is fluorene. In a preferred embodiment, one of XjX2 is § ^ 0 and the other is H. In a more specific example, n is. In another more specific embodiment, the η system is 6. In a more specific example, one of Xll% X2 is 3 15 and the other is H, R is an ethylene group, the heart and the heart are each a methyl group, and R disk

^ The four nitrogen radicals to which one is linked are one and one, R5 is η, and m is $. In another preferred embodiment, one of χι and & is N, 糸 is Η, and the total of ... + "is preferably 6. 20 and in another: a more specific embodiment, Xl and & One of them is Ν, which is H, and R 'is an ethylenic group, and the other is methyl' R ^ R4 together with the connection with the atom. Atoms form 1 16 200305780 发明, invention description Γ ~ \ 一 Ν The ON ′ group R5 is Η, m is 5, and η + η2 == 6.

In another preferred embodiment, one of X and χ2 is NR (where R is a Ci_Cu alkyl group), and the other is η. In a more specific example, one of Xl and & is nch3 5, and the other is Η; is phenyl substituted fluorenyl, and & is ethyl • ', and R3 and & Is methyl. In another preferred embodiment, one of ^ and X2 is NQH5, and the other is H; Ri is phenyl substituted methyl, and R2 is ethyl; and Rs and I are both fluorenyl . The compound of formula (I) can be prepared by a method of 10 including the following steps: reacting a compound of formula (Π) with a lactone compound of formula (III) to form the compound of formula ⑴ Compound: (H〇-R) -χ2 (HO-R ^ -Xj

(II) The definitions of 15 Ri, R2, R3, R4 and Rs are the same as those defined by the above formula (I), where X represents: H, S, 0, N or NR (where R is a c) _c ] 2 alkyl group), X2 represents: H, S, 0, N or NR (where, w, r R is a cc 17 200305780 玖, description of the alkyl group of the invention), s is 0 or 1, but there is The condition is that when Xi and X2 are not Η, X1 == X2, and S is 1; and when Xi or X2 is Η, s is 0; —— 5 (ΙΠ)

Where q is an integer from 1 to 4. With regard to the compound of formula (Π), its preparation can be performed with reference to conventional methods, for example, the synthetic techniques disclosed in the aforementioned documents mentioned above, including Luigi Angiolini et al., Journal of Applied · 10 Ploymer Scinece (1995), 55: 1477-1488; US 4,582,862, US 5,145,885, US 5,506,279, US 5,837,746, WO 96/20795, US 6,048,667, and the like.

The lactone compound having the chemical formula (in), which can be used in the method of the present case, may be selected from the group consisting of: / 5-propiolactone 15, 7-butolactone , 5-valerolactone and ε-caprolactone. In a preferred embodiment, the lactone compound of formula (III) is ε-caprolactone. These lactone compounds are commercially available, for example, from DAICEL Chemical Co. 20 The advantages of using the lactone compound of formula (III) as a polymerizable chain source are: (1) the molecular weight of the product can be easily controlled, 18 200305780 玖, description of the invention (2) high pigment wetness, (3) high UV stability, (4) low toxicity (biodegradable), and (5) low viscosity. 5 The method in this case can use one which can be used in the chemical formula (III).

It is a catalyst for ring-opening polymerization of an ester compound. Catalysts suitable for the method of the present case are, for example, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate or other titanate-containing compounds , Stannous octoate, dibutyl-tin-oxide, dibutyl-tin-dilaurate, n-butyl-tin tris (alkanoate) or other organotin compounds, stannous chloride, stannous bromide or other stannous halide compounds (see US 6,037,393) 〇15 In a preferred embodiment, the method of the present invention is based on a tin-containing catalyst

Being carried out in the presence of the agent. In a more specific example, the method in this case is performed in the presence of n-butyl-tin tris (alkanoate) (SCAT-24). In a preferred embodiment, the compound of formula (II) used in the method of the present case is obtained by reacting a compound of formula (II ′) with a compound of formula (IV) Generated: 19 200305780 ridge, invention description

(II,) where the definitions of 3 Han4 and Rs are the same as those defined by the above chemical formula, 5

Yl means: 111, (: Bu Yi, 1, or cyano, Y2 means: H, F, CbBr, k ^^ |, but with the condition that when neither Y! Nor Y2 is Η, γ1 = γ2 where 10 X Is S'0 'or NR (where R is a Ci_c ^ group),

The meaning of R is the same as that defined by the above formula ⑴; and when X is S, 0, or NR, R, is H; and when χ is NH, 'R' 'is R'OH. With regard to the compound of formula (II,), its preparation can be performed with reference to conventional methods. For example, the compound of formula (II,) can be prepared by referring to the relevant disclosure of US 4,582,862, and according to the following synthetic route, Amine group is introduced into a corresponding aryl alkyl ketone compound: 20 200305780 玖 Description of the invention

R h! HNR3R4 > Y2

^ Where Hal represents halogen, and R 丨 to I, and Υι and \, ^ 'are the same as those defined by the aforementioned chemical formula (IΓ). In a preferred embodiment of the present invention, the chemical compound (Π) used is one in which one of Υι and y2 is Η, and the other is 有, and the other is Η ' And the other is? Or α. In another, preferred embodiment of the present invention, the compounds having the chemical formula (π,) are: compounds in which γ4γ2 are all compounds. 10 15. In a preferred embodiment of the present invention, the compound having the chemical formula (Π) is a group in which ~ and ^ are each a group selected from the group consisting of Group compounds: methyl, ethyl, propyl-substituted methyl and phenyl-substituted propyl. In a more specific embodiment, both & and ^ are methyl. In another more preferred embodiment, R is methyl substituted with ^, and & is ethyl. In a preferred embodiment of the present invention, the compound having the chemical formula (Π ′) is _ which among them are formed together with & together with a compound atom with a nitrogen group attached thereto. In the present invention, The other one is a better specific property, which is used to compound compounds with the formula (Π)-one of which & and & each separately-a selection 21 20 200305780 玖, the description of the invention comes from the following group Compounds of groups in the group: methyl, ethyl, propyl, and hydroxy-substituted propyl.

