CN1453272A - Novel morpholone derivative and its prepn and use - Google Patents
Novel morpholone derivative and its prepn and use Download PDFInfo
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- CN1453272A CN1453272A CN 03110380 CN03110380A CN1453272A CN 1453272 A CN1453272 A CN 1453272A CN 03110380 CN03110380 CN 03110380 CN 03110380 A CN03110380 A CN 03110380A CN 1453272 A CN1453272 A CN 1453272A
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Abstract
The present invention reveals one kind of novel morpholone derivative and its preparation process and use as light initiator for light polymerized composite.
Description
Technical field
The present invention relates to a kind of morpholinyl ketone (morpholinoketone) derivative and preparation method thereof and purposes of the novelty that can be used as light trigger.
Technical field
Compared to traditional lithography technique, UV cured printed The Application of Technology aspect is more extensive, it not only can be applied to making traditional stone plate seal China ink (lithographic ink), graph China ink (offset ink), relief printing plate seal China ink (letter press ink), elasticity relief printing plate seal China ink (Flexo ink), intaglio printing ink (gravureink), silk screen printing seal China ink (silk screen ink) etc., more can be applied in the manufacturing of printed circuit board (PCB), photo-resist, solder flux shielding (solder masker, other have to be commonly called as be green lacquer), dielectric base material etc.Generally speaking, the UV process of setting needs wedding agent (binder), photopolymerizable monomer and light trigger, and wherein this light trigger can make this monomer generation polymerization and generate polymkeric substance in the short period of time of UV irradiation.
The photochemical polymerization reaction of using unsaturated monomer and prepolymer is a kind of commonly used existing method of industrial applicability widely.US 3,661, penetrate the solvent-free printing ink composition of solidified but 614 disclose a kind of width of cloth, it is made of following substantially: (1) is a kind of pentaerythritol acrylate, methacrylic ester or the itaconic ester of 20wt% to 98wt% approximately, (2) a kind of halogenated aromatic, the alicyclic or aliphatic hydrocrbon light trigger of about 2wt% to 80wt%, wherein halogen atom is connected directly on the carbochain of the ring structure of aromatics and alicyclic compound and aliphatic cpd, and (3) a kind of colorant.
US 4; 672; 079 discloses the polymerizability or the polymerisable aromatic-aliphatic ketone of the light trigger that can be provided as polyreaction; be preferably 2-hydroxy-2-methyl (4-ethenylphenyl ethyl ketone) [2-hydroxy-2-methyl (4-vinylpropiophenone)]; 2-hydroxy-2-methyl-p-(1-methyl ethylene) Propiophenone (2-hydroxy-2-methyl-p-(1-methylvinyl) propiophenone); p-vinyl benzene formyl radical hexalin (p-vinylbenzoylcyclohexanol); p-(1-methyl ethylene) benzoyl-hexalin (p-(1-methylvinyl) benzoyl-cyclohexanol) and these oligomerization and polymerisate are suitable for the light trigger as the photopolymerization reaction of ethylene linkage unsaturated monomer and prepolymer.
US 4,943, and 516 disclose a kind of photosensitive thermosetting resin composition, and it includes: (a) a kind of photosensitivity prepolymer contains at least two ethylene linkage unsaturated link(age)s at its molecular cell; (b) a kind of light trigger; (c) a kind of vinyl monomer of photopolymerization and/or a kind of organic solvent are as thinner; (d) a kind of finely powdered epoxy compounds, its minute sub-unit contain at least two epoxide groups, and in the solvent that will be used, show limited solvability; And (e) a kind of solidifying agent for used for epoxy resin optionally.The storage time that the revealed meeting of this photosensitive thermosetting resin composition represents good video picture character and susceptibility and segment length's time is provided.When be directed to coating, expose to the open air, video picture and post curing treatment, this photosensitive thermosetting resin composition can be formed one and corrode the good solder flux shielding pattern of showing in nature of resistance or the like at attaching property, insulation resistance, electrolyte.
US 4,582,862 disclose a kind of photo curable colored composition, and it includes: (a) tackiness agent of the undersaturated photopolymerization of alkene key, (b) a kind of pigment of 5-60% weight meter, and (c) 0.1-20% weight meter a kind of has the light trigger of the chemical formula (I) that this case discloses.Especially, the 2-methyl isophthalic acid that in this case, is disclosed-[4-(methylthio group) phenyl]-2-morpholinyl third-1-ketone (2-methyl-1-[4-(methylthio) phenyl]-2-morpholino-propane-1-one, MMMP) become the light trigger that is widely used now, particularly be applied to being added with in the UV system of pigment, for example solder flux shielding and UV printing ink.According to newspaper, MMMP is not undermining the ray velocity (photospeed) and the mechanical properties that can provide good under the non-yellowing properties matter of self.
But, when using MMMP, in solidifying the post-treatment processing, can occur the problem of unpleasant odor because of the volatile sulfur resistates, and the application on the industry is restricted.Especially, when MMMP is used in UV printing ink or solder flux shielding, can produce the problem from gentleness to tedious unpleasant odor in various degree, it is because the 4-methylthio phenyl formaldehyde (4-methylthiobenzaldehyde) with volatility stink that the photofragmentation effect (photofragmentation) of MMMP is generated that unpleasant odor is led.
Because the selection of operational light trigger is limited, the user often must stand the unpleasant odor problem of MMMP, or derivative (Luigi Angiolini et al., Journal of Applied.Ploymer Scinece (1995), the 55:1477-1488 of use MMMP; US 4,582, and 862, US 5,145,885, US5,506,279, US 5,837, and 746, WO 96/20795, US 6,048,667), US 5,145 particularly, (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one BDMB) is used as the substitute of MMMP to the 2-phenmethyl-2-dimethyl amido-1-that is disclosed in 885 (4-morpholino base phenyl) fourth-1-ketone.
Use MMMP and BDMB as for the pigment system (such as Cyan pigment) of main light trigger for some, can need excessive milled processed that whole light triggers is incorporated into, this can facilitate too early curing and cause ink viscosity increase or even gel, so need to add a polymerization stabilizer such as MEHQ (MEHQ).But this stablizer still can delay ray velocity at last.On the other hand, MMMP and BDMB tend to improve the viscosity of the printing ink generated, for the low-viscosity application of needs (such as elasticity relief printing plate), this be not like.
Therefore, based on the existing in prior technology shortcoming, have a novel substance that need remove to develop the light trigger that can be provided as photopolymerizable composition.
