TWI277834B - 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

1277834 玖, the description of the invention (the description of the invention should be stated: the technical field, prior art, content, embodiment and schematic description of the invention) L-invention of the technical field of the invention 3 FIELD OF THE INVENTION The present invention relates to Novel morpholinolcetone derivatives of photoinitiators and methods for their preparation and use. C Prior Art 3 Background of the Invention UV curing printing technology is more widely used than conventional lithographic printing techniques, and can be applied not only to the manufacture of conventional lithographic inks, lithographic inks (offset inks). ), letterpress ink, flexo ink, gravure ink, silk screen ink, etc., can be applied to printed circuit boards (printed) Circuit board), photoresist, solder masker (also known as green lacquer), dielectric substrate 15 (dielectric substrate) and the like. In general, the UV hardening process requires a binder, a photopolymerizable monomer, and a photoinitiator, wherein the photoinitiator can polymerize the monomer in a short period of UV irradiation. A polymer is formed. The photochemical polymerization of the unsaturated monomer and the prepolymer is a commonly used conventional method having a wide range of industrial applications. No. 3,661,614 discloses a radiation curable solventless printing ink composition which generally consists of: (1) from about 20% to 98% by weight of a pentaerythritol acrylate, methacrylic acid An ester or itaconate, (2) a halogenated aromatic, alicyclic 1277834 oxime, inventive family or aliphatic hydrocarbon photoinitiator of about 2 wt ° / 〇 to 80 wt ° / ,, wherein the halogen atom is Directly attached to the ring structure of the aromatic and alicyclic compounds and to the carbon chain of the aliphatic compound, and (3) a colorant. US 4,672,079 discloses poly5- or polymerizable aromatic-aliphatic ketones which are useful as photoinitiators for the polymerization, preferably 2-hydroxy-2-methyl (4-ethylglycol) [2-hydroxy-2-methyl(4-vinylpropiophenone)], 2-yl-2-methyl-/7-(1-indolylethyl)-propenylbenzene (2-11; 7(11>〇)乂)^2-11161:1171---(1-methylvinyl)propiophenone), p-ethylene benzoylcyclohexanol-vinylbenzoylcyclohexanol, p-(l-methylethionyl)benzamide P-(l-methylvinyl)benzoyl-cyclohexanol and these polymerization and polymerization products are suitable as ethylenically unsaturated monomers and prepolymers (prep〇iymer) A photoinitiator for photopolymerization. US 4,943,516 discloses a photosensitive thermosetting resin composition comprising 15 (a) a photosensitive prepolymer having at least two ethylenically unsaturated bonds in its molecular unit; (b) a light-initiating bond (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 A limited solubility is exhibited in the solvent to be used; and (e) a curing agent for the epoxy resin. The photosensitive thermosetting resin composition is disclosed to exhibit good imaging properties and sensitivity as well as to provide a long shelf life. When introduced into coating, exposure, development, and post-cure treatment, the photosensitive thermosetting resin composition can be formed to exhibit a property of adhesion, insulation resistance, electrolytic corrosion resistance, etc., 1277834 玖The invention describes a good solder resist pattern. No. 4,582,862 discloses a photocurable colored composition comprising: (a) an olefin bond-unsaturated photopolymerizable binder, a pigment of 5-6 Å/min by weight, and (c) 〇1_2 One of the 重量% by weight of the photoinitiator of the formula (I) as disclosed in the 5th. In particular, 2-methyl-l-[4-(methylthio)phenyl] (2-methyl-l-[4-(methylthio)phenyl]] -2-morpholino-propane-l-one5 MMMP) has become a widely used photoinitiator today, especially in pigmented UV systems such as solder masks (s〇ider 10 masker) With UV inks. It has been reported that MMMP can provide good photospeed and mechanical properties without compromising its own non-ubiquitous nature.

MMMP However, when MMMP is used, it will cause a problem of bad odor due to the volatile sulfur residue contained therein during the post-curing processing, which limits its industrial application. In particular, when MMMP is applied to UV inks or solder resists, there is a problem of varying degrees of mild odor from mild to unpleasant, which is caused by photofragmentation of MMMP (photofragmentation) The resulting 4-methyl thiobenzoic acid (4-metliylthiobenzaldehyde) having a volatile odor of 20 odors. 1277834 玖, invention description Because of the limited choice of available photoinitiators, 'users often have to endure the odor 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 5,5,6,279, US 5,837,746, WO 96/20795, US 6,048,667) 'Specifically 2 phenyl fluorenyl groups disclosed in US 5,145,885 2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butan-l-〇ne, BDMB ) as a replacement for MMMP.

For some pigment systems (such as Cyan pigments) that use MMMP and BDMB as the primary photoinitiator, an excessive amount of grinding treatment may be required to incorporate all of the photoinitiator, which may result in premature curing. One of the stickiness of the ink is increased or even gelled, and thus it is necessary to add a polymerization stabilizer such as p- 15-anisole (MEHQ). However, the stabilizer will eventually delay the speed of light. Furthermore, MMMP and BDMB tend to increase the viscosity of the resulting ink, which is undesirable for applications that require low viscosity, such as elastic reliefs. Therefore, based on the shortcomings of the prior art, there is a need to develop new materials which are available as photoinitiators for photopolymerizable compositions. [明内^L] I2?7834, description of the invention Summary of the invention There are usul species under the column. In the first aspect, the invention provides a compound of formula (I): H0

0 κ〇^%τ° 〇

\), I /IV where Χι denotes: Η, S, 0, N or NR (wherein an alkyl group), and 2 represents: H, S, 0, N [or NR (wherein an alkyl group), but · Conditional if both Xt and x7 are not Ha: R is a CVCu R is a CVC12 10

Xi = x2 ; w represents: a crc12 alkylene group or a group of the formula CH2〇CH2V, wherein p is an integer from 1 to 4;

Ri and R2 each independently represent: fluorene, phenyl, or CVC12 alkyl, C2-C12 alkenyl, <^-(:12 alkoxy; substituted 3 and R4, respectively, optionally substituted by phenyl Represents a C丨_c6 alkyl group which is optionally substituted by a radical,

The R3 and I together with the nitrogen atom to which they are attached form a cyclic group selected from the group consisting of: 10 1277834 发明, invention description