In a preferred embodiment of the present invention, the compound having the chemical formula (Π) is a compound in which & is η, f, Cl, Br, I, phenyl, or C ^ C6 alkyl. . In a more specific example, & is Η.

3 Compounds of formula (IV) are commercially available, for example, from BASF Corporation. In a preferred embodiment, the compound having the chemical formula 10 (IV) used in the present invention is hs (r, oh), wherein R is an ethylene group. In another preferred embodiment, the compound of formula (IV) used in the present invention is NH (R, 0H) 2, where R is an ethylenic group. In another preferred embodiment, the compound of formula (IV) used in the present invention is RNH (R'0H), wherein the ruler is a methyl or 15 ethyl group, and R is An ethene group.

In a preferred embodiment of the present invention, the compound having the formula (II,) used in the preparation method of the present case is a compound, wherein ya! One of Y2 is H, and the other is F, a, Br, or 1; Ri and R2 are each methyl; r3 and r4 together with the gas atom to which they are attached form a group; and R5 series Is Η; the compound of formula (IV) used in the preparation method of the present case is hs (r, 0h), where R 'is an ethylidene group; and, the thus-formed compound having the formula The compound of m is induced to react with the ε_caproine, and produces 22 20 200305780 Kan. The invention shows that one of χι and X2 is the compound s of formula (I), and the other is H. In another specific example of the invention, the compound having the chemical formula (η,) used in the error-making method of the present case is _ compounds, and one of .1 and Υ2 is Η, And the other is F, a, Br or: 'I and I are methyl groups respectively; 1 and the heart together with the nitrogen atom attached to it Γ ~ \ —N 〇

10 U forms a U group; and R5 is Η; the compound having the formula (IV) used in the preparation method of the present case is nh (r, oh) 2, and its R, which is an ethyl group Moreover, the compound of formula („) thus generated is introduced to react with the caprolactone phase to generate the compound of formula ⑴, where either of & and & is N , And the other is H; and _2 = 6.

In another preferred embodiment of the present invention, it is used in the preparation method of the present case. The compound of formula (2,) is a compound in which one of ΥΑΥ2 in 15 is H, and the other is Bufenfen or Gong, and Ri and R2 are each selected from the group consisting of Groups in methyl, ethyl, propyl, phenyl substituted methyl and phenyl substituted propyl; R3 and R4 are each fluorenyl, and Rs is H; used in the preparation method of this case The compound of formula (IV) is rnh (r, oh) 20 'wherein R is methyl or ethyl, and R is an ethylenic group; and' The compound thus formed has the formula (Π The compound) was induced to react with ε-caprolactam S 'to form the compound of formula ⑴, of which 23 200305780 发明, description of the invention

One of Xi and X2 is NR (R is methyl or ethyl), and the other is Η.

The invention also covers the use of the compound of formula (I). According to the present invention, the compound of formula (I) can be used as a photoiniator 5 and it does not cause the bad odor problem usually associated with MMMP. The polymerized composition does not have the problem of increased viscosity. Therefore, according to the available methodologies that are well known in the art, the compound of formula (I) according to the invention is formulated with the following components: photopolymerizable monomer compounds, photosensitizers 10, pigments Or dyestuffs, and other additives commonly used by those skilled in the art to prepare photopolymerizable compositions, such as oligomers, photosensitizers, and amines synergists) and other physical property modifiers. 15 The compound of formula (I) according to the present invention is expected to be used

It is used in various industrial applications, for example, in the industrial applications related to photo-initiators mentioned in the aforementioned previous documents. For example, the compound of formula (I) according to the present invention can be formulated in UV inks or coatings as a photoinitiator. The compounds of formula (I) according to the present invention are also expected to be used in combination with conventional photoinitiators, such as those disclosed in the aforementioned documents, especially disclosed in US 4,672,079 . The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only. 24 200305780 发明, Description of the invention < Example 1 > Synthesis of MMMP-3 and MMMP-6

This example illustrates how to synthesize a compound according to the present invention, such as 6-hydroxy-hexanoic acid 5- (5- {2- [4- (2-fluorenyl-2-morpholine-4-yl-propanonium ) Phenylsulfonyl] -ethoxycarbonyl} pentyloxycarbonyl) -pentyl ester (6-5 hydroxy-hexanoic acid 5- (5- {2- [4- (2-methyl-2-morpholin- 4-yl-propionyl) -phenylsulfanyl] -ethoxycarbonyl) -pentyloxycarbonyl) pentyl ester, MMMP-3) and 6-acyl-hexanoic acid 5- (5- {2- [4- (2-methyl-2-? Fluoroline-4-yl-propionyl) phenylsulfonyl] -ethoxycarbonyl} -tetrakis (pentyloxycarbo) -pentylsulfonyl (6-hydroxy-hexanoic acid 5- (5- { 2- [4- (2-methyl-2-10 morpholin-4-yl-propionyl) -phenylsulfanyl] -ethoxycarbonyl}-tetra (pentyloxycarbonyl) pentyl ester, MMMP-6) and their intermediates 1. [4 ( 2-hydroxyethylthio) -phenyl] 2-methyl-2-morpholinopropan-1-one (l- [4- (2-Hydroxyethylthio) -phenyl] -2-methyl-2-morpholino- propan-1-one, compound 2), the relevant synthetic pathway is shown below:

MMMP-3: n = 3 MMMP-6: η-6

The molecular weight of the synthesized product compound can be changed by adjusting the molar ratio of compound 2 to ε-caprolactone, as shown in MMMP-3 and 25 15 200305780 玖, description of the invention MMMP-6. A. Synthesis of 1- 丨 4 (2-Ethylethylthio;) _ phenyl] -2_methyl_2_morpholinylpropan-1-one (Compound 2): 〇

5 Place 94.8 g (1.21 mol) of mercaptoethanol and 600 ml of toluene in a 1-liter three-necked round bottom flask 'followed by 48.6 g (1.21 mol) of NaOH. The mixture was brought to reflux for 6 hours, at which point the water formed was collected by a Dean-Stark device. The toluene solvent was removed by distillation, and 10 250 ml of DMF was added to the solid cake. After the solution has cooled to room temperature, add 250 g at a time.

(0.93 mol) of 1- (4-fluorophenyl) -2-methyl-2-morpholinyl-1-acetone (Compound 1, prepared according to US Patent No. 4,5 82,862), and formed The mixture was heated under a nitrogen atmosphere at 50 ° C overnight. The mixture was cooled to room temperature, diluted with 1 liter of toluene, and washed with 15 water, 2% aqueous NaOH solution and brine Odne). The organic layer was separated and concentrated under vacuum to obtain a yellow viscous oil, which was further purified by recrystallization to yield an off-white 纟 〇ff-white 彡 crystal (90% yield, melting point: 62 -64 ° C). B. Synthesis of MMMP-3. 20 20 g of 200 g C.65 mol) of compound 2, 88.5 g of 6-caprolactone and 8 g of tin catalyst [trade name SCAT-24, purchased from Japan A total of 26 200305780 玖, invention description

Sankyo Organic Chemistry Co., Ltd.] was placed in a 500 ml three-necked round bottom flask equipped with a condenser and under a nitrogen blanket. The mixture was heated to 80-85 ° C for 2 hours. Add 44.3 g of ε-caprolactone and 4 g of SCAT-24 to the above flask every 40 minutes, do 4 times, and maintain the temperature for another hour. The resulting mixture was washed with water, 2% aqueous NaOH solution and brine. The organic layer was concentrated under vacuum to obtain a light tan oil (398 g, 95% yield). Measured properties of the title compound 10 NMR (CDC13, 400 Μ: ζ): δ 8.46 (d, / = 8.4 Hz, 2 Η), 7.29 (d? J = 8.4 Hz? 2 H), 4.26 (t, J-6.9 Hz ? 2 H)? 4.02 (t? J = 6.5 Hz? 6 H), 3.65 (t, J = 3.8 Hz, 4 H), 3.60 (t, / -6.5 Hz, 3.20 (t, / = 6.9 Hz, 2 H), 2.53 (t, J = 3.8 Hz, 4 H), 2.25-2.30 (m, 9 H), 1.51-1.65 (m, 20 H), 1.3 (M · 42 (m, 10 15 H) , 1.27 (s, 6 H). IR (KBr): 3501, 2942, 2865, 1741, 691,

1588, 1563, 1475, 1402, 1364, 1158, 1120, 1093, 980, 882, 761 cm-1 o According to the 1H NMR data obtained, the n value of the obtained product compound is 3. Relative to the molecular weight of MMMP is 279, the molecular weight of the obtained product compound is about 650. C. Synthesis of MMMP-6: MMMP-6 was synthesized in the same manner as MMMP-3, except that 354 g instead of 88.5 g of ε-caprolactone was used to form a light yellow brown paste (light tan paste) (97% yield). 27 200305780 发明, Description of the invention Properties measured by the title compound: 'H NMR (CDC13, 400 MHz): δ 8.46 (d, J = 8.4 Hz 2 H), 7.29 (d, J = 8.4 Hz? 2 H), 4.26 (t, J = 6.9 Hz, 2 H), 4 〇2 (t, J = 6.5 Hz, 12 H), 3.65 (t, J = 3.8 Hz, 4 H), 3.60 (t, y ~ 5 6.5 Hz, 3.20 (t, = 6.5 Hz, 2 H), 3.20 (t, J = 6.9 HZ? M, z H), 2.53 (t, J = 3, 8 Hz, 4 H), 2.25-2.30 (m, 18 H ), 1 · 51-1 · 65 (m 40 H), 1.30-1.42 (m, 20 H), 1.27 (s, 6 H). Based on the 1H NMR data obtained, the oral value of the obtained compound is 6 'And the molecular weight is about 9 6 0. 10 D · The physical properties of MMMP-3 and MMMP-6 are compared. Compared with MMMP-6, it is a paste at room temperature, and MMMP-3 is a light paste at room temperature. Amber liquid. The coagulation point of MMMP-3 is about C 'and it will not be cured after standing for 30 days under it. The following table ^ lists the physical properties comparison of MMMP-3 and MMMP-6. MMMP -3 MMMP-6 Color * (pure) 4.5 4.8 Viscosity at 70 ° F 1200 cps Viscosity of paste at 100 ° F 423 cps 1743 cps Density 1.082 1.092 * Calculated in Gardner units. ≪ Implementation 2 > This example illustrates how to synthesize another compound according to the present invention, that is, compound 5, and its intermediate product ^ {4acid_ (2_hydroxyj-ethyl) -20 octadecyl] fluorenyl- 2-morpholinyl-1_acetone (1_ {4- [1313- (2-11 > ^ 〇 灯-? &Quot;-ethyl) -amino]} _ 2-methyl-2_morpliolino-l-propanone, compound 4) 28 200305780 发明, Description of the invention 'The relevant synthetic pathway is as follows:

