阅读说明：本技术 液态光引发化合物及其应用 (Liquid photoinitiating compound and its application ) 是由 张玮骏 曲清蕃 吴皇旻 于 2019-02-25 设计创作，主要内容包括：本发明提供一种液态光引发化合物及其应用,其中该化合物具下式I的结构：[式I]<Image he="461" wi="700" file="DDA0001977096310000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>于式I中,R<Sub>1</Sub>与R<Sub>2</Sub>各自独立为H或C<Sub>1</Sub>-C<Sub>3</Sub>烷基,且R<Sub>3</Sub>为H或甲基。(The invention provides a liquid photoinitiating compound and application thereof, wherein the compound has a structure shown in the following formula I: [ formula I ]] In formula I, R 1 And R 2 Each independently is H or C 1 ‑C 3 Alkyl, and R 3 Is H or methyl.)

1. A liquid photoinitiating compound having the structure of formula I:

[ formula I ]

In formula I, R₁And R₂Each independently is H or C₁-C₃Alkyl, and R₃Is H or methyl.

2. The compound of claim 1, wherein R is₁And R₂Each independently is methyl, ethyl, n-propyl or isopropyl.

3. The compound of claim 2, having the structure of formula Ia:

[ formula Ia ]

4. A compound according to any one of claims 1 to 3, for use as a photoinitiator.

5. A photopolymerizable composition characterized by comprising:

a first photoinitiator which is a compound according to any one of claims 1 to 3;

a photopolymerizable component; and

optionally a solvent.

6. A photopolymerizable composition according to claim 5 wherein said photopolymerizable component is an ethylenically unsaturated monomer, an ethylenically unsaturated oligomer, or a combination thereof.

7. A photopolymerizable composition according to claim 6 wherein said photopolymerizable component is an acrylate-based monomer, an acrylate-based oligomer, or a combination thereof.

8. A photopolymerizable composition according to claim 5 further comprising a second photoinitiator selected from the group consisting of: acylphosphine oxide, 9, 10-dialkoxy onion (9,10-dialkyloxy anthracene; i.e. a compound of formula

9. A photopolymerizable composition according to claim 5 further comprising a photosensitizer selected from the group consisting of: benzophenones (benzophenones) and oxa-sulfur

10. A photopolymerizable composition according to claim 5 further comprising an additive selected from the group consisting of: pigments, amine synergists (amine synergist), and combinations thereof.

11. A photopolymerizable composition according to claim 5 wherein the first photoinitiator is present in an amount ranging from 0.1 wt.% to 15 wt.%, based on the total weight of the photopolymerizable composition.

Technical Field

The present invention relates to a liquid photoinitiating compound and its application in photopolymerizable composition.

Background

A photoinitiator (photoinitiator) is a substance that absorbs light energy, such as visible light or ultraviolet light, to reach an excited state, and performs a roche Type I (Norrish Type I) photoreaction to cleave its free radical, thereby initiating the crosslinking polymerization of monomers or oligomers to achieve a curing effect.

Ciba corporation developed the first solid initiator product suitable for dark UV inks in 1990 "

369 "(related patent: US 5,077,402), the chemical structure of which is shown below, is a Roche Type I photoinitiator, and willThe free radicals are split to initiate the cross-linking polymerization of the monomers or oligomers to achieve the curing effect.

[369]

369 has excellent photoinitiating properties and does not generate odor either by itself or after irradiation, but has poor solubility in general UV inks and needs to be dissolved by a step of polishing, heating or the like.

369 in an amount of more than 4% by weight is at risk of precipitation, and the precipitation is more pronounced especially in low temperature use environments such as cold regions. More recently, the development of new and more recently developed devices

369 the European Union were listed as the substance with the highest reproductive toxicity, and this topic was continuously being explored and is being noted by the market, which makes it at risk of being banned.

Ciba company of

369 thereafter, a solid photoinitiator product of the following structure is pushed out "

379 "(related patent: US 7,247,659B 2).

379 although the solubility in some monomers and resins is improved, they are still solid photoinitiators, and they must be heated and ground to be used in ink formulations, which is still inconvenient. In addition to this, the present invention is,

379 also has reproductive toxicity problems.

[379]

In recent years, the demand for low viscosity inks has been increasing due to the vigorous development of printing technologies such as digital printing (digital printing), gravure printing (gravure printing), and flexographic printing (flexographic printing). Low viscosity inks prefer to use liquid photoinitiators that are more easily dispersed and have better solubility, since low viscosity inks typically do not provide sufficient shear to perform the milling dispersion process required for solid photoinitiators.

Examples of liquid photoinitiators include the following compounds 93, 95, 96 and 100 described in US 5,077,402, but these compounds have a slow light speed in black ink systems and are odorous after use and have therefore never been commercialized.