Han 5 indicates: Η, F, Cl, Br, I, nitro, phenyl, C-Ci2 or Q-Cu alkoxy; when Χι or X2 is Η, k is 〇; when Xi or Χ2 is s 〇 or NR day, k is 1 , and when X or χ 2 is n, the 匕 is 2; m is an integer from 2 to 5; and when k is 1, The η system is an integer from 1 to 20, and when the k is 2, η = ηι + η 42 〇, where ηι is an integer from summer to 10 for each. In a second aspect, the present invention provides a process for the manufacture of a compound of formula (I) as described above, which comprises the steps of: a compound having the following chemical formula (II) and a chemical formula ( The lactone compound phase reacts to form the compound of formula (1):

The definitions of heart, anti-2, 乂3, 乂4xing & are the same as those defined for the above compound of formula (1),

1277834 玖, invention description alkyl group), X2 means: H, S, 0, N or NR (where r is a Ci-Ci2 5 but conditionally when both X and x2 are not χ, χ1 = χ2 And s is and when X][4X2 is Η, s is 〇; Ο ·〇

(III) wherein q is an integer from 1 to 4. The lactone compound 10 of the formula (III) which can be used in the method of the present invention is selected from the group consisting of: /3-propiolactone, 7" - butinesine (7-butyl) 〇lact〇ne), 5-valerolactone and ε-caprolactone. Preferably, the compound having the chemical formula (in) is ε-caprolactone.

In a preferred embodiment, the method of the present invention is carried out in the presence of a tin-containing catalyzed 15 agent. Preferably, the process is carried out in the presence of n-butyl-tin tris (alkanoate, SCAT-24). In a preferred embodiment, the compound of the formula (Π) used in the method of the present invention is produced by reacting a compound of the following formula (IV) with a compound of the following formula (IV): 12 1277834 玖, invention description〇

among them

The definitions of R1, R2, I, r4 and r5 are the same as those defined by the above chemical formula (1).

Υι indicates: Η, F, Cl, Br, I or cyano, Y2 does not: Η, F, a, Br, I or cyano, but conditionally when both Yi and Y2 are not ,, Yi = Y2; R,, XR, 〇H (IV) wherein 10 X is S, 〇, NH or NR (wherein R is a CVCi2 alkyl group),

R' is defined as the same as defined in the above formula (1); and when X is S, 0 or NR, R, is Η; and when X is NH 15, R' is r, 〇 h. The invention also encompasses the use of the compound of formula (I). For example, the inventors of the present invention have found that the compound of the formula (1) can be used as a photoinitiator (Ph〇t〇iniator). Thus, the compound of the formula (I) of the present invention and the photopolymerizable monomer compound can be formulated into a photo-sustainable composition such as a printing ink. Other objects, features, and advantages of the invention will be apparent from the description of the appended claims appended claims

C. Detailed Description of the Invention] In order to overcome the problem of bad odor of MMMP, the present invention attempts to change the molecular structure of MMMP by linking a polymerizable link to the thiol moiety of MMMP, and has developed one having the following Compound of formula (1): 15

Medium (I) X! represents: Η, S, 〇, N or NR (wherein R is an alkyl group), and X2 represents: Η, S, 〇, N or NR (wherein R is a CIA alkyl group) ),

However, it is a condition that when both X1 and & are not H, χΐ = χ2; R represents no CpC丨2 alkylene group or a group of formula _(CH2〇CH2V, wherein p is a whole wife's text from 1 to 4.

Ri and R] each represent a substituted CVCu alkyl group, : Η 'phenyl group, or a phenyl group, a c2-c12 group, or a crC12 oxy group; 14 1277834 玖, invention description Han 3 and R 4 Further, a CrC6 alkyl group which is optionally substituted by a hydroxyl group, or Han 3 and I together with a nitrogen atom to which it is bonded form a cyclic group selected from the group consisting of

N-H and

R5 represents: H, F, Cl, Br, I, nitro, stupid, Cl-Cl2 alkyl or CVC12 alkoxy; when the field Χ or X2 is Η, the 'k is 〇; when Χι or χ2 is When s, 〇 or NR, k is 1; when X! or X2 is N, k 10 is 2; m is an integer from 2 to 5; and when k is 1, n is Is an integer from i to , and when & is 2, η=ηι+η<2〇, where ~ and n2 are each an integer from ι to 1〇. 15 In a preferred embodiment, m is 5. In a preferred embodiment, R' is a Ci_C6 alkylene group, particularly an ethyl group, or a chemical formula of _(cH2〇CH2)· or -CH2〇CH2CH2〇CH2- Group. Preferably, h and R2 are each a group selected from the group consisting of methyl, ethyl, propyl, phenyl substituted methyl and phenyl substituted C. base. In a preferred embodiment, & and R2 are both A 15 1277834. Inventive Description In another preferred embodiment, & is a phenyl substituted methyl group and R2 is an ethyl group. In a specific example, R3 and R4 are each a group selected from the group consisting of methyl, ethyl, propyl and propyl substituted by a base. In a more preferred embodiment, rjr4 is a methyl group. In a specific example, R3 Xiao R4 together with the nitrogen atom to which it is attached forms a group. 10 15

In a specific example of the car parent, R5 is Η, F, a, Br, I, a base or a Cl<6 alkyl group. In a more preferred embodiment, R5 is Η. / In a preferred embodiment, one of X! and Χ2 is s or 0 and the other is H. In a more preferred embodiment, the η system is . In another more preferred embodiment, the η system is 6.