A · [bis- (2-light-r-ethyl) -amine]} Synthesis of 2-methyl-2-morpholinylacetone (compound 4): 5 10.0 g (0 · (037 mo1) of fluorophenyl) -2-methyl-2-morpholinyl-1-acetone and 58.9 g (0.56 mol) of dithanolamine

Place in a 100 ml three-necked round bottom flask and heat to 150x: for 24 hours. The resulting solution was cooled, diluted with 100 ml of ethanol, and then washed with water and brine. The solvent was removed by a rotary evaporator to obtain a yellow oil (11 g, 88% yield). B · Preparation of Compound 5: 11.0 g (0.033 mol) of compound 4, 17.9 g of ε-caprolactone and 1.8 g of tin catalyst (SCAT-24) were placed in a container equipped with a condenser under nitrogen A 100 ml three-necked round bottom flask under protection. The mixture 15 was heated to 80-85 ° C for 1.5 hours. Every 30 minutes, a mixture consisting of 90 g of ε-caprolactone and 0.9 g of SCAT-24 was added to the above-mentioned flask, and made 3 times. Maintain the temperature for another hour. Reaction mixing 29 200305780 玖, invention description The objects were then cooled to room temperature and diluted with 200 ml of methylbenzyl. After that, it was washed with water and brine, and the organic layer was concentrated under vacuum to obtain a viscous oil (29.8 g, 90% yield). Based on the 1H NMR data, it is estimated that 5 + co- ^ of compound 5. 5 < Example 3 >

This example illustrates how to synthesize another compound according to the present invention, 3690, namely 2-Oxpenone, 2-{{4- [2- (dimethylamino) -1-oxy-2- (Phenylfluorenyl) butyl] phenylbutanylaminoethyl ethyl ester (2-〇 乂 60311〇116,2-{{4- [2- (dimethylamino) -l-oxo-2- (phenylmethyl) butyl] phenyl } -10 methylamino} -ethyl ester) [Note: 2-oxepanone is ε-canetezine] and its intermediate product 369N, which is 2- (dimethylamino) -1- {4-[(2 -Hydroxyethyl) fluorenylamino] phenylphenyl 2-phenylfluorenyl-1-T_ (2- (Dimethylamino) -1-{4-[(2-hydroxyethyl) methylamino] phenyl} -2-phenylmethyl- 1 -butanone), the relevant synthetic pathway is shown below:

1. ε-caprolactone 2. Scat-24

Wherein η may be an integer from 1 to 10, preferably 1-6. Α. 2- (dimethylamino) _1- {4-[(2-hydroxyethyl) methylamino] phenylbenzene 2-30 15 200305780 玖, description of the invention phenylmethyl-1-butanone ( Synthesis of compound 369N):

Add 100 g of 2- (difluorenylamino) -1- (4-fluorophenyl) -2-phenylmethyl_1-butanone (2-dimetliylamino-l- (4-fluorophenyl) -2- plienylmethyl-l-butanone) (compound 369F, prepared according to the disclosure 5 of US 5,077,402) and 600 g of 2- (methylamino) ethanol [2- (methylamino) ethanol] in a 2L reaction flask, After homogeneous stirring, purge 5 times with nitrogen. After warming to 150 ° C and uniformly stirring for 3 hours, 50 g of the compound 369F was added to the reaction flask, and the reaction was continued for 2 hours. Then, 50 g of the compound 369F was added to the reaction flask, and the reaction was continued for 10 hours for 4 hours. . Finally, after the reaction temperature was reduced to 40 ° C, 470 g of the remaining 2- (methylamino) ethanol was distilled out under the conditions of 48 ° C and 2.0 torr, and then 200 g of toluene and 400 g of Water, remove the water layer after uniform stirring, add 200 g of water, and stir evenly for 10 minutes. Then remove the water layer and remove toluene to obtain compound 369N. 15 Measured properties of the title compound:

! H NMR (CDC13, 200 MHz): δ 8.35 (d, J = 9.0 Hz, 2 H), 7.20-7.27 (m9 5 H)? 6.66 (d, J = 9.0 Hz, 2 H), 3.82 (t, J = 6.0 Hz, 2 H), 3.56 (t, J = 6.0 Hz, 2 H), 3.22 (s, 2 H), 3.06 (s, 3 H), 2.38 (s, 6 H), 1.40-2.10 ( m, 2 H), 0.72 (t, J = 7.4 Hz, 3 H). 20 B. 2-Oxpenone, 2-{{4- [2- (Diamidoamino) -1-oxy-2- (phenylmethyl) butyl] phenyl} -methyl Synthesis of 2-oxepanone, 2-{{4- [2-(dimethylamino) -l-oxo-2- (phenyImethyl) butyl] phenyl} -methylamino} -ethyl ester, compound 3690) : To the compound 369N obtained in the above step A was added 150 g of 31 200305780 玖, description of the invention. Ε-caprolactone, and when heated to 15 rc, 〇43 g was added to 仏 24. In the reaction history 犄 4 After 78 hours, 78 g of ε-caprolactone was added and the reaction was continued for 4 hours. Finally, the remaining ε-caprolactone was removed under the conditions of 50 μg and 2 tons, and 401 g of red brown transparent and thick was obtained. Liquid (yield 5 93.7%). Measured properties of the title compound (η = 3): Ή NMR (CDCls, 200 MHz): δ 8.36 (d, y = 8.7 Hz, 2 H), 7.19-7.27 (m, 5 H), 6.64 (d, J = 8.7 Hz, 2 H), 4.28 (t, 2 H),% 4.03-4.06 (m, 4 H), 3.61-3.67 (m, 4 H), 3.19 (s, 2 H), 3.05 (s, 3 10 H), 2.60 (b, 1H), 2.35 (s, 6 H), 2.27-2.31 (m, 6 H), 1.80-2.20 (m, 2 H), 1.61- 1.69 (m, 12 H), 1.34-1.41 (m, 6 H), 0.68 (t, J = 7.4 Hz , 3 H) 〇IR (KBr): 3514, 2940, 2866, 1734, 1657, 1642, 1593, 1547, 1462, 1379, 1249, 1183, 823, 704, 662 cm. 15 UV (λ max) = 335.1 nm ° Calculated based on 1H NMR data, the product obtained is a compound of 3 = 3690 with a molecular weight of about 650. < Experiment 1 > Comparison of light speed properties and odor properties is to test the compounds of the present invention, compared with the conventional Whether MMMp, 20 is suitable as a photoinitiator, and in this test, MMMpj, MMMP · 6, and compounds were applied to printing inks having the composition shown in Table 2 below. The comparison of Baizhi's MMMP for photospeed performance and odor properties. Materials · 32 200305780 发明, Description of the invention 1. MMMP: Available from Ciba Speciality Chemicals Holding Inc. under the trade name Irgacure 907. 2. MMMP-3 The compound prepared according to Example 1 above. 3. MMMP-6: Compound prepared according to the above Example 1. 5 4. Compound 3690: Compound prepared according to the above Example 3.

5. Ethyl Michler's ketone: Available from Chitec Chemical Co., Ltd., Taiwan, ROC ·, under the trade name Chivacure EMK, which is used for printing Photosensitizer for photopolymerization of ink. 10 6. Isopropyl thioxanthone: Available from Chititan Chemical Co., Ltd., Chivacure ITX, which is used as a photosensitizer in the photopolymerization of printing inks. 7. Trimethylolpropane triacrylate (TMPTA): available from UCB Chemical Co., which is a monomer compound used in photopolymerization of printing inks.

8. Eberyl 3702: available from UCB Chemical Co. as an oligomer in photopolymerization of printing inks. 9. Fastogen Blue 5380-E (C.I.B.-15: 3): Available from Dainppon Ink and Chemical Co. as a pigment in printing inks. 20 Methods A. Composition of test inks: The above compounds are formulated into four different test inks as shown in Table 2 below. 33 200305780 发明, Description of invention Table 2. Composition of test ink Ink 1 Ink 2 Ink 3 Ink 4 MMMP 4 * 1 — — MMMP-3 One MMMP-6 One 12 Compound 3690 8 * 2 0.5 0.5 0.5 Isopropylthioxanthone 1.0 1.0 1.0 1.0 TMPTA 25 25 25 25 Ebecryl 3702 " 60 60 60 60 Fastogen Blue 5380-E (CIB-15: 3) 5 5 5 5 Tri-1 Kun mill grinding 2 Times __ 氺 3 — —: By weight •• Based on the same equivalent weight as the standard: implemented by blending instead of grinding

5 B. Photopolymerization of test ink: An ink layer of 10 μm is applied to a standard cardboard, and a Fusion D-type lamp (Fusion model: F300S) is used to irradiate the ink under 300 W / in Cure to form a coating. C. Photospeed measurement: Record the light speed of the test ink in in / niin units until a non-stick coating is formed.

D. Determination of odor: for testing odor, at 80. The coating formed by the test ink was heated at 0 ° for a period of 5 minutes, and it was evaluated whether the coating released an odor during the period. The final assessment was classified as "irritating odor" or "none". 15 Results ... The four test inks listed in Table 2 were led to a light speed and odor test. The results obtained are shown in Table 3 below. 34 200305780 Rose, description of invention Table 3. Comparison of light speed performance and odor properties Ink 1 Ink 2 Ink 3 Ink 4 Light speed (in / min) 640 620 540 ~~ 7¾ ^ 'Odor irritating odor after curing No odor The odor can be clearly seen from Table 3. The serious odor problems existing in ink 丨 will not occur in ink 2 (including MMMP-3), ink 3 (including MMMP-6) and ink 4 (including compound 3690). In addition, the light speeds of 5 ink 1 and ink 2 are similar based on the same equivalent. This confirms the effectiveness of the ink using the compound of the present invention as a photoinitiator to form a polymerizable structure of a coating layer upon irradiation. Furthermore, when the compound of the present invention is used, there is an advantage in that when manufacturing printing inks, the ink composition can be formulated only by blending without grinding. 10 < Experiment 2 > Viscosity performance comparison To test the compound of the present invention, compared to the conventional MMMp, what effect will it have on the viscous properties of the finished product, especially under summer shipping and storage conditions? And the four inks shown in Table 2 were used to perform the viscosity performance test, where the test inks were introduced to simulate the transport in summer 15 and the minimum heat treatment under storage conditions over a period of time. Method 'Store the ink in an oven set at 60 ° C and remove a portion of the test ink for analysis at the intervals specified in Table 4 below. Viscosity was measured by using a viscometer 20 (model Rvdv-i) from Brokfiled, and recorded in centipoise ((^ magic units). Results: Four of the listed in Table 2 Each test ink was introduced to the tackiness test, so the results of the invention are shown in Table 4 below. Table 4: At 60 ° C, the change of the viscosity of the ink with respect to time is small. Ink 1 Ink 2 Ink 3 Ink 4 0 6280 * 1 ~ 4400 4120 3800 24 6480 5000 4500 Gelatinized 64 8270 6510 5700 Gelatinized 200 12400 9640 9200 Gelatinized: Unit is centipoise (CPS).