[summary of the invention]
Aspect first, the invention provides a kind of compound with following chemical formula (I):
Wherein
X
1Expression: H, S, O, N or NR, R wherein are a C
1-C
12Alkyl group,
X
2Expression: H, S, O, N or NR, R wherein are a C
1-C
12Alkyl group,
But condition is to work as X
1With X
2Neither when being H, X
1=X
2
R ' expression a: C
1-C
12Alkylidene group (C
1-C
12Alkylene group) or a chemical formula be-(CH
2OCH
2)
p-group, wherein p be one by 1 to 4 integer;
R
1With R
2Expression: H respectively separately, phenyl, or optionally by C that phenyl replaced
1-C
12Alkyl, C
2-C
12Thiazolinyl, C
1-C
12Alkoxyl group;
R
3With R
4Represent a C who is optionally replaced separately respectively by hydroxyl
1-C
6Alkyl,
Perhaps R
3With R
4Be selected from following cyclic group together with forming one with institute banded nitrogen-atoms:
With
R
5Expression: H, F, Cl, Br, I, nitro, phenyl, C
1-C
12Alkyl or C
1-C
12Alkoxyl group;
Work as X
1Or X
2During for H, k is 0; Work as X
1Or X
2During for S, O or NR, k is 1; And work as X
1Or X
2During for N, k is 2;
M be one by 2 to 5 integer; And
When k is 1, n be one by 1 to 20 integer, and when k is 2, n=n
1+ n
2≤ 20, n wherein
1With n
2Respectively be one by 1 to 10 integer.
Aspect second, the invention provides a kind of as mentioned above method of compound that is used to make with chemical formula (I), its step that comprises is: make a kind of compound and a kind of lactone compound phase reaction with chemical formula (III) with following chemical formula (II), and generate the compound that this has chemical formula (I):
Wherein
R
1, R
2, R
3, R
4With R
5Definition with identical to the above-mentioned definition that has in the chemical formula (I),
X
1Expression: (wherein R is a C for H, S, O, N or NR
1-C
12Alkyl group),
X
2Expression: (wherein R is a C for H, S, O, N or NR
1-C
12Alkyl group),
S is 0 or 1,
But condition is to work as X
1With X
2Neither when being H, X
1=X
2, and s is 1; And work as X
1Or X
2During for H, s is 0;
Wherein q be one by 1 to 4 integer.
Can supply this lactone compound of the usefulness of this case method to be selected from following group: beta-propiolactone, gamma-butyrolactone, δ-Wu Neizhi and 6-caprolactone with chemical formula (III).Preferably, this lactone compound with chemical formula (III) is a 6-caprolactone.
In a preferred embodiment, this case method is to carry out in the presence of a kind of stanniferous catalyzer.Preferably, this case method be in three alkane carboxylic acid normal-butyl tin (SCAT-24] existence under carry out.
In a preferred embodiment, the employed compound that this has chemical formula (II) of this case method is by a kind of compound and a kind of compound phase reaction with following chemical formula (IV) with following chemical formula (II ') is generated:
Wherein
R
1, R
2, R
3, R
4With R
5Definition and above-mentioned chemical formula (I) in definition identical,
Y
1Expression: H, F, Cl, Br, I or cyano group,
Y
2Expression: H, F, Cl, Br, I or cyano group,
But condition is to work as Y
1With Y
2Neither when being H, Y
1=Y
2
R " XR ' OH (IV) is wherein
X is that (wherein R is a C for S, O, NH or NR
1-C
12Alkyl group),
The definition of R ' is identical with definition in the above-mentioned chemical formula (I); And
When X is S, O or NR, R " be H; And when X is NH, R " be R ' OH.
This purposes with compound of chemical formula (I) is also contained in the present invention.For example, this case contriver finds that this compound with chemical formula (I) can be used as a light trigger and uses.Therefore, compound and the photopolymerizable monomer compound with chemical formula (I) of the present invention can be mixed with a kind of photopolymerizable composition, for example a kind of printing-ink.
Other purposes of the present invention, feature and advantage after the illustration with reference to following detailed description and preferred embodiment, will become obvious.
[detailed description of the invention]
For overcoming the unpleasant odor problem of MMMP institute tool, the present invention attempts by changing the molecular structure of MMMP on the methyl sulphur part that a polymerizability is linked to MMMP, and develops a kind of compound with following chemical formula (I):
Wherein
X
1Expression: (wherein R is a C for H, S, O, N or NR
1-C
12Alkyl group),
X
2Expression: (wherein R is a C for H, S, O, N or NR
1-C
12Alkyl group),
But condition is to work as X
1With X
2When being not H, X
1=X
2
R ' expression a: C
1-C
12Alkylidene group or a chemical formula are-(CH
2OCH
2)
p-group, wherein p be one by 1 to 4 integer;
R
1With R
2Expression: H respectively separately, phenyl, or optionally by C that phenyl replaced
1-C
12Alkyl, C
2-C
12Thiazolinyl, C
1-C
12Alkoxyl group;
R
3With R
4Represent a C who is optionally replaced separately respectively by hydroxyl
1-C
6Alkyl, perhaps R
3With R
4Together with forming a cyclic group that is selected from the following group with institute banded nitrogen-atoms:
With
R
5Expression: H, F, Cl, Br, I, nitro, phenyl, C
1-C
12Alkyl or C
1-C
12Alkoxyl group;
Work as X
1Or X
2During for H, k is 0; Work as X
1Or X
2During for S, O or NR, k is 1; And work as X
1Or X
2During for N, k is 2;
M be one by 2 to 5 integer; And
When k is 1, n be one by 1 to 20 integer, and when k is 2, n=n
1+ n
2≤ 20, n wherein
1With n
2Respectively be one by 1 to 10 integer.
In a preferred embodiment, m is 5.
In a preferred embodiment, R ' is a C
1-C
6Alkylidene group, particularly ethylidene, or be one with chemical formula-(CH
2OCH
2)-or-CH
2OCH
2CH
2OCH
2The group of-expression.
Preferably, R
1With R
2Be respectively one and be selected from following group: the propyl group that methyl that methyl, ethyl, propyl group, phenyl replace and phenyl replace.In a preferred embodiment, R
1With R
2Be all methyl.In another preferred embodiment, R
1Be the methyl of phenyl replacement, and R
2Be ethyl.
In a preferred embodiment, R
3With R
4It is a group that is selected from the following group that constitutes separately respectively: the propyl group that methyl, ethyl, propyl group and hydroxyl replace.In a better concrete example, R
3With R
4Be all methyl.