In a more preferred embodiment, one of & and Χ2 is s and the other is H, R, which is an extended ethyl group ring, and each of R and R2; is a methyl group, R3 and r4 together with the nitrogen atom to which they are attached form a W group 'R5 is H, and the claw is 5. - In another case, the preferred specific financial value is N, the other is H, and the sum of n! + n2 is preferably 6. In the better case t, X, and 2 are ordered to be ^ and the other is H, R, which is an exoethyl group, && and each is W, R3# R4 The hydrogen atom associated with the ruthenium is formed - 16 20 1277834 玖, the invention describes the alkyl group) s is 0 or 1, but conditionally, when both Xi and X2 are not Η, X! = X2, and s is 1; and when 乂丨 or X2 is Η, s is 0; —— 5 (ΙΠ)

Where q is an integer from 1 to 4. With regard to the compound of the formula (II), its preparation can be carried out by referring to a conventional method, for example, a synthesis technique disclosed in the above-mentioned prior documents, 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 formula (in) which can be used in the method of the present invention can be selected from the group consisting of: /5 - propiolactone 15 , 7 - butylene (γ - Butylolactone), (5-valerolactone) and ε-caprolactone. In a preferred embodiment, the lactone compound of formula (III) is ε-hexyl The lactone compound is commercially available, for example, from DAICEL Chemical Co. 〇20. The advantage of using the lactone compound of formula (III) as a source of polymerizable chains is : (1) The molecular weight of the product can be easily controlled, 18 1277834 玖, invention instructions (2) high pigment wettability, (3) high UV stability, (4) low toxicity (biodegradable), and (5) Low viscosity. 5 The process can be carried out using a catalyst which can be used in the ring-opening polymerization of the lactone compound of the formula (III). The catalyst suitable for the process of the present invention is, for example, tetraethyl titanate (tetraethyl titanate) Titanate), tetrapropyl titanate (tetrap Rotyl titanate), tetrabutyl titanate or other titanate-containing compound, stannous octoate, dibutyl-tin-oxide, dibutyltin dilaurate (dibutyl-tin-dilaurate), a tri-n-butyl-tin tris (alkanoate) or other organotin compound, stannous chloride, stannous bromide or other stannic compounds (see US) 6,037,393) ° 15 In a preferred embodiment, the process is carried out in the presence of a tin-containing catalyst. In a more preferred embodiment, the process is based on tri-n-butyl-butyltin [n-butyl] In the presence of -tin tris (alkanoate), SCAT-24]. In a preferred embodiment, the compound of formula (II) used in the method of the present invention is obtained by having one of the following chemical formulas ( The compound of Π ') is formed by reacting with a compound of the following formula (IV): 19 1277834

(II,) where

Ri, R2, R3, r4 and r5 are defined as those defined by the above formula (I), Υι means: Η, F, Cl, Br, I or cyano, Y2 means: H, F, Cl, Br, I or cyano' but with the proviso that when both ι and γ2 are not Η, Yi = Y2 ; R,, XR, OH (IV) where X is S, Ο, NH or NR (where R is a Ci-Cu alkyl group), R' is defined as the same as defined in the above formula (I); and when X is S, Ο or NR, R'' is Η; and when X is nh When R'' is R'OH. With respect to the compound of the formula (II,), the preparation can be carried out by referring to a conventional method. For example, the preparation of the compound of the formula (II,) can be carried out according to the related disclosure of US Pat. No. 4,582,862. The group is introduced into a corresponding arylalkyl ketone compound. 20 1277834 玖, description of the invention

Where Hal represents Nansu, and R1 to R5 and Y! and γ2 are defined as those defined by the above chemical formula (Π,). In a preferred embodiment of the present invention, the compound of the formula (Π) used is one in which one of the towels 1 and A is Η, and the other is a compound of ^^. Earth, '~ There is - who is Η' and the other _ is? Or α. In another comparative example of the present invention, the compound of the formula (π,) used in the invention is a compound in which both Υ and Υ2 are F or C1. 10-15. In a preferred embodiment of the present invention, the compound of the formula (Π) used is one in which + and & are individually selected from the group consisting of: A compound of a group consisting of a methyl group, an ethyl group, a propyl group, a phenyl group substituted with a phenyl group, and a phenyl group substituted with a phenyl group. In a more preferred embodiment, R1 and R are some methyl groups. In another more preferred embodiment, R丨 is a phenyl-substituted methyl group and 1 is an ethyl group. In a preferred embodiment of the present invention, the compound of the formula (Π) used is a + & and R4 together with a nitrogen atom bonded thereto to form a

The compound of the group 〇 is another preferred embodiment of the present invention, and the compound of the formula U) is used as a towel I and & respectively, a single 21 1277834 发明, invention A compound exemplifying a group from the group consisting of methyl, ethyl propyl, and propyl substituted by a base. In a preferred embodiment of the invention, the compound of the formula (Π') used is one wherein &

a compound of li, Br, I 5 , phenyl or crc6. In a better specific example, the heart is Η. The compound of formula (IV) is commercially available, for example, from BASF Corporation. In a preferred embodiment, the compound of formula 10 (IV) used in the present invention is hs(r, oh), wherein R is an exoethyl group. In another preferred embodiment, the compound of formula (IV) used in the present invention is NH(R, 〇H) 2 wherein R is an ethyl group. In another preferred embodiment, the compound of formula (IV) used in the present invention is RNH (R, 〇H), wherein the system is a methyl group or a 15 ethyl group, and the R' system It is an ethyl group. In a preferred embodiment of the present invention, the compound of the formula (Π) used in the preparation method of the present invention is a compound, wherein one of γι and Υ2 is Η, and the other is f, CBr or I; Ri and R2 are each methyl; 1 and I together with the nitrogen atom to which they are attached