As can be seen from the above Table 4, compared with the ink 5 containing the conventional MMMP, the ink containing the present compound has a lower initial viscosity, and the ink containing the MMMP-3 or MMMP-6 is more resistant to gelation . <Experiment 3> Comparison of MMMP-3 and compound 3690 with BDMB This experiment further compares the differences in light speed performance of MMMP-3 and compound 3690 with BDMB and in-10 can stability without stabilizers. . Material '1. BDMB ·· Available from Ciba Specialty Chemicals Holding Inc.

Under the trade name Irgacure 369. 2. MMMP-3: Compound prepared according to the above Example 1. 15 3. Compound 3690. A compound prepared according to the above Example 3. 4. Ethyl MiChler ’s ketone: See Experiment 1 above. 5. Isopropyl thioxanthone: see experiment 1 above 6. Trimethylolpropane triacrylate (TMPTA): see experiment 1 above. 20 7. Eberyl 3702 · See Experiment 1 above. 36 200305780 发明. Description of the invention 8. Carbon black: available from Degusa as a pigment in printing inks. Method A. Composition of test inks: Using a standard three-roll mill, the components not listed in Table 5 below were formulated into three different test inks. Table 5: Composition of the test ink Ink &quot; T ~ Ink 6 Ink 7 BDMD 5 1 MMMP-3 10 Compound 3690 __ 10 Ethylmizol® 0.5 '0.5 0.5 Isopropylσ-xetanone rp Tfc yT T | rp A 1.0 1.0 1.0 One TMPTA 25 ~ ~ 25 — ~ 25 ^ Ebecryl 3702 ου ο 'One ~~~ 60 ^ Carbon black grinding times 3 ~~ 3 ~ ^ _ 3 ~ 3 ^ B. Test photopolymerization of ink: reference experiment 1 way. C. Measurement of light speed (photospeed): Refer to the method of Experiment 1 D. Measurement of odor: Refer to the method of Experiment 1. 10 E · Viscosity measurement: Refer to the method of Experiment 2. Latent potential: The three test inks listed in Table 5 were led to light speed, odor, and sexual performance tests, and the results are shown in Table 6 below. ^ Table 6: Comparison of MMMP-3 and compound 369〇

Light speed (in / mon) Odor viscosity after curing (cps, initial) Viscosity (at 60 ° C, 24 days 6 viscosity (at 60 ° C, 100 hours) 37 15 200305780 As can be clearly seen from the above-mentioned exemplary experiments and descriptions, compared with the conventional MMMP and BDMB, the MMMP-3, MMMP-6 and the compound 3690, especially MMMP-3 according to the present invention, have the following unique characteristics: 5 1 The odor problem is completely overcome; 2. The light speed performance of the MMMP-3 of the present invention is equivalent to that of the conventional MMMP and BDMB under the same equivalent weight;

3. Lower viscosity can be achieved, which is conducive to the application of flexographic printing or gravure printing inks; 10 4. There is no longer a problem of premature gelling, which is a constant headache. Viscosity is achievable and the formula composition can provide longer storage life; 5. Stabilizers can be eliminated, which not only simplifies the formulation work and saves manufacturing costs; and 6. Does not require grinding treatment, which saves labor costs and time. 15 In addition, the compound 3690 in this case has a faster drying speed than MMMP-3.

Coming fast and comparable to BDMD. Although compound 3690 and BDMD will also encounter the problem of gelation, this problem can be solved after adding 0.5% stabilizer, and when using compound 3690 of this case, it does not need to be ground, and it will reduce the viscosity of the ink system. The conventional BDMD is 20 excellent. All patents and documents cited in the present invention specification are incorporated in their entirety into this case as reference material. In case of conflict, the detailed description (including definitions) of the invention specification of this case will prevail. Although the present invention has been described by the above detailed description and preferred embodiments, 38 200305780

By way of explanation, the present invention should not be construed as being limited; on the contrary, the present invention is an overview. Many other different equivalent changes and modifications. Therefore, without deviating from the essence of the present invention, the simple equivalent changes and modifications made by Dafan 5 in accordance with the scope of the patent application and the content of the invention description of the present invention should still fall within the scope of the patent of the present invention. t schema brief description I (none) 10 [representative table of main components of the schema]

39

Claims (1)