In another preferred embodiment, R
3With R
4Together with forming one with institute banded nitrogen-atoms
Group.
In a preferred embodiment, R
5Be H, F, Cl, Br, I, phenyl or C
1-C
6Alkyl.In a better concrete example, R
5Be H.
In a preferred embodiment, X
1With X
2In the middle of have one for S or O, and another is H.In a better concrete example, n is 3.In another better concrete example, n is 6.
In a better concrete example, X
1With X
2In the middle of have one for S, and another is H, R ' is an ethylidene group, R
1With R
2Be methyl separately respectively, R
3With R
4Together with forming one with institute banded nitrogen-atoms
Group, R
5Be H, and m is 5.
In another preferred embodiment, X
1With X
2Have one to be N, and another is H, and n
1+ n
2Sum total be preferably 6.
In a better concrete example, X
1With X
2In the middle of have one for N, and another is H, R ' is an ethylidene, R
1With R
2Be respectively methyl separately, R
3With R
4Together with forming one with institute banded nitrogen-atoms
Group, R
5Be H, m is 5, and n
1+ n
2=6.
In another preferred embodiment, X
1With X
2In the middle of have one for NR (wherein R is a C
1-C
12And another is H alkyl group).In a better concrete example, X
1With X
2In the middle of have one for NCH
3, and another is H; R
1Be the methyl of phenyl replacement, and R
2Be ethyl; And R
3With R
4Be all methyl.In another better concrete example, X
1With X
2In the middle of have one for NC
2H
5, and another is H; R
1Be the methyl of phenyl replacement, and R
2Be ethyl; And R
3With R
4Be all methyl.
This compound with chemical formula (I) can prepare by a kind of method that comprises the following step: make a kind of compound and a kind of lactone compound phase reaction with chemical formula (III) with following chemical formula (II), and generate the compound that this has chemical formula (I):
Wherein
R
1, R
2, R
3, R
4With R
5Definition and above-mentioned chemical formula (I) in definition identical,
X
1Expression: (wherein R is a C for H, S, O, N or NR
1-C
12Alkyl),
X
2Expression: (wherein R is a C for H, S, O, N or NR
1-C
12Alkyl),
S is 0 or 1,
But condition is to work as X
1With X
2Not during for H, X
1=X
2, and s is 1; And work as X
1Or X
2During for H, s is 0;
Wherein q be one by 1 to 4 integer.
Has the compound of chemical formula (II) about this, its preparation can be carried out with reference to previous methods, for example, be disclosed in the synthetic technology in the above-mentioned mentioned preceding case document, comprise Luigi Angiolini et al., Journal of Applied.Ploymer Scinece (1995), 55:1477-1488; US 4,582, and 862, US 5,145,885, US 5,506,279, US 5,837,746, WO 96/20795, US 6,048,667 etc.
Can be selected from following for this lactone compound that this case method is used: beta-propiolactone, gamma-butyrolactone, δ-Wu Neizhi and 6-caprolactone with chemical formula (III).In a preferred embodiment, this lactone compound with chemical formula (III) is a 6-caprolactone.These lactone compounds are commercially available, for example, and can be available from DAICEL Chemical Co..
Use this lactone compound to be used as the advantage that polymerizability chain source had to be with chemical formula (III):
(1) can easily control the molecular weight of product,
(2) high pigment wetting quality,
(3) high UV stability,
(4) hypotoxicity (biological decomposable), and
(5) low viscosity.
This case method can use a catalyzer that can be used for the ring-opening polymerization of this lactone compound with chemical formula (III) to carry out.The catalyzer that is applicable to this case method is, for example, tetraethyl titanate (tetraethyltitanate), metatitanic acid orthocarbonate (tetrapropyl titanate), tetrabutyl titanate (tetrabutyltitanate) or other contain titanate compound, stannous octoate (stannous octoate), dibutyl tin oxide (dibutyl-tin-oxide), dibutyl tin two lauric acid salt (dibutyl-tin-dilaurate), a kind of three alkane carboxylic acid normal-butyl tin [n-butyl-tin tris (alkanoate) or other organo-tin compounds, tin protochloride, (US 6 for tin protobromide or other halogenation stannous compound, 037,393).
In a preferred embodiment, this case method is carried out under a kind of existence of stanniferous catalyzer.In a better concrete example, this case method is carried out under the existence of three alkane carboxylic acid normal-butyl tin [SCAT-24].
In a preferred embodiment, the employed compound that this has a chemical formula (II) of this case method generates by a kind of compound and a kind of compound phase reaction with following chemical formula (IV) with following chemical formula (II '):
Wherein
R
1, R
2, R
3, R
4With R
5Definition and above-mentioned chemical formula (I) in definition identical,
Y
1Expression: H, F, Cl, Br, I or cyano group,
Y
2Expression: H, F, Cl, Br, I or cyano group,
But condition is to work as Y
1With Y
2Not during for H, Y
1=Y
2
R " XR ' OH (IV) is wherein
X is that (wherein R is a C for S, O, NH or NR
1-C
12Alkyl),
The definition of R ' is same as that and defines identical for above-mentioned chemical formula (I) is middle; And
When X is S, O or NR, R " be H; And when X is NH, R " be R ' OH.
Has the compound of chemical formula (II ') about this, its preparation can be carried out with reference to previous methods, for example, this preparation with compound of chemical formula (II ') can be with reference to US 4,582,862 relevant announcement according to following route of synthesis, and is introduced into amido in the arylalkyl ketone compound of a correspondence:
Wherein Hal represents halogen, and R
1To R
5And Y
1With Y
2Definition and above-mentioned chemical formula (II ') in definition identical.
In a preferred embodiment of the present invention, the compound that this that uses has chemical formula (II ') is Y
1With Y
2In the middle of have one for H, and another is the compound of F, Cl, Br or I.More preferably, Y
1With Y
2In have one for H, and another is F or Cl.In another preferred embodiment of the present invention, the compound that this that is used has chemical formula (II ') is Y
1With Y
2Be all the compound of F or Cl.
In a preferred embodiment of the present invention, the compound that this that uses has chemical formula (II ') is R
1With R
2It is a compound that is selected from following groups separately respectively: the propyl group that methyl that methyl, ethyl, propyl group, phenyl replace and phenyl replace.In a better concrete example, R
1With R
2Be all methyl.In another better concrete example, R
1Be the methyl of phenyl replacement, and R
2Be ethyl.