The formation of one, one "^ group, and the Rs system is Η; the compound of formula (IV) used in the preparation method of the present invention is HS(r, 〇h), and the R system is a stretch And an ethyl group; and the compound of the formula (II) thus produced is introduced to react with caprolactone to form 22 20 1277834, and the invention is described in which one of X1 and & Compound S having the formula (I) and the other being H. In another preferred embodiment of the present invention, the compound of the formula (π,) used in the preparation method of the present invention is a compound, one of which is ruthenium and the other is F, cl. , Br*工' Ri total R2 is methyl; R3 and 1 together with the nitrogen atom -N 〇10 I attached to form a sulfonium group; and R5 is H; used in the preparation method of the present invention The compound of the formula (IV) is NH(R 〇H) 2 , wherein R is an ethyl group; and the compound of the formula (Π) thus produced is introduced to ε- Caprolactone is reversed to form a compound of formula (I) wherein one of X and χ2 is Ν and the other is Η; and ηι+η2==6. In another preferred embodiment of the present month, the compound of the formula (Π) used in the preparation method of the present invention is a compound in which one of the Υι and one of them is Η, and the other Is f, C, Br or I, and each of Ri and R2 is a group selected from the group consisting of methyl, ethyl, propyl, phenyl substituted methyl and phenyl substituted a propyl group; each of I and h is a methyl group, and Rs is a H; the compound of the formula (IV) used in the preparation method of the present invention is rnh(r, oh) 20 wherein the size is methyl or ethyl a group, wherein R is an ethyl group; and the compound of formula (π) thus produced is introduced to react with ε-caprolactone to form the compound of formula (I), wherein 23 1277834 玖, Invention Description One of X! and X2 is NR (R is methyl or ethyl), and the other is Η. The invention also encompasses the use of the compound of formula (I). According to the present invention, the compound of the formula (I) can be used as a photoinitiator 5, and it does not cause the problem of bad odor normally associated with hydrazine, and a compound containing the compound of the formula (I) The photopolymerizable composition does not have a problem of increased viscosity. Thus, according to the methodology available in the art, the compound of formula (1) according to the invention is formulated with the following components: photopolymerizable monomeric compounds, photosensitizers, pigments or pigments. (dyestuffs), and other additives commonly used by those skilled in the art to prepare photopolymerizable compositions, such as oligomers, photosensitizers, and amine synergists. And other physical property modifiers (physical property modifiers). The compound of the formula (1) according to the present invention is expected to be used in various industrial applications, for example, the industrial application of the photoinitiator mentioned in the above-mentioned prior documents. For example, the compound of formula (1) according to the present invention can be formulated as a photoinitiator in UV inks or coatings. Compounds of formula (I) having the formula 20 according to the invention are also contemplated for use in combination with conventional photoinitiators, such as those disclosed in the aforementioned documents, in particular as disclosed in U.S. Patent 4,672,079. . The invention will be further illustrated by the following examples, but it should be understood that these examples are for illustrative purposes only. 24 1277834 玖, 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-Methyl-2-morpholine-4-yl-propenyl)phenyl hydrazino]-ethoxymethyl}-indenyl-Wilyl)-mercaptoacetic acid (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-jing 5-hexyl-hexanoic acid 5-(5-{2-[4,(2-mercapto-2-oxafolin-4-yl-propenyl)phenylsulfonyl]-ethoxycarbonyltetra(pentyl) 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 its intermediate l-[4(2-hydroxyethylthio)-phenyl] 2-mercapto-2-propofolinyl propan-1-one (l -[4-(2-Hydroxyethylthio)-phenyl]-2-methyl-2-morpholino-propan-1 -one, compound 2), the relevant synthetic route is as follows:

NaOH, stupid and then DMF H0

1 Caprolactone SCAT-24 ΜΜΜΡ-3: η = 3 ΜΜΜΡ-6: η = 6 wherein the molecular weight of the product compound synthesized can be changed by adjusting the molar ratio of compound 2 to ε-caprolactone, Such as ΜΜΜΡ-3 and 25 15 1277834 玖, invention description MMMP-6 is. A. 1_丨4<2-Hydroxyethylthiophenyl]-2-methyl-2-moffinylpropan-1-one (Compound 2) Synthesis: 0

5 94.8 g (1.21 mol) of mercaptoethanol and 600 ml of toluene were placed in a 1 liter three-necked round bottom flask' followed by 48.6 g (1.21 mol;) of Na〇H. The mixture was introduced to reflux for 6 hours, at which time the formed water was collected by a Dean-Stark apparatus. The toluene solvent was removed by distillation, and 10 250 ml of DMF was added to the solid agglomerate. After the solution was cooled to room temperature, 250 g (0.93 mol) of 1-(4-fluorophenyl)-2-methyl-2-moffinyl-1-propanone (Compound 1, according to US patent) was added in one portion. Prepared according to No. 4,582,862, and the resulting mixture was heated at 50 ° C overnight under a nitrogen atmosphere. The mixture was cooled to room temperature, diluted with 1 liter of toluene, and washed with 15 water, 2% NaHH aqueous solution and brine (brine). The organic layer was separated and concentrated under vacuum to give a yellow viscous oil, which was further purified by recrystallization to yield a pale white ff-white crystal (90% yield, melting point·· 62-64 ° C). Β· Synthesis of MMMP-3: 20 200 g (0.65 mol) of compound 2, 88.5 g of 6-caprolactone and 8 g of tin catalyst [trade name SCAT-24, purchased from Japan's third total 26 1277834, Sankyo Organic Chemistry Co., Ltd. was placed in a 500 ml three-necked round bottom flask equipped with a condenser and protected under nitrogen. The mixture was heated to 80-85 ° C for 2 hours. 44.3 g of ε-caprolactone and 4 g of SCAT-24 were added to the above flask every 4 minutes for 4 times, and the temperature was maintained for another hour. The resulting mixture was washed with water, 2% aqueous NaOH and brine. The organic layer was concentrated under vacuum to give a light tan oil (398 g, 95% yield). Properties measured for the title compound '· 10 NMR (CDC13? 400 MHz): δ 8.46 (d? J = 8.4 Hz, 2 H)? 7.29 (d5 J = 8.4 Hz, 2 H), 4.26 (t, J - 6.9 Hz? 2 H)? 4.02 (t, / 2 6.5 Hz, 6 H), 3.65 (t, / = 3.8 Hz, 4 H), 3.60 (t, / = 6.5 Hz, 3.20 (t, J = 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), 1.30-1.42 (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_i o Based on the obtained 1H The NMR data estimated that the obtained product had an n value of 3. The molecular weight relative to MMMP was 279, and the molecular weight of the obtained product 20 was about 650. C. Synthesis of MMMP-6: Synthetic with the same MMMP-3 To synthesize MMMP-6, only 354 g instead of 88·5 g of ε-caprolactone was used to form a light tan paste (97% yield). 27 J277834 kan, invention description Properties of the title compound: NMR (CDC13? 400 MHz): δ 8.46 (d? J = 8.4 Hz, 2 H), 7.29 (d, J = 8·4 Hz, 2 H), 4·2 ό (t, / = 6.9 Hz, 2 H), 4·02 “, h 6.5 Hz, 12 H), 3.65 (t, J = 3.8 Hz, 4 H), 3.60 (t, 5 6·5 Hz, 3 · 20 (t, / = 6.5 Hz, 2 H), 3.20 (t, J = 6.9 Hz, 2 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 obtained 1H NMR data, the obtained product has an n value of 6, and the molecular weight is 6. About 960. 1 The physical properties of MMMP_3 and MMMP-6 are compared to MMMP-6 as a paste at room temperature, and MMMP-3 is a light amber liquid at room temperature. The condensed point of MMMP-3 is about ^5 C or so and it will not be cured after standing for 3 days at 〇c. Table 1 below lists the physical properties of MMMP-3 and MMMP-6. MMMP-3 MMMP-6 color* (pure) 4.5 4.8 Viscosity at 70°F 1200 cps Paste Viscosity at 100°F 423 cps 1743 cps Density 1.082 1.092 * Calculated in Gardner units. <Example 2> This example illustrates how to synthesize another compound according to the present invention, that is, compound 5, and its intermediate product 1-{4-[bis-(2-hydroxy-r-ethyl)-20 Amino]}2-methyl-2-norfosyl-1-propanyl g (1_{4-[1^-(2-117(11:〇和7-7"- ethyl)-amino]} -2-methyl-2-moi,pholino-l-propanone,compound 4) 28 1277834 玖, description of the invention, the relevant synthetic pathways are as follows:

A. Synthesis of 1-{4[bis-(2-hydroxy-r-ethyl)-amino]}2-methyl-2-morpholine-yl-acetone (compound 4): 5 will be 10.0 g ( 0.037 mol) of 1-(4-fluorophenyl)2-methyl-2-norfosolin-1-propanone with 58.9 g (0.56 mol) of diethanolamine placed in a 100 ml three neck The round bottom flask was heated to 150 ° C for 24 hours. The resulting solution was cooled, diluted with 100 ml of ethanol, washed with water and brine, and removed by a rotary evaporator. Solvent 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) was placed in a three-neck round bottom flask equipped with a condenser and protected under nitrogen. The mixture 15 was heated to 80-85 ° C for 1.5 hours. Each 30 minutes will be 9.0. A mixture of ε-caprolactone of g and g·9 g of SCAT-24 was added to the above flask for 3 times. The temperature was maintained for another hour. The reaction mixture was 29 1277834 发明, invention description It was cooled to room temperature and diluted with 200 ml of hydrazine. After washing with water and brine, the organic layer was concentrated under vacuum to give a viscous oil (29.8 g, 90% yield). 1H NMR data calculation, compound 5 = 1 + 112 = 6. 5 <Example 3> This example illustrates how to synthesize another compound 3690 according to the present invention, namely 2-oxipenone, 2- {{4-[2-(Dimethylamino)-1-oxy-2-(phenylmethyl)butyl]phenylmethylaminoethyl ethyl bromide (2-〇乂6-port 311〇1^, 2-{{4-[2-(dimethylamino)-l-oxo-2-(phenylmethyl)butyl]phenyl} -10 methylamino}-ethyl ester) [Note: 2-oxepanone is ε - 己内 S] cum The intermediate product is 369 Ν, which is 2-(dimethylamino)-1-{4-[(2-hydroxyethyl)decylamino]phenyl}-2-phenylindol-1-T- ( 2-(Dimethylamino)-1 - {4-[(2-hydroxyethyl)methylamino]phenyl} -2-phenylmethyl-1 -butanone), the synthetic route is as follows:

1. ε-caprolactone 2. Scat-24

Wherein η may be an integer from 1 to 10, preferably from 1 to 6. 2-. 2-(Dimethylamino)-1-{4-[(2-hydroxyethyl)methylamino]phenyl b-2- 30 15 1277834 玖, invention description phenylmercapto-1-butene Synthesis of ketone (compound 369N): 100 g of 2-(didecylamino)-1-(4-fluorophenyl)-2-phenylmethyl-1-butanthene (2-dimethylaniino-l- (4-fluorophenyl)-2-phenylmethyl-l-butanone (compound 369F, prepared as disclosed in US Pat. No. 5,077,402) and 600 g of 2-(methylamino)ethanol In a 2 L reaction flask, the mixture was uniformly stirred and then purged with nitrogen (puri: ge) 5 times. After heating to 150 ° C and stirring for 3 hours, 50 g of compound 369F was added to the reaction flask, and the reaction was continued for 2 hours, and then 50 g of compound 369F was added to the reaction flask, and the reaction was continued for 4 hours. . Finally, after the reaction temperature was lowered to 40 ° C, the remaining 2-(methylamino)ethanol was distilled off at 470 g at 48 ° C and 2.0 ton·, and 200 g of toluene and 400 g were added. The water was uniformly stirred, and the aqueous layer was removed. Then, 200 g of water was added, and the mixture was uniformly stirred for 10 minutes, and then the aqueous layer was removed, and the benzene was removed to obtain Compound 369N. 15 Properties of the title compound: NMR (CDC13, 200 MHz): δ 8.35 (d, J = 9.0 Hz, 2 H), 7.20-7.27 (m, 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, / = 7.4 Hz, 3 H). 20 B. 2-Oxpexone, 2_{{4-[2-(dimethylamino)-1-oxy-2-(phenylmethyl)butyl]phenyl}decylamino Synthesis of ethyl ethyl ester (2-〇{〇2^,2-{{4_[2-(dimethylamino)-l-oxo-2-(phenylmethyI)butyl]phenyl}-methylamino}-ethyl ester, compound 3690) ··········· After the reaction for 4 hours, 7 8 g of ε-caprolactone was added and the reaction was continued for 4 hours. Finally, the remaining ε-caprolactone was removed at 50 ° C and 2 torr to obtain 401 g of red. Brown transparent viscous liquid (yield 5 93.7%). Properties of the title compound (n=3): H NMR (CDC13? 200 MHz): δ 8.36 (d, J = 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, 1 H), 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 (t9 J = 7.4 Hz, 3 H). IR (KBr): 3514, 2940, 2866, 1734, 1657, 1642, 1593, 1547, 1462, 1379, 1249, 1183, 823, 704, 662 cm-1. 15 UV (λ max) two 335.1 nm. The product obtained was n = 3 compound 3690 having a molecular weight of about 650 based on 1H NMR data. <Experiment 1> Comparison of optical speed performance and odor property To test the compound of the present invention, whether 20 is suitable as a photoinitiator compared to the conventional MMMP, and in this test, MMMP-3, MMMP-6 The compound 3690 was applied to a printing ink having the composition shown in Table 2 below for comparison with a conventional MMMP for photospeed performance and odor properties. Material '· 32 1277834 玖, Invention Description 1. MMMP: Available from ciba Speciality Chemicals Holding Inc. ’ Trade name irgacure 907. 2·ΜΜΜΡ-3: A compound obtained according to the above Example 1. 3. ΜΜΜΡ-6: A compound obtained according to the above Example 1. 5 4. Compound 3690: a compound obtained according to the above Example 3. 5. Ethyl Michler’s ketone: available from the country