200305780 Patent application scope 1. A compound with the following chemical formula ⑴ With a NR (where R is a CrCi2 Xι: H, S, 0, N, or alkynyl group), x2: Η, S, 0, N, or NR (where R is a Ci-Ci2 alkynyl group) ), But the condition is that when X and X2 are not Η, Xi = &amp;; R, which means: a c 丨 -c 丨 2 alkylene group (Ci_c 丨 2 alkylene 10 15 group) or a chemical formula is -(cH2〇CH2) p- group, where p is an integer from 1 to 4; R! and R2 respectively represent ... Η, phenyl, or Ci- optionally substituted by phenyl c12 alkyl, C2-Cl2 alkenyl, Ci-Ci2 alkoxy; R3 and R4 each represent a Cl_c6 alkyl group which is optionally substituted by a hydroxyl group, or R3 and R4 together with the nitrogen atom bonded thereto form one Select / ~ \ / \ 一 N \ 一 NN—Η from the cyclic groups in the following groups: JU and 40 200305780, the scope of patent application R5 means: Η, F, a, Br, I, nitro, benzene When X or X2 is Η, k is 0; when X! Or χ2 is s, 50 or NR, k is 1; and when X! Or χ2 When the system is N, the k system is 2; the m system is one from 2 to 5. An integer; and when k is 1, η is an integer from i to 20, and when k is 2, η == ηι + η &lt; 2〇, where ηι and η: each is from 10 Integer to 10. 2. The compound according to item 丨 in the scope of patent application, wherein R is an ethylenyl group. 3 · If the scope of patent application is the first! And &amp; one of which is S or 0 'and the other is η. 15 4. The compound according to item 1 of the scope of patent application, wherein R is an ethylenic group. 5. The compound according to item 1 in the scope of patent application, wherein m is 5. 6. The compound according to item 5 of the patent application, wherein n is 3. 7. A compound as claimed in item 5 in which n is 6. 208 · The compound according to item 1 of the scope of patent application, wherein Ri and R2 are each a group selected from the group consisting of methyl, ethyl, propyl, and phenyl groups. Methyl and phenyl substituted propyl. 9. If the compound in the 8th scope of the patent application, both Rl and r2 are 41 200305780, the scope of the patent application is methyl. 10. The compound according to item 8 of the patent application, wherein R! Is phenyl substituted methyl and R2 is ethyl. 11. For example, the compound in the scope of patent application, wherein R3 and R4 are each a group selected from the group consisting of: fluorenyl, ethyl, propyl, and hydroxy-substituted propyl . 12. For the compound in the scope of patent application item 1, wherein R3 and R4 together r ~ \ -N 〇 together with the nitrogen atom to form a ^-* ^ group. 13. For example, the compound in the scope of patent application No. 1 in which: one of 10 XS and X2 is S, the other is Η, R 'is an ethylenyl group, Ri and R2 are separately Is methyl 5 / \ 一 Ν Ο R3 and R4 together with the nitrogen atom attached to it form a ^ I Group, 15 R5 is fluorene, and m is 5. 14. The compound as claimed in item 13 of the patent application, in which n is 3. 1 5. The compound according to item 13 of the patent application scope, wherein η is 6. 16. For the compound in the scope of patent application No. 1 in which one of X! And X2 is N and the other is Y. 17. The compound as claimed in claim 16 wherein R 'is an ethylenic group. 42 200305780 Scope of Application for Patent 18. For example, the compound in the scope of application for item 17 in which m is 5. 19. If the compound in the scope of the patent application No. 18, the sum of η + η2 is 6 020. · If the compound in the scope of the patent application No. 16, where &amp; and &amp; each 5 is one selected from the following The groups in the group: methyl, ethyl, propyl, phenyl-substituted methyl, and phenyl-substituted propyl. 2 1. The compound of scope 20 of the patent application, wherein both &amp; and &amp; are methyl. 22. The compound of item 16 in the scope of the patent application, in which r3 and r4 are each a group selected from the group consisting of: fluorenyl, ethyl, propyl and hydroxy substituted Propyl. 23 · The compound according to item 16 of the scope of patent application, wherein r3 and r4 together with the nitrogen atom to which / \-N 〇 is attached form a \-^ / group. 24. For the compound in the scope of patent application, one of 15 Xl and one of them is N, and the other is H, R 'is an ethylenyl group, Ri and R2 are respectively A Group, Ν Ο R3 and R4 together with the nitrogen atom to which it is attached form a '-1 ^ 1 group, 20 R5 is Η, m is 5, and iii + n2 = 6 ° 43 20003 578 〇 Pick up the patent scope 25. For the compound in the first scope of patent application, one of X! And X2 is NR (where R is f group or ethyl), and the other is Η, R is An ethylid group, 5 Ri is a phenyl-substituted methyl group, I is an ethyl group, 1 and r4 are each a methyl group, The system is η, and the m system is 5. 102. A compound according to any one of claims 1 to 25 of the scope of patent application, which can be used as a photoinitiator. 27. A method for manufacturing a compound having the chemical formula (I) as defined in the scope of the patent application, including the steps of: 々 a compound having the following chemical formula (II) and a compound having the chemical formula 15 ( ΙΠ) reacts with the lactone compound to form the compound of formula ⑴: 〇 The definitions of h, R2, R3, R4, and R5 are the same as those defined in 20 of the scope of the patent application. Xi represents ... Η, S, 0, N, or NR (where R is a Ci_c 44 200305780 (Patent application, alkyl group), X2 means: Η, s, 0, N or nr (where R is a Ci—Cu alkyl group), but only when X and X2 are not Η XlsX2, and s is 1; and when X! Or X2 is Η, s is 0; (III) where q is an integer from 1 to 4. 28. The method of claim 27, wherein the method is performed in the presence of a tin-containing catalyst. 10 29. The method according to item 28 of the patent application, wherein the method is performed in the presence of n-butyl-tin tris (alkanoate, SCAT-24). 30. The method according to item 27 of the scope of patent application, wherein the lactone compound having the formula (III) is selected from the group consisting of 15 • Lu-propenesi (/ 5 -propiolactone ), Butyrolactone (_ butylolactone), 5-valerolactone (5 _ ^ 1 „〇1 &amp; to 0116) and ε _ caprolactone (6-caprolactone). Method, wherein the lactone compound having the formula (III) is ε-caprolactone. 