In a preferred embodiment of the present invention, the compound that this that uses has chemical formula (II ') is R
3With R
4Together with forming one with institute banded nitrogen-atoms
The compound of group.
In another preferred embodiment of the present invention, the compound that this that uses has chemical formula (II ') is R
3With R
4It is a compound that is selected from following groups separately respectively: the propyl group that methyl, ethyl, propyl group and hydroxyl replace.
In a preferred embodiment of the present invention, the compound that this of use has chemical formula (II ') is a wherein R
5Be H, F, Cl, Br, I, phenyl or C
1-C
6The compound of alkyl.In a better concrete example, R
5Be H.
This compound with chemical formula (IV) is commercially available, for example, and can be available from BASFCorporation.
In a preferred embodiment, the compound that this has chemical formula (IV) used in the present invention is HS (R ' OH), and wherein R ' is an ethylidene.In another preferred embodiment, the compound that this has chemical formula (IV) used in the present invention is NH (R ' OH)
2, wherein R ' is an ethylidene.In another preferred embodiment, the compound that this has chemical formula (IV) used in the present invention is RNH (R ' OH), and wherein R is a methyl or ethyl, and R ' is an ethylidene.
In a preferred embodiment of the present invention, the compound that this that is used for this case preparation method has chemical formula (II ') is compound, wherein a Y
1With Y
2In the middle of have one for H, and another is F, Cl, Br or I; R
1With R
2Be methyl separately respectively; R
3With R
4Together with forming one with institute banded nitrogen-atoms
Group; And R
5Be H; This compound with chemical formula (IV) that is used in this case preparation method is HS (R ' OH), and wherein R ' is an ethylidene; And this compound with chemical formula (II) that generates like this is directed to and the 6-caprolactone phase reaction, and generates the compound that this has chemical formula (I), wherein X
1With X
2In the middle of have one for S, and another is H.
In another preferred embodiment of the present invention, being used in the compound that among this case preparation method this have chemical formula (II ') is compound, wherein a Y
1With Y
2In the middle of have one for H, and another is F, Cl, Br or I; R
1With R
2Be methyl separately respectively; R
3With R
4Together with forming one with institute banded nitrogen-atoms
Group; And R
5Be H; This compound with chemical formula (IV) that is used for this case preparation method is NH (R ' OH)
2, wherein R ' is an ethylidene; And this compound with chemical formula (II) that generates like this is directed to and the 6-caprolactone phase reaction, and generates the compound that this has chemical formula (I), wherein X
1With X
2In the middle of have one for N, and another is H; And n
1+ n
2=6.
In another preferred embodiment of the present invention, the compound that this that is used for this case preparation method has chemical formula (II ') is compound, wherein a Y
1With Y
2In the middle of have one for H, and another is F, Cl, Br or I; R
1With R
2Be respectively one separately and be selected from following groups: the propyl group that methyl that methyl, ethyl, propyl group, phenyl replace and phenyl replace; R
3With R
4Be respectively methyl separately, R
5Be H; Be used in this compound with chemical formula (IV) among this case preparation method and be RNH (R ' OH), wherein R is methyl or ethyl, and R ' is an ethylidene; And this compound with chemical formula (II) that generates like this is directed to and the phase reaction of e-caprolactone, and generates the compound that this has chemical formula (I), wherein X
1With X
2In the middle of have one for NR (R is methyl or ethyl), and another is H.
This purposes with compound of chemical formula (I) is also contained in the present invention.According to the present invention, this has chemical formula (I) compound and can be used as a light trigger and use, and it can not produce the unpleasant odor problem relevant with MMMP usually, and a photopolymerizable composition that contains this case chemical formula (I) compound can not increase problem by toughness yet.Therefore, learn according to the detailed methods availalbe of knowing in this skill, come together to fill a prescription according to chemical formula of the present invention (I) compound and following component: the photopolymerizable monomer compound, photosensitizers, pigment or dyestuff, and other are to have the knack of the additive that this technology personage is usually used in preparing photopolymerizable composition, such as oligomeric, photosensitizers (photosensitizers), amine addition agent and other rerum natura properties-correcting agent.
The expection compound with chemical formula (I) according to the present invention can be used for various industry to be used, and for example, uses on the industry of the relevant light trigger of being mentioned in the case document before above-mentioned.For example, the compound with chemical formula (I) according to the present invention can be filled a prescription and be used as a light trigger in UV ink (UV inks) or coating.Compound with chemical formula (I) according to the present invention also can be used in combination with traditional light trigger by expection, is disclosed in light trigger in the aforementioned documents such as those, particularly in US 4,672, is disclosed in 079.
The present invention puts up with following embodiment and is described further, but will be appreciated that, these embodiment are the usefulness for illustrating only.
＜embodiment 1〉MMMP-3 and MMMP-6 synthetic
How the present embodiment explanation synthesizes a kind of foundation compound of the present invention; for example 6-hydroxyl-caproic acid 5-(5-{2-[4-(2-methyl-2-morpholine-4-base-propionyl) phenyl sulfahydantoin]-ethoxy carbonyl-pentyloxy carbonyl)-the amyl group ester (6-hydroxy-hexanoic acid 5-(5-{2-[4-(2-methyl-2-morpholin-4-yl-propionyl)-phenylsulfanyl]-ethoxycarbonyl}-pentyloxycarbonyl) pentylester; MMMP-3) with 6-hydroxyl-caproic acid 5-(5-{2-[4-(2-methyl-2-morpholine-4-base-propionyl) phenyl sulfahydantoin]-ethoxy carbonyl-four (amyl group oxygen carbonyl)-amyl group esters (6-hydroxy-hexanoic acid 5-(5-{2-[4-(2-methyl-2-morpholin-4-yl-propionyl)-phenylsulfanyl]-ethoxycarbonyl}-tetra (pentyloxycarbonyl) pentyl ester; MMMP-6) and intermediate product 1-[4 (2-hydroxyl ethylmercapto group)-phenyl] 2-methyl-2-morpholinyl third-1-ketone (1-[4-(2-Hydroxyethylthio)-phenyl]-2-methyl-2-morpholino-propan-1-one; compound 2), Xiang Guan route of synthesis is as follows:
The molecular weight of the product compound that is wherein synthesized can be changed with the mol ratio of 6-caprolactone by adjusting compound 2, shown in MMMP-3 and MMMP-6 promptly is.