Chitec Chemical Co., Ltd., Taiwan, R.O.c., under the trade name Chivacure EMK, is used as a photosensitizer in photopolymerization of printing inks. 10 6. Isopropyl thioxanthone: available from the country of Chitin Chemical Co., Ltd. under the trade name Chivacure ITX, which is used as a photosensitizer in photopolymerization of printing inks. 7. Trimethylolpropane triacrylate (TMPTA): available from UCB Chemical Co. as a monomeric compound in photopolymerization of printing inks.

8. Eberyl 3702: available from UCB Chemical Co. as a polymer in photopolymerization of printing inks. 9. Fastogen Blue 5380-E (C.I.B.-15:3) ·· is available from Dainppon Ink and Chemical Co. as a pigment in printing inks. 20 Method, A. Composition of test ink: The above compounds were formulated into four different test inks as shown in Table 2 below. 33 1277834 玖, invention description table 2. composition of test ink ink 1 ink 2 ink 3 ink 4 MMMP 4*1 one - MMMP-3 one 8 * 2 - MMMP-6 - one 12 compound 3690 8 * z ethyl rice bran _ 0.5 0.5 0.5 0.5 Isopropyl thioxanthone 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 Three-roll mill grinding 2 times - 氺j 一一*: by weight *2: one by weight based on the same equivalent weight: instead of grinding method by blending 5 B. Photopolymerization of test ink: one ink of 10 μηι The layers were applied to a standard cardboard and cured using a Fusion D-lamp (Fusion Model: F300S) at 300 W/in to form a coating. C. Determination of photospeed: Record the light speed of the test ink in in/min until a non-stick coating is formed. D. Determination of odour: To test the odor, the coating formed from the test ink was heated under 8 Torr for a period of 5 minutes, and it was evaluated whether the coating had a release-odor during the period. The final assessment is classified as "irritating odor" or "none". 15 Results, the four test inks listed in Table 2 were taken to the light speed and odor test and the results are shown in Table 3 below. 34 1277834 玖, Invention Description Table 3. Comparison of Light Velocity Performance and Odor Properties Ink 1 Ink 2 Ink 3 Ink 4 Light Speed (in/min) 640 620 540 700~ The odor irritating odor after curing is odorless, odorless and odorless As is clear from Table 3, the serious odor problem of the ink 1 does not occur in the ink 2 (including MMMP-3), the ink 3 (including MMMp_6), and the ink 4 (containing the compound 3690). Further, the optical velocities of 5 ink 1 and ink 2 are similar on the basis of the same equivalent. This confirms the effectiveness of the polymerizable structure in which the ink of the present invention as a photoinitiator is irradiated to form a coating. Further, when the compound of the present invention is used, there is an advantage in that, in the case of producing a printing ink, the ink composition can be formulated by merely blending without being subjected to grinding treatment. 1〇 <Experiment 2 &gt; Comparison of Viscosity Performance is to test the effect of the compound of the present invention on the viscosity properties of the finished product compared to the conventional MMMp, especially in summer. Next, the viscous performance tests were carried out with the four inks shown in Table 2, wherein the test inks were introduced to simulate the summer of the transport 15 and the minimum heat treatment of the storage conditions over a period of time. Method: Store the ink in an oven set to 6 〇〇c and take a portion of the test ink for analysis at the time interval specified in Table 4. The viscous system was determined by using a viscometer 20 (model RVDV-D) from Br〇〇kfiled and recorded in centipoise (cps). Results 'The four tests listed in Table 2 The ink was introduced to the viscous performance test, 35 1277834 玖, the results of the invention are shown in the following Table 4. Table 4: The viscosity of the ink changes with respect to time at 60 ° C. Ink 1 Ink 2 Ink 3 Ink 4 0 6280*1 - 4400 4120 3800 24 6480 5000 4500 Gelation 64 8270 6510 5700 Gelation 200 12400 9640 9200 Gelation ^: The unit is centipoise (CPS). As can be seen from Table 4 above, compared to the conventional MMMP Ink 5, the ink containing the compound of the present invention has a lower initial viscosity, and the ink containing MMMP-3 or MMMP-6 is more resistant to gelation. <Experiment 3>MMMP-3 and Compound 3690 and BDMB Comparison This experiment further compares the difference between MMMP-3 and compound 3690 and BDMB in terms of light speed performance and intensifier stability (in-10 can stability). Material* 1. BDMB: Available from Ciba Specialty Chemicals Holding Inc., trade name Irg Acure 369. 2. MMMP-3 · A compound prepared according to the above Example 1. 15 3. Compound 3690: a compound obtained according to the above Example 3. 4. Ethyl Michrone (ethyl MiChler's ketone) : See experiment 1 above. 5. Isopropyl thioxanthone: See experiment 1 above. 三 6. Trimethylolpropane triacrylate (TMPTA): See experiment 1 above. 20 7. Eberyl 3702 · see above Experiment 1. 36 1277834 玖, conclusion of the invention: It is clear from the above illustrative experiments and description that MMMP-3, MMMP-6 and compound 3690 according to the present invention, in particular, compared to the conventional MMMP and BDMB, MMMP-3 has the following unique characteristics: 5 1. The odor problem is completely overcome; 2. The optical speed performance of the MMMP-3 of the present invention is based on the same MMMP and BDMB. The equivalent is lower; 3. The lower viscosity can be achieved, which is beneficial to the application of elastic flexographic printing or gravure ink; 10 4. There is no longer a problem of premature gelation , a constant viscosity system is achievable Formulation composition can provide longer shelf life; 5. stabilizer may not be required, and not only simplifies further formulation work saving manufacturing costs; and 6 do not need polishing process, saving time and labor costs. In addition, the compound 3690 in this case is faster than MMMP-3 in drying speed and is equivalent to BDMD. Although compound 3690 and BDMD will suffer the same problem of gelation, this problem can be solved after the addition of 〇·5 % stabilizer, and when using compound 3690, no grinding is required, and the viscosity of the ink system is lowered. Therefore, the more conventional BDMD is 20 excellent. All of the patents and documents cited in the specification of the present invention are incorporated herein by reference in their entirety. In case of conflict, the detailed description of the invention in this case (including definitions) will prevail. While the invention has been described by the foregoing detailed description and the preferred embodiments of the invention, the description of the invention is not to be construed as being limited thereto; rather, the present invention is intended to be Various other equivalent changes and modifications can be made by the skilled artisan from the technical content and implementation disclosed in the present specification. Therefore, without departing from the spirit of the invention, the simple equivalent changes and modifications made by the present invention within the scope of the invention and the scope of the invention are still within the scope of the invention. t Schematic description 3 (none) _ 10 [The main components of the diagram represent the symbol table] 39