20 32. The method according to item 27 of the application for a patent, wherein the compound having the formula (II) is used It is generated by reacting a compound having the following chemical formula (π,) with a compound having the following chemical formula (IV). Ri NlR3 I R4 (II,) where R !, ruler 2, R3, R4, and R5 are the same as those who are defined in item 1 of the scope of patent application. Υι means: H, F, C1, Br, Ϊ, or cyano, Y2 means: H, F, ci, Br, I, or cyano, but with the condition that when neither y nor A is H, Yet 10 r ,, xr, oh (IV) X is S, 0, NH or NR (where R is a Ci-Ci2 alkyl group), The definition of R 'is the same as that defined in item 1 of the scope of patent application; and 15 "when x is s, 0 or NR, R" is Η; and when X is ΝΗ, R "is Is r'oh. 33. The method of claim 32 in the scope of patent application, wherein among the compounds of formula (Π,) used, one of y and Y2 is η, and the other is F, Cl, Br, or I . 20 34. The method of claim 33 in the scope of patent application, wherein in the compound of formula (Π,) used, ah! One of them is Y, and the other one is F. 35. The method of claim 33 in the scope of patent application, wherein among the compounds of formula (Π,) used, one of Υι # γ2 is h and the other is C1. 5 36. The method according to item 32 of the towel material, wherein the towel is ρ in the compound of the formula (Π) used. 37. The method according to item 32 of the patent application, wherein in the compound having the formula (Π,), both Υ and γ2 are 0. 38. The method according to item 32 of the scope of patent application, wherein in the compound having the formula # 10 (π ′), ^ and K are each a group selected from the group consisting of Group: methyl, ethyl, propyl, phenyl substituted methyl and phenyl substituted propyl. 39. The method according to item 38 of the scope of patent application, wherein in the compound of formula (Π,) used, both Xin and &amp; are methyl. 5 40. The method of claim 38, wherein &amp; is a methyl substituted with a benzyl group, and R2 is an ethyl group. 41. The method according to claim 32, in which the compound of formula (Π,) used is 1 and &amp; each is a group selected from the group consisting of : Methyl, ethyl, propyl substituted with 20 and hydroxy. 42. The method according to item 32 of the scope of patent application, wherein in the compound of formula (Π ′) used, 1 and &amp; together with the nitrogen Γ ~ \ —N 〇 atom attached thereto form a ^ A group. 47 200305780 Patent application scope 43. If the method of patent application scope item 32 is used, the compound of formula (iv) used in # is HS (R, 0H), and R is a diethyl ether Group. 44. The method of claim 32 in the scope of patent application, wherein the compound having the formula (IV) is NH (R, OH) 2, and R is an ethylene group. 45. The method of claim 32 in the scope of patent application, wherein the compound of formula (iv) is RNH (R, 0H), R is a methyl group, and R 'is- Ethylene group. · 1046 · The method according to item 32 of the scope of patent application, wherein the compound of formula (iv) used is RNH (R, 0H), and R is an ethyl group, and R ' It is an ethylenic group. 47. The method according to item 32 of the scope of patent application, wherein among the compounds of formula (π,) used, one of I and Υ2 15 is Η, and the other is F, C, Br, or 1 ; 1 and methyl are respectively methyl; &amp; and I together with the nitrogen atom attached thereto form N — a group; and R5 is Η; the compound of formula (IV) used is Is hs (r, 0h), and R is an ethylidene group, and the compound of formula (Π) thus generated is introduced to react with ε_caprolactone to form the A compound of the formula ⑴ in which one of X1 and X2 is s and the other is 系. 48. The method according to item 46 of the scope of patent application, in which the compound η is 3 in the compound having the formula (I). 49. The method according to claim 46, wherein n is 6 in the compound of formula (I) produced. 50. The method according to item 32 of the scope of patent application, wherein 5 of the compounds of formula (Π,) used is one of Υ | and% is Η, and the other is 1; 111 and &amp; Each is methyl; R3 and R4 together with the nitrogen atom attached to them form Γ ~ \ -N 0 to a U group; and is Η; the compound of formula (IV) used is NH (R, OH) 2, and R 'is an ethylenyl group, and as such The resulting compound of formula (11) is introduced to react with ε · caprolactone to form the compound of formula ⑴, where one of X 丨 and X2 is N and the other is Η ; And n 1 + Π2 = 6 〇51 51, such as the method of the scope of patent application No. 32, where Among the compounds of formula (n,) used, one of Y! And A is Η, and the other is F, a, Br, or 1; &amp; and &amp; From the group consisting of: methyl, ethyl, propyl, phenyl-substituted methyl, and phenyl-substituted propionyl; ^ and h are each methyl, and R5 is For fluorene, the fluorene compound of formula (IV) used is in which R is methyl or ethyl, and R is an ethylenic group, and 49 200305780 was generated as a result of the scope of patent application. The compound of formula (π) is induced to react with e-caprolactone to form the compound of formula ⑴, where one of 乂 丨 and 乂 2 is NR (R is methyl or ethyl), And the other is Η. 5 52 · —A photopolymerizable composition comprising a photopolymerizable monomer compound and a compound of formula (I) as in any one of claims 1 to 25 of the scope of patent application. 53. The photopolymerizable composition according to item 52 of the patent application, further comprising a pigment or dye. 10 54. A printing ink comprising a compound of formula (I) as a photoinitiator as in any one of claims 1 to 25 of the scope of patent application. 50 200305780 Lu, (1), the designated representative of the case is: _ _ (2), the component representative symbols of the representative diagram are simply explained: (no picture) Chai, if there is a chemical formula in this case, please reveal the features that can best show the invention Chemical formula: 4