A.1-[4 (2-hydroxyl ethylmercapto group)-phenyl]-2-methyl-2-morpholinyl third-1-ketone (compound 2) synthetic:
The mercaptoethanol (mercaptoethanol) of 94.8g (1.21mol) and 600ml toluene are placed three neck round-bottomed flasks of a l litre, add the NaOH of 48.6g (1.21mol) then.Mixture is directed to reflow treatment and went through 6 hours, and collects formed water this moment by a Dean-Stark device.Toluene solvant is removed by distillation, connects and solid block is added the DMF of 250ml.After treating that solution is cooled to room temperature; 1-(4-the fluorophenyl)-2-methyl-2-morpholinyl-1-acetone (compound 1 that once adds 250g (0.93mol); according to United States Patent (USP) the 4th; 582; prepared for No. 862); and formed mixture is heated under 50 ℃ and spends the night under the atmosphere of a nitrogen protection.Mixture is cooled to room temperature, is diluted, and cleaned with water, the 2%NaOH aqueous solution and salt solution (brine) with 1 liter toluene.Organic layer is separated and is concentrated under vacuum, and obtains a yellow toughening oil, further by recrystallize with purifying, and generate a canescence (off-white) crystallisate (90% productive rate, fusing point: 62-64 ℃).
B.MMMP-3's is synthetic:
[commodity are called SCAT-24 with the compound 2 of 200g (0.65mol), the 6-caprolactone of 88.5g and the tin catalyst of 8g; available from the synthetic limited-liability company of three total machines of Japan (Sankyo OrganicChemistry Co., Ltd.)] place one to be equipped with a condenser and to be in 500 milliliters three neck round-bottomed flasks under the nitrogen protection.Mixture is heated to 80-85 ℃ and lasts 2 hours.The 6-caprolactone of 44.3g and the SCAT-24 of 4g be added in the above-mentioned flask in per 40 minutes, do 4 times, and kept this temperature 1 hour again.Formed mixture connects and cleans with water, the 2%NaOH aqueous solution and salt solution.Organic layer is concentrated under vacuum, and obtains a khaki oil (light tan oil) (398 grams, 95% productive rate).
The character that title compound records:
1H?NMR(CDCl
3，400MHz)：δ8.46(d，J＝8.4Hz，2H)，7.29(d，J＝8.4Hz，2H)，4.26(t，J＝6.9Hz，2H)，4.02(t，J＝6.5Hz，6H)，3.65(t，J＝3.8Hz，4H)，3.60(t，J＝6.5Hz，3.20(t，J＝6.9Hz，2H)，2.53(t，J＝3.8Hz，4H)，2.25-2.30(m，9H)，1.51-1.65(m，20H)，1.30-1.42(m，10H)，1.27(s，6H).IR(KBr)：3501，2942，2865，1741，691，1588，1563，1475，1402，1364，1158，1120，1093，980，882，761cm
-1。
According to gained
1H NMR data calculate that the n value of products therefrom compound is 3.Molecular weight with respect to MMMP is 279, and the molecular weight of products therefrom compound is about 650.
C.MMMP-6's is synthetic:
Synthesize MMMP-6 with the synthesis mode identical with MMMP-3, difference is to use 354g but not the 6-caprolactone of 88.5g, forms a cervine paste (97% productive rate).
The character that title compound records:
1H?NMR(CDCl
3，400MHz)：δ8.46(d，J＝8.4Hz，2H)，7.29(d，J＝8.4Hz，2H)，4.26(t，J＝6.9Hz，2H)，4.02(t，J＝6.5Hz，12H)，3.65(t，J＝3.8Hz，4H)，3.60(t，J＝6.5Hz，3.20(t，J＝6.5Hz，2H)，3.20(t，J＝6.9Hz，2H)，2.53(t，J＝3，8Hz，4H)，2.25-2.30(m，18H)，1.51-1.65(m，40H)，1.30-1.42(m，20H)，1.27(s，6H).
According to gained
1H NMR data calculate that the n value of products therefrom compound is 6, and molecular weight is about 960.
The physical properties of D.MMMP-3 and MMMP-6 relatively
MMMP-6 at room temperature is a paste, and MMMP-3 at room temperature is a light amber liquid.The thawing point of MMMP-3 is about about-15 ℃, can not solidify after leaving standstill 30 days under 0 ℃.1 physical properties of listing MMMP-3 and MMMP-6 of tabulating down compares.
Table 1
| ????MMMP-3 | ????MMMP-6 | |
| Color * (pure matter) | 4.5 | 4.8 |
| Viscosity in 70 | 1200cps | Paste |
| Viscosity in 100 | 423cps | 1743cps |
| Density | 1.082 | 1.092 |
* calculate with Gardner unit.
＜embodiment 2 〉
How the present embodiment explanation synthesizes another kind of according to compound of the present invention, that is compound 5 and intermediate product 1-{4-[pair-(2-hydroxyl-γ-ethyl)-amido thereof] } 2-methyl-2-morpholinyl-1-acetone (1-{4-[bis-(2-hydroxy-γ-ethyl)-amino]-2-methyl-2-morpholino-1-propanone, compound 4), relevant route of synthesis is as follows:
A.1-{4[two-(2-hydroxyl-r-ethyl)-amido] } 2-methyl-2-morpholinyl-1-acetone (compound 4) synthetic:
1-(4-the fluorophenyl)-2-methyl-2-morpholinyl-1-acetone of 10.0g (0.037mol) and the diethanolamine of 58.9g (0.56mol) are placed the three neck round-bottomed flasks of a 100ml, and be heated to 150 ℃ and last 24 hours.Formed solution is cooled, and is diluted with the ethanol of 100ml, and water and salt solution are cleaned afterwards.Remove solvent by rotary evaporator, and obtain a yellow oil (11g, 88% productive rate).
B. the preparation of compound 5:
Place one to be equipped with a condenser and to be in 100 milliliters three neck round-bottomed flasks under the nitrogen protection tin catalyst (SCAT-24) of the 6-caprolactone of the compound 4 of 11.0g (0.033mol), 17.9g and 1.8g.Mixture is heated to 80-85 ℃ and lasts 1.5 hours.One be added in the above-mentioned flask by the 6-caprolactone of 9.0g and the mixture that SCAT-24 constituted of 0.9g in per 30 minutes, do 3 times.Kept this temperature 1 hour again.Reaction mixture connects and is cooled to room temperature, and is diluted with the toluene of 200ml.Afterwards, cleaned with water and salt solution, organic layer is concentrated under vacuum, and obtains a toughening oil (29.8 grams, 90% productive rate).
Foundation
1H NMR data are calculated, the n of compound 5
1+ n
2=6.