Claims (1)

1277834|(四)年^作修(A) is replacing page 一L 一...like-*·-&quot;一u__|M|'_ηβηι 4 Pickup, Patent Application No. 092108013 Patent Application Patent Revision Amendment :June, 1994. 1. A compound having the following chemical formula (I): Wherein Xi represents: H, S, 〇, N or a dish (wherein R is a 卟C12 alkyl group), \ represents: 11, 3, 〇1 or a service (wherein a compound (^ C12 alkyl group) , wherein X1 and X2 are not simultaneously Η, and wherein when both X1 and 2 are not Η, Xi &gt; and 2 ·, R, represent: - a C% 2 alkyl group (Ci_Ci2aikyi_ group) or a group of the formula -(CH2OCH2)p_, wherein p is an integer from 1 to 4, K and R2 are each represented by: hydrazine, phenyl, or a Cl_Cl2 alkyl group optionally substituted by a phenyl group. , C2_C12 alkenyl or CVCu alkane group; R3 and IU each independently represent a Ci-C6 danyl group selectively substituted by a hydroxy group 1277834, the patent application scope or R_3 and R4 together with a nitrogen atom bonded thereto Forming together a cyclic group selected from the group below R5 means: H, F, C, ΒΓ, Ι', phenyl, Ci_Ci2, or C1_C12 alkoxy; ...................... .................................................. .................................................... When Xl or When χ2 is H, k is 0; when &amp; or X2 is S, Ο or NR, k is 1; and when Xl or &amp; is N, k is 2; m is an integer from 2 to 5; When k is 1, n is an integer from [to plus; and when k is 2, η = ηι + ηβ20, where ~ and seven are each an integer from 1 to 10. 2. A compound of claim i, wherein R is an ethyl group. 3. A compound as claimed in claim 1, wherein one of &amp; and Χ2 is S or 〇, and the other is Η. 4. A compound as claimed in claim 1 wherein m is 5. 5. A compound of claim 3, wherein R is an ethyl group. 6. For the compound of claim 5, wherein n is 3. 7. The compound of claim 5, wherein the η system is 6. 8. The compound of claim 1, wherein &amp; and ruler 2 are each a group selected from the group consisting of: 1277834 pick, patent application base, ethyl, propyl a phenyl group substituted with a phenyl group and a phenyl group substituted with a phenyl group. 9. A compound of claim 8 wherein both Ri and & are methyl. 5. A compound according to claim 8 wherein R1 is a phenyl substituted indenyl group and r2 is an ethyl group. u·如土111 is a group selected from the group consisting of methyl, ethyl, propyl and hydroxy substituted propyl groups. 10 12. The compound of claim 1, wherein r3 together with the nitrogen atom to which the fluorene-N oxime is attached forms a group/group. 3. The compound of claim 1, wherein: one of Χι and X2 is S, and the other is η, which is an ethyl group, 15 Rl and 2 are each methyl And R3 and R4 together with the nitrogen atom to which they are bonded form an i 0 U group, R 5 is Η, and m is a compound of 5th patent of the patent term, wherein the η system is 3. 5. The compound of claim 13 wherein the η system is 6. 16. If you apply for a compound of the specific item i, among them &amp; & &3; 3,778,834, the patent application is one of N, and the other is H. 17. A compound according to claim 16 wherein R is an ethyl group. 18. The compound of claim 17 of the patent application, wherein the m system is 5 〇. For example, the compound of the 18th item of the patent application scope, wherein the total of ηι+η2 is 6 〇.......... .................................................. ............................................... .................................................. .................................................. .................................................. .................................................. ............................ 20. The compound of claim 16 wherein Ri and R2 are each selected individually. Groups from the group consisting of methyl, ethyl, propyl, phenyl substituted indenyl and phenyl substituted propyl. 21. The compound of claim 20, wherein both Ri and r2 are sulfhydryl groups. • A compound as claimed in claim 16 wherein each of them is a group selected from the group consisting of thiol, ethyl, propyl and hydroxy substituted propyl groups. 23. A compound as claimed in claim 16, wherein R4 together with the nitrogen atom to which it is attached forms a \_y. Group. 24. The compound of claim 1, wherein one of χι and X2 is N and the other is η, which is an ethyl group, and Ri and R2 are each methyl, I and h Together with the nitrogen atoms connected to it, form a Ϊ277834 pick, patent application scope -N 〇 a group, k is 2 m for 5, and 5, ^1+Π2 = 6 0 25·^ίtmMM9 L compound, wherein one of Χι and X2 is NR (where R is methyl or ethyl) And the other is oxime, an ethyl group, 10 Ri is a phenyl substituted methyl group, h is an ethyl group, I and r4 are each a methyl group, I is a fluorene, and m is 5. The compound of any one of claims 1 to 15 which is useful as a photoinitiator. 27. A method for the manufacture of a compound of formula (I) as defined in claim 1 of the patent application, comprising the steps of: a compound having the formula (II) and a compound 2 The compound of the formula (III) is reacted to form the compound of the formula (I): 1277834 wherein R R5 is the same as those of the ........... ~....·..-......................................——_... .. —..... Χι means: H, S, 〇, n痞nr〆甘a such as r A NR (where R is a Ci-C12 alkyl group), x2 means: ^, (^ or call Wherein Han is a core C12 alkyl group), s is 0 or 1; 10 pick, patent application scope (H0-R)-X2 (Π) where 'Χ4Χ2 cannot be H at the same time, and 'When both &amp; and X2 are not ', and 8 is 1; and when &amp; or Χ2 is Η, s is 〇; Ο ^ , ( HI) ✓, q is an integer from 1 to 4. 28. The method of claim 27, wherein the method is carried out in the presence of a tin-containing catalyst. 