[US 5,077,402]

TW I277834 the liquid photoinitiators listed in example 3, although solving the odor problem, showed only light speeds

369 to one tenth, and so has not been commercialized.

[ TW I277834 example 3]

In addition, there is a liquid photoinitiator product, as shown in compound I below, whose light speed follows

369 close, but after illumination, there was a serious odor problem.

[ Compound I ]

The liquid compound IIa of the formula described in TW I564276 has a structure represented by the formula

369 the approximate light speed, no smell, but acute toxicity after oral administration and brown-black color.

[ Compound IIa of TW I564276 ]

Thus, the liquid photoinitiators currently available for dark and black inks are not perfect, and each has its drawbacks.

Disclosure of Invention

In view of the disadvantages of the conventional photoinitiators, the present invention provides an Oxazolidine (Oxazolidine) derivative photoinitiator which has (1) a liquid state at a low temperature of 50 ℃ and (2) an approximate light velocity

369. The (3) no odor is generated after the self and illumination, and (4) no oral acute toxicity, and the like, thereby solving all the problems of the prior liquid photoinitiator for the black ink system. In addition, the photoinitiator has the advantages of light initial color, high purity and the like, and can fully meet the requirements of the industry on liquid photoinitiators. Accordingly, the present invention is directed to at least the objects of the invention which will be described hereinafter.

It should be noted that although the photoinitiators disclosed in US 5,077,402 and US 7,732,504B2 encompass photoinitiators having oxazolidine structures, the photoinitiators of the present invention are not taught, and one of ordinary skill in the art would not expect the excellent efficacy of the photoinitiators of the present invention based on the broad teachings of US 5,077,402 and US 7,732,504B2, including being liquid at a low temperature of 50 ℃, having good light speed, having no odor and toxicity, and the like, and especially not expecting the results of the photoinitiators of the present invention having no oral acute toxicity.

It is an object of the present invention to provide a liquid photoinitiating compound having the structure of formula I:

[ formula I ]

In formula I, R₁And R₂Each independently is H or C₁-C₃Alkyl, and R₃Is H or methyl. The C is₁-C₃Alkyl groups include methyl, ethyl, n-propyl and isopropyl.

In some embodiments, the aforementioned compounds have the structure of formula Ia:

[ formula Ia ]

Another subject of the invention relates to the use of the aforementioned compounds as photoinitiators.

It is a further object of the present invention to provide a photopolymerizable composition comprising:

a first photoinitiator, which is the aforementioned compound;

a photopolymerizable component; and optionally a solvent.

In some embodiments, the photopolymerizable component is an ethylenically unsaturated monomer, an ethylenically unsaturated oligomer, or a combination thereof. Examples of the ethylenically unsaturated monomer include acrylate-based monomers, and examples of the ethylenically unsaturated oligomer include acrylate-based oligomers.

In some embodiments, the photopolymerizable composition further comprises a second photoinitiator selected from the group consisting of: acylphosphine oxide, 9, 10-dialkoxy onion (9,10-dialkyloxy anthracene; i.e. a compound of formula

Wherein R is alkyl) and combinations thereof.

In some embodiments of the invention, the photopolymerizable composition further comprises a photosensitizer selected from the group consisting of: benzophenones (benzophenones) and oxa-sulfur

The classes (thioxanthones), their ketals (Michler' sketons), anthraquinones (anthraquinones), and combinations thereof.

In some embodiments, the photopolymerizable composition further comprises an additive selected from the group consisting of: pigments, amine synergists (amine synergist), and combinations thereof.

In some embodiments, the first photoinitiator is present in an amount of 0.1 wt% to 15 wt%, based on the total weight of the photopolymerizable composition.

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, some embodiments accompanied with figures are described in detail below.

Detailed Description

Some specific embodiments according to the present invention will be specifically described below; the invention may, however, be embodied in many different forms without departing from the spirit thereof, and the scope of the invention should not be construed as limited to the specific embodiments set forth herein.

As used in this specification and throughout the claims that follow, unless otherwise indicated, the terms "a" and "an" and "the" and similar referents are to be construed to cover both the singular and the plural.

As used herein (and in the claims, unless otherwise specified, "first," "second," and the like are used solely to distinguish one element or component from another as illustrated and not necessarily to imply a sequence.

Unless otherwise indicated, in the present specification (especially in the claims) the alkyl group is a variety of alkyl groups comprising structures having a linear, branched, cyclic or a combination thereof.

Liquid photoinitiating compounds

The liquid photoinitiating compounds of the present invention have the structure of formula I:

[ formula I ]

In formula I, R₁And R₂Each independently is H or C₁-C₃Alkyl, and R₃Is H or methyl. In some embodiments of the invention, R₁And R₂Each independently is methyl, ethyl, n-propyl or isopropyl, and R₃Is H. In the examples that follow, the first photoinitiator has the structure of formula Ia:

[ formula Ia ]

The following examples are provided to illustrate the synthesis of the liquid photo-initiation compound of the present invention, and are not repeated herein.