＜embodiment 3 〉
How the present embodiment explanation synthesizes another according to compound 3690 of the present invention, that is 2-Ou Kesipeng ketone, 2-{{4-[2-(dimethyl amido)-1-oxygen base-2-(phenyl methyl) butyl] phenyl }-the methyl amido }-ethyl ester (2-oxepanone, 2-{{4-[2-(dimethylamino)-1-oxo-2-(phenylmethyl) butyl] phenyl}-methylamino}-ethyl ester) [annotate: 2-oxepanone is 6-caprolactone] and intermediate product 369N thereof, be 2-(dimethyl amido)-1-{4-[(2-hydroxyethyl) the methyl amido] phenyl }-2-phenyl methyl-1-butanone (2-(Dimethylamino)-1-{4-[(2-hydroxyethyl) methylamino] phenyl}-2-phenylmethyl-l-butanone), relevant route of synthesis is as follows:
Wherein n can be one by 1 to 10 integer, is preferably 1-6.
A.2-methyl amido (dimethyl amido)-1-{4-[(2-hydroxyethyl)] phenyl }-2-phenyl methyl-1-butanone (compound 369N) synthetic:
2-(dimethyl amido)-1-(4-fluorophenyl)-2-phenyl methyl-1-butanone (2-dimethylamino-1-(4-fluorophenyl)-2-phenylmethyl-1-butanone (compound 369F with 100g, with reference to US 5,077,402 disclosure prepares) place the reaction flask of a 2L with 2-(methyl amido) ethanol of 600g, purged 5 times with nitrogen after evenly stirring.Be warming up to 150 ℃ and evenly stir 3 hours after, the compound 369F of 50g is added in the reaction flask, continue the compound 369F that reaction lasts after 2 hours 50g again and be added in the reaction flask, continue reaction and last 4 hours.After at last temperature of reaction being reduced to 40 ℃, to react under 48 ℃ of conditions with 2.0 holders after remaining 2-(methyl amido) ethanol distillation goes out 470g, added the toluene of 200g and the water of 400g, after evenly stirring water layer is removed, the water that adds 200g more evenly stirred 10 minutes, water layer was removed again, and remove toluene, promptly obtain compound 369N.
The character that title compound records:
1H?NMR(CDCl
3，200MHz)：δ8.35(d，J＝9.0Hz，2H)，7.20-7.27(m，5H)，6.66(d，J＝9.0Hz，2H)，3.82(t，J＝6.0Hz，2H)，3.56(t，J＝6.0Hz，2H)，3.22(s，2H)，3.06(s，3H)，2.38(s，6H)，1.40-2.10(m，2H)，0.72(t，J＝7.4Hz，3H)。
B.2-Ou Kesipeng ketone, 2-{{4-[2-(dimethyl amido)-1-oxygen base-2-(phenyl methyl) butyl] phenyl }-the methyl amido }-ethyl ester (2-oxepanone, 2-{{4-[2-(dimethylamino)-1-oxo-2-(phenylmethyl) butyl] phenyl}-methylamino}-ethyl ester, compound 3690) synthetic:
Gained compound 369N among the above-mentioned steps A is added the 6-caprolactone of 150g, and when being heated to 150 ℃, added the Scat-24 of 0.043g.After reaction lasts 4 hours, add the 6-caprolactone of 78g again and continue reaction and last 4 hours, at last 50 ℃ with 2 conditions of holding in the palm under remove remaining 6-caprolactone, and obtain the reddish brown transparent thick liquid (productive rate 93.7%) of 401g.
The character that title compound (n=3) records:
1H?NMR(CDCl
3，200MHz)：δ8.36(d，J＝8.7Hz，2H)，7.19-7.27(m，5H)，6.64(d，J＝8.7Hz，2H)，4.28(t，2H)，4.03-4.06(m，4H)，3.61-3.67(m，4H)，3.19(s，2H)，3.05(s，3H)，2.60(b，1H)，2.35(s，6H)，2.27-2.31(m，6H)，1.80-2.20(m，2H)，1.61-1.69(m，12H)，1.34-1.4l(m，6H)，0.68(t，J＝7.4Hz，3H)。
IR(KBr)：3514，2940，2866，1734，1657，1642，1593，1547，1462，1379，1249，1183，823，704，662cm
-1。
UV(λ
max)＝335.1nm。
Foundation
1H NMR data calculate that products therefrom is the compound 3690 of n=3, and its molecular weight is about 650.
The comparison of＜experiment 1〉ray velocity performance and adour properties
Be the test The compounds of this invention, compared to MMMP in the past, whether be suitable as light trigger, and in this test, MMMP-3, MMMP-6 and compound 3690 are applied to respectively have in the printing-ink of forming shown in the tabulation 2 down, and next and existing MMMP does the comparison on ray velocity performance and the adour properties.
Material:
1.MMMP: can be available from Ciba Speciality Chemicals Holding Inc., commodity are called Irgacure 907.
2.MMMP-3: according to the foregoing description 1 prepared compound.
3.MMMP-6: according to the foregoing description 1 prepared compound.
4. compound 3690: according to the foregoing description 3 prepared compounds.
5. ethyl Michler's keton (ethyl Michler ' s ketone): can be available from strange titanizing (the Chitec Chemical Co. of limited-liability company of this country, Ltd., Taiwan, R.O.C.), commodity are called ChivacureEMK, and it is used as the photosensitizers in the photopolymerization of printing-ink.
6. isopropyl thioxanthone (isopropyl thioxanthone): can be available from the strange titanizing limited-liability company of this country, commodity are called Chivacure ITX, and it is used as the photosensitizers in the photopolymerization of printing-ink.
Viscoat 295 (trimethylolpropane triacrylate, TMPTA): can be available from UCB Chemical Co., it is as the monomeric compound in the photopolymerization of printing-ink.
8.Eberyl 3702: can be available from UCB Chemical Co., it is as the oligopolymer in the photopolymerization of printing-ink.
9.Fastogen Blue 5380-E (C.I.B.-15:3): can be available from Dainppon Ink andChemical Co., it is as the pigment in the printing-ink.
Method:
A. test the composition of printing ink:, above-claimed cpd is filled a prescription into four kinds of different test printing ink according to tabulating shown in 2 down.