29. The method of claim 28, wherein the method is carried out in the presence of n-butyltin dialkylcarboxylate [n-butyl seven n's her coffee SCAT-24]. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> Ester (/3-propiolactone), r-butyrolactose (7-butylolactone), 5-valerolactone (5-valerolactone) and £__caprolactone. 31. If the method of claim 30 is applied, the method of using the chemical Α (ιιι) for esterification rebellion..................... .................................................. ..............................-................... 32. The method of claim 27, wherein the compound of formula (II) is used by a compound having the following chemical formula (Π) and a compound having the following chemical formula (IV) Generated by phase reaction: 0 (II,) where Ri R2 R3, R4 are defined in the same way as those defined in item 1 of the scope of the patent application, Υι means: Η, F, Cl, Br, I or cyano, meaning ·, F, Cl, Br, I or cyano, wherein Yl and Y2 are not simultaneously Η, and wherein when both Yl and Y2 are not ,, Yj = (IV) R,, XR, 〇H, 20 1277834 The scope of patent X is S, 〇, NH or NR (where R is a Ci_c12 alkyl group), and the meaning of R is the same as that defined in item 1 of the scope of the patent application; and when X is S When 0 or NR, R" is H; and when χ is NH, R, is R, 〇H. 33·-« 32 , ^^ Among the compounds of the formula (Π,), Υι and One of Υ2 is Η, and the other is F, c 玢 or 卜. 10. • The method of applying for patent 帛 33, in which the compound of the formula (Π,) is used, Υι and One of Υ2 is Η, and the other is 。. 35. The method of claim 33, wherein the compound of the formula (Π) is used , one of Y1 and γ2 is Η, and the other is C. 36. The method of claim 32, wherein among the compounds of the formula (Π,), 1 and Υ2 are The method of claim 32, wherein in the compound of the formula (π,) in which 2 〇 δ is used, both 丫 and Υ 2 are C1. 38. The method of item 32, wherein among the compounds of formula ("), wherein 1 and R2 are each a group selected from the group consisting of methyl, ethyl and propyl groups; a phenyl-substituted methyl group and a phenyl-substituted propyl group. 39. The method of claim 38, wherein in the compound of the formula (π,), Rl and R2 are both methyl hydrazine 40. The method of claim 38, wherein the center is a phenyl-substituted fluorenyl group, and R2 is an ethyl group. The method of claim 32, wherein In the compound of the formula (Π,), the heart and R4 are each completely Self-cutting _ ...-............................................. .................................................. a propyl group substituted with a propyl group and a hydroxy group. 42. The method of claim 32, wherein the compound of the formula (Π) is used after being used Medium, &amp; and r4 together with the nitrogen atom to which N-〇 is attached form a ^/group. 43. The method of claim 32, wherein the compound of formula (IV) is HS(R, OH) and R is an exoethyl group. 15 44. The method of claim 32, wherein the compound of formula (IV) is NH(R,OH)2 and R is an ethyl group. 45. The method of claim 32, wherein the compound of formula (IV) is RNH (R'OH) and R is 20 . ', a methyl group, and R, It is a stretched ethyl group. 46. The method of claim 32, wherein the compound of formula (IV) is RNH(R, OH), and R is an ethyl group, and R is a stretch Ethyl group. The method of claim 32, wherein in the compound of the formula (Π,), one of Yl and Y2 is H, and the other is ^^ , order or l; Ri and R2 are each methyl; 厌3 and R4 together with the nitrogen source attached thereto And the R5 system is Η; the sub- together with the one-group/group negatively used, the straight f S(IV) compound 谗 is HS (R'OH), and the R' is an ethyl group. And the compound of the formula (π) thus produced is introduced to react with ε-caprolactone to form the compound 10 of the formula (1), wherein one of X and X2 is s, and the other One is Η. 48. The method of claim 47, wherein in the compound of formula (I) produced, the η system is 3. 49. The method of claim 47, wherein in the compound far from formula (I), the η system is 6. 5. The method of claim 32, wherein in the compound of the formula (Π,), one of Y1 and γ2 is H, and the other is F, ci, Br Or I; Ri and R2 are each a sulfhydryl group; Rs and r4 together with a nitrogen atom to which they are attached form a W group; and Rs is a hydrazine; the chemical formula used is The compound of IV) is NH(R'〇H)2, and R' is an exoethyl group, and 10 1277834 picks up, the patented range is such that the compound of formula (11) is introduced to The compound of the formula (1) is formed by reacting with ε-caprolactone, wherein one of X! and X2 is oxime, and the other is oxime; and 111+112=6. 5 51. The method of claim 32, wherein in the compound of formula (π,) used, Υι and ^ ^ ^ ^ Η 5 ^ 3 # % F &quot; Cl - Br ^ I ; Rj and R2 are each a group selected from the group consisting of fluorenyl, ethyl, propyl, phenyl-substituted methyl and phenyl-substituted propyl; heart and R4 The compound of the formula (IV) is RNH (R, QH), the + R is methyl or ethyl, and the towel r is an ethyl group. a group, and 5 the compound of the formula (Π) thus produced is introduced to react with ε-hexidine to form the compound of formula (1), wherein one of the 1 and 12 is gNR (R It is a thiol or ethyl group, and the other is hydrazine. And a compound of the formula (I). 53. The photopolymerizable composition of claim 52, further comprising a pigment or dye. 54. Use of a compound of the formula (I) having the chemical formula 11 1277834, as claimed in any one of claims i to 25, for use as a photoinitiator of a printing ink. 12