Use of liquid photoinitiating compounds

The liquid photoinitiating compound is liquid at the low temperature of 50 ℃, can be used as a liquid photoinitiator to initiate photopolymerizable monomers or oligomers to perform cross-linking polymerization reaction and solidify, and has a special structure which unexpectedly enables the compound to show characteristics different from the prior photoinitiator, thereby having a plurality of advantages. Specifically, the liquid photoinitiating compound of the present invention has excellent light velocity performance (photo performance), is liquid at a low temperature of 50 ℃, has excellent solubility, low chroma, and the like, has little influence on the viscosity of a system when added to a photopolymerizable system, and has long-term storage stability, and thus can be particularly applied to low-viscosity UV inks (e.g., inks having a viscosity of less than 1000 centipoise (cps)), light-Color UV inks, Color resists, Black matrices, and Solder resists. In addition, the liquid photoinitiating compound of the present invention has high production purity and can meet the registration standard of chemical substance regulations in various countries.

Accordingly, the present invention also provides a photopolymerizable composition comprising a first photoinitiator, a photopolymerizable component, and optionally a solvent, wherein the first photoinitiator is a compound of formula I.

The kind of the photopolymerizable component is not particularly limited, and may be any photopolymerizable substance in the presence of a photoinitiator, including photopolymerizable components commonly used in photopolymerizable systems such as UV inks. In some embodiments of the invention, the photopolymerizable component is an ethylenically unsaturated monomer, an ethylenically unsaturated oligomer, or a combination thereof. Examples of the ethylenically unsaturated monomer include, but are not limited to, acrylate-based monomers, and examples of the ethylenically unsaturated oligomer include, but are not limited to, acrylate-based oligomers.

The optional solvent may be any solvent that can dissolve or disperse the components of the composition, but does not react with it, including solvents commonly used in photopolymerizable systems such as UV inks. Examples of solvents include, but are not limited to: water; aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, tetrachloromethane, n-hexane and cyclohexane; aromatic hydrocarbon solvents such as toluene, benzene and xylene; ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone; ester-based solvents such as ethyl acetate and butyl acetate; alcohol-based solvents such as methanol, ethanol, n-propanol and isopropanol; and ether solvents such as dimethyl ether, diethyl ether and methyl ethyl ether.

The content of the first photoinitiator in the photopolymerizable composition of the invention is not particularly limited and may be formulated as desired by one of ordinary skill in the art. In general, to achieve the desired photopolymerization cure, the first photoinitiator can be present in an amount of, but not limited to, 0.1 wt% to 15 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, or 9 wt%, based on the total weight of the photopolymerizable composition.

In addition to the first photoinitiator, the photopolymerizable compositions of the invention may also optionally contain other ingredients that contribute to the photoinitiating effect, such as photosensitive ingredients or other photoinitiating ingredients. Thus, in some embodiments of the present invention, the photopolymerizable composition further comprises a second photoinitiator, a photosensitizer, or a combination thereof.

The second photoinitiator can be any photoinitiating component other than the first photoinitiator, examples of which include, but are not limited to, acylphosphine oxide, 9, 10-dialkoxy onion, or combinations thereof. The kind of the photosensitizer is also not particularly limited, and examples thereof include, but are not limited to, benzophenones, oxysulfurs

A flavonoid, a milone, an anthraquinone, or a combination thereof. In the examples which follow, 2, 4-diethyloxysulfide is used in the photopolymerizable composition

(product name:

DETX) as a photosensitizer. The contents of the second photoinitiator and the photosensitizer are not particularly limited and may be formulated as desired by those of ordinary skill in the art.

The photopolymerizable composition of the invention may optionally further comprise one or more additives to impart desired properties to the resulting product after curing of the composition. For example, pigments may be added to impart color to the product or amine synergists may be added to enhance the curing performance, such as increasing the surface cure speed of the composition and the mirror effect upon drying. Examples of pigments include, but are not limited to, dioxinsTitanium oxide, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, titanium cobalt green, cyan blue, cobalt blue, azo pigments, phthalo pigments (phthalocyanines), acridone pigments (quinoidal pigments), isoindolinone pigments (isoindolinone based pigments), perylene pigments (perylene based pigments), thioindigo pigments (thio indigo based pigments), and metal complex pigments. In the present specification, amine synergists are additives well known to those skilled in the art and generally refer to reactive amines, such as low molecular weight tertiary amines, that promote photoinitiation reactions. Examples of amine synergists include, without limitation, methyldiethanolamine, dibutylethanolamine, triethylamine, triethanolamine, and commercially available products thereof including those available from the Kitthiki technologies, Inc

115、

EPD、

OPD, and the like.

The invention will now be further illustrated by the following specific embodiments.