The composition of table 2. test printing ink
| Printing ink 1 | Printing ink 2 | Printing ink 3 | Printing ink 4 | |
| MMMP | 4* 1 | - | - | |
| MMMP-3 | - | 8* 2 | - | |
| MMMP-6 | - | - | 12 | |
| Compound 3690 | 8 *2 | |||
| The ethyl Michler's keton | 0.5 | 0.5 | 0.5 | 0.5 |
| Isopropyl thioxanthone | 1.0 | 1.0 | 1.0 | 1.0 |
| TMPTA | 25 | 25 | 25 | 25 |
| Ebecrvl?3702 | 60 | 60 | 60 | 60 |
| Fastogen?Blue?5380-E (C.I.B.-15：3) | 5 | 5 | 5 | 5 |
| Three-roller mill grinds | 2 times | -* 3 | - | - |
*
1: by weight
*
2: with identical equivalent weight is benchmark
*
3: substitute lapping mode in the fusion mode and implement
B. test the photopolymerization of printing ink: with one is that the ink lay of 10 μ m is applied on the fiber board of a standard, uses a Fusion D-type lamp (Fusion model: F300S), make ink solidification and form a coating under the irradiation of 300W/in.
C. the mensuration of ray velocity: with the inch per minute clock is that the ray velocity of test printing ink is noted down till forming sticking coating by unit.
D. the mensuration of smell: be the test smell, in 80 ℃ down heating last by the formed coating of test printing ink 5 minutes during, and assess this coating whether the smell of disengaging arranged in this period.Final assessment is classified as " irritating smell " or " nothing ".
The result:
Four listed in the table 2 test printing ink carry out ray velocity and smell test, and gained the results are shown in down in the tabulation 3.
The comparison of table 3. ray velocity performance and adour properties
| Printing ink 1 | Printing ink 2 | Printing ink 3 | Printing ink 4 | |
| Ray velocity (in/min) | 640 | 620 | 540 | 700 |
| Smell after the curing | Irritating smell | Odorlessness | Odorlessness | Odorlessness |
Can know by table 3 and to find out that printing ink 1 existing serious smell problem can not come across printing ink 2 (containing MMMP-3), printing ink 3 (containing MMMP-6) and printing ink 4 (containing compound 3690).In addition, be under the benchmark with identical equivalent, printing ink 1 is similar with the ray velocity of printing ink 2.This has confirmed to use this case compound to form the validity of the polymerizability structure of coating through irradiation as the printing ink of light trigger.Moreover when using compound of the present invention, it is when making printing-ink that an advantage is arranged, and can only prepare the printing ink composition and need not give milled processed with the fusion mode.
The comparison of＜experiment 2〉adhering performance
Be the test The compounds of this invention, compared to MMMP in the past, which kind of influence is adhesion properties to the finished product made can produce, particularly summer transport with condition of storage under, and carry out the adhering performance test with four kinds of printing ink shown in the table 2, wherein these test printing ink are directed to simulation transporting with the minimum heat treated of condition of storage during summer and go through for some time.
Method:
Printing ink is deposited in the baking oven that a temperature is set to 60 ℃, and performed an analysis in the test printing ink that the specified timed interval in 4 of tabulating is down taken out a part.Viscosity is by using one to measure available from the viscometer (model RV DV-1) in Brookfiled, and notes down with centipoise (CPS) unit.
The result:
Four listed in the table 2 test printing ink carry out the adhering performance test, and gained the results are shown in down in the tabulation 4.
Table 4: under 60 ℃, the viscosity of printing ink is with respect to the variation of time
| Hour | Printing ink 1 | Printing ink 2 | Printing ink 3 | Printing ink 4 |
| 0 | 6280*1 | 4400 | 4120 | 3800 |
| 24 | 6480 | 5000 | 4500 | Gel |
| 64 | 8270 | 6510 | 5700 | Gel |
| 200 | 12400 | 9640 | 9200 | Gel |
*
1: unit is centipoise (CPS).
By above-mentioned table 4 as can be known, compared to the printing ink that contains MMMP in the past, contain this case compound printing ink have lower initial viscosity, and the printing ink that contains MMMP-3 or MMMP-6 has more resistance for gel.
The comparison of＜experiment 3〉MMMP-3 and compound 3690 and BDMB
This experiment is further compared MMMP-3 and compound 3690 and BDMB in ray velocity performance and the difference on the tinning stability under the no stablizer (in-can stability).
Material:
1.BDMB: can be available from Ciba Specialty Chemicals Holding Inc., commodity are called Irgacure 369.
2.MMMP-3: according to the foregoing description 1 prepared compound.
3. compound 3690: according to the foregoing description 3 prepared compounds.
4. ethyl Michler's keton (ethyl MiChler ' s ketone): referring to above-mentioned experiment 1.
5. isopropyl thioxanthone (isopropyl thioxanthone): referring to above-mentioned experiment 1.
6. trihydroxymethyl propane triacrylate (TMPTA): referring to above-mentioned experiment 1.
7.Eberyl 3702: referring to above-mentioned experiment 1.
8. carbon black (carbon black): can be available from Degusa, as the pigment in the printing-ink.
Method:
A. test the composition of printing ink: use the three-roll grinder of a standard, below the component shown in the tabulation 5 is mixed with three kinds of different test printing ink.
Table 5: the composition of test printing ink
| Printing ink 5 | Printing ink 6 | Printing ink 7 | |
| BDMD | 5 | - | - |
| MMMP-3 | - | 10 | - |
| Compound 3690 | 10 | ||
| The ethyl Michler's keton | 0.5 | 0.5 | 0.5 |
| Isopropyl thioxanthone | 1.0 | 1.0 | 1.0 |
| TMPTA | 25 | 25 | 25 |
| Ebecryl?3702 | 60 | 60 | 60 |
| Carbon black | 3 | 3 | 3 |
| Grind number of times | 3 times | - | - |
B. test the photopolymerization of printing ink: the mode with reference to experiment 1 is carried out.
C. the mensuration of ray velocity (photospeed): the mode with reference to experiment 1 is carried out.
D. the mensuration of smell: the mode with reference to experiment 1 is carried out.
E. the mensuration of adhering performance: the mode with reference to experiment 2 is carried out.
The result:
Three listed in the table 5 test printing ink are directed to ray velocity, smell and adhering performance test, and gained the results are shown in down in the tabulation 6.
The comparison of table 6:MMMP-3 and compound 3690 and BDMB
| Printing ink 5 | Printing ink 6 | Printing ink 7 | |
| Ray velocity (in/mon) | 550 | 530 | 560 |
| Smell after the curing | Do not have | Do not have | Do not have |
| Viscosity (cps is when initial) | 6670 | 3740 | 4600 |
| Viscosity (under 60 ℃, 24 hours) | Gel | 3780 | Gel |
| Viscosity (under 60 ℃, 100 hours) | Gel | 6200 | Gel |
Conclusion:
Can know and find out,, to have following unique property with describing from above-mentioned exemplary experiment according to MMMP-3 of the present invention, MMMP-6 and compound 3690, particularly MMMP-3 compared to MMMP and BDMB in the past:
1. the smell problem is fully overcome;
2. be under the benchmark with identical equivalent weight, the ray velocity performance of MMMP-3 of the present invention is suitable with MMMP in the past and BDMB institute tool;
3. lower viscosity can be reached to be caused, and helps the application of elasticity letterpress (flexographic printing) or gravure printing ink;
4. no longer include the problem of headachy too early gel, constant viscosity is attainable, and compound composition can provide longer storage time;
5. no longer need stablizer, also save manufacturing cost and not only simplify prescription work; And
6. do not need milled processed, and save labour costs and time.
In addition, this case compound 3690 on rate of drying than MMMP-3 to come fast and suitable with BDMD.Though compound 3690 and BDMD can suffer from the problem of gel equally, but this problem can solve behind the stablizer of interpolation 0.5%, and when using this case compound 3690, does not need to grind, and can reduce the viscosity of ink set, so BDMD more in the past is excellent.
All patents quoted from this case description of the invention and document are merged in this case with as with reference to data with its integral body.If to some extent when conflicting, the detailed description of this case description of the invention (comprise be defined in) will be got the upper hand.
Though the present invention is explained by above-mentioned detailed description and preferred embodiment, the present invention should not be interpreted as being subjected to limit; Relatively, the present invention is real contain general, the technology contents that is disclosed from this case description of the invention as the people who knows this skill when implementing to consider, multiple other different equivalent that can make change and with modify.Therefore, do not departing under the essential ideas of the present invention, the simple equivalent of being done according to the present patent application claim and description of the invention content changes and modifies generally, all should still belong in the scope that patent of the present invention contains.
Claims (5)
1. compound is characterized in that this compound has following chemical formula (I):
Wherein
X
1Expression: H, S, O, N or NR, R wherein are a C
1-C
12Alkyl group,
X
2Expression: H, S, O, N or NR, R wherein are a C
1-C
12Alkyl group,
But condition is to work as X
1With X
2Neither when being H, X
1=X
2
R ' expression a: C
1-C
12Alkylidene group or chemical formula are-(CH
2OCH
2)
p-group, wherein p be one by 1 to 4 integer;
R
1With R
2Expression: H respectively separately, phenyl, or optionally by C that phenyl replaced
1-C
12Alkyl, C
2-C
12Thiazolinyl, C
1-C
12Alkoxyl group;
R
3With R
4Represent a C who is optionally replaced separately respectively by hydroxyl
1-C
6Alkyl,
Perhaps R
3With R
4Be selected from following cyclic group together with forming one with institute banded nitrogen-atoms:
With
R
5Expression: H, F, Cl, Br, I, nitro, phenyl, C
1-C
12Alkyl or C
1-C
12Alkoxyl group;
Work as X
1Or X
2During for H, k is 0; Work as X
1Or X
2During for S, O or NR, k is 1; And work as X
1Or X
2During for N, k is 2;
M be one by 2 to 5 integer; And
When k is 1, n be one by 1 to 20 integer, and when k is 2, n=n
1+ n
2≤ 20, n wherein
1With n
2Respectively be one by 1 to 10 integer.
2. compound as claimed in claim 1 is characterized in that:
X
1With X
2In have one for S, and another is H,
R ' is an ethylidene,
R
1With R
2Be methyl separately respectively,
R
3With R
4Together with forming one with institute banded nitrogen-atoms
Group,
R
5Be H, and
M is 5.
3. compound as claimed in claim 1 is characterized in that:
X
1With X
2In have one for NR, wherein R is methyl or ethyl, and another is H,
R ' is an ethylidene,
R
1Be the methyl of phenyl replacement,
R
2Be ethyl,
R
3With R
4Be methyl separately respectively,
R
5Be H, and
M is 5.
4. photopolymerizable composition is characterized in that:
Said composition includes photopolymerizable monomer compound and the compound with chemical formula (I) as claimed in claim 1.
5. photopolymerizable composition as claimed in claim 4 is characterized in that:
Said composition also includes a dyestuff or pigment.
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|---|---|---|---|
| CN 03110380 CN1202098C (en) | 2002-04-26 | 2003-04-08 | Novel morpholone derivative and its prepn and use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02118919.6 | 2002-04-26 | ||
| CN02118919 | 2002-04-26 | ||
| CN 03110380 CN1202098C (en) | 2002-04-26 | 2003-04-08 | Novel morpholone derivative and its prepn and use |
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|---|---|
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| CN1202098C CN1202098C (en) | 2005-05-18 |
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ID=29271367
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012317A (en) * | 2012-12-23 | 2013-04-03 | 惠州市华泓新材料有限公司 | Alkyl phenyl derivative and application of alkyl phenyl derivative as photoinitiator |
| CN107188996A (en) * | 2016-03-14 | 2017-09-22 | 奇钛科技股份有限公司 | liquid photoinitiator and application thereof |
| TWI677492B (en) * | 2018-07-17 | 2019-11-21 | 奇鈦科技股份有限公司 | Liquid photo initiating compound and uses of the same |
-
2003
- 2003-04-08 CN CN 03110380 patent/CN1202098C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012317A (en) * | 2012-12-23 | 2013-04-03 | 惠州市华泓新材料有限公司 | Alkyl phenyl derivative and application of alkyl phenyl derivative as photoinitiator |
| CN107188996A (en) * | 2016-03-14 | 2017-09-22 | 奇钛科技股份有限公司 | liquid photoinitiator and application thereof |
| CN107188996B (en) * | 2016-03-14 | 2018-10-26 | 奇钛科技股份有限公司 | liquid photoinitiator and application thereof |
| TWI677492B (en) * | 2018-07-17 | 2019-11-21 | 奇鈦科技股份有限公司 | Liquid photo initiating compound and uses of the same |
| CN110724111A (en) * | 2018-07-17 | 2020-01-24 | 奇钛科技股份有限公司 | Liquid photoinitiating compound and its application |
| CN110724111B (en) * | 2018-07-17 | 2023-02-17 | 奇钛科技股份有限公司 | Liquid photoinitiating compound and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1202098C (en) | 2005-05-18 |
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