阅读说明：本技术 用于红光和近红外的三组分光引发系统 (Three-component photoinitiation system for red and near infrared ) 是由 奥德·赫洛伊丝·博纳尔迪 雅克·拉莱维 法布里斯·莫莱-萨瓦里 塞莉纳·迪耶特兰 迪迪埃·吉 于 2018-12-20 设计创作，主要内容包括：本发明涉及用于红光和近红外诱导的光聚合的新光引发组合物、其用于光聚合反应的方法和通过这种方法获得的聚合物。(The present invention relates to novel photoinitiating compositions for red and near infrared induced photopolymerization, processes for their use in photopolymerization reactions and polymers obtained by such processes.)

1. A photoinitiating composition comprising:

(a) an absorbing dye that is an electron donor when exposed to a red to near infrared light source;

(b) an oxidizing agent suitable for polymerization and capable of generating free radicals and/or cations by electrons transferred from the dye when exposed to a red to near infrared light source;

(c) a reducing agent suitable for regenerating the dye; and

(d) an optional oxygen scavenger.

2. The photoinitiating composition of claim 1, wherein the absorbing dye is selected from cyanine, phthalocyanine, dithiolene or porphyrin dye.

3. The photoinitiating composition of claim 1 or 2, wherein the oxidizing agent is selected from the formula ((R)_A)₂I⁺X_A ^-Or (R)_A)₃S⁺X_A ^-An onium salt of (a); wherein R is_AEach occurrence of (A) independently represents C_6-10Aryl moiety or C_1-10An alkyl moiety; wherein the aryl moieties may each be further substituted by one or more straight or branched chain C_1-6Alkyl moiety or C_6-10Aryl moiety substituted; and wherein X_A ^-Represents a suitable counterion, e.g. B (PhF)₆)₄ ^-、PF₆ ^-、SbF₆ ^-Or Cl^-。

4. The photoinitiating composition of any one of claims 1 to 3 wherein the iodonium salt is:

5. the photoinitiating composition of any of claims 1 to 4, wherein the reducing agent c) and oxygen scavenger d) are one compound.

6. The photoinitiating composition of any one of claims 1 to 5, wherein the reducing agent is selected from the group comprising phosphine compounds or amine compounds.

7. Use of the photoinitiating composition according to any one of claims 1 to 6 in a polymerization reaction.

8. Use according to claim 7, wherein the polymerization reaction is a radical and/or cationic polymerization.

9. Use according to claim 7 or 8, wherein the polymerization reaction comprises at least one polymerizable component selected from:

(i) ethylenically unsaturated monomers, the polymerization of which can be carried out by free radical polymerization; and/or

(ii) Ethylenically unsaturated monomers or epoxy-containing monomers or oxetane-containing monomers or vinyl ether-containing monomers or lactide monomers or lactone monomers or caprolactone monomers; the polymerization thereof may be effected by cationic polymerization.

10. Use according to any one of claims 7 to 9, wherein the ethylenically unsaturated monomer whose polymerization is carried out by free-radical polymerization is an acrylate or methacrylate.

11. Use according to any one of claims 7 to 10, wherein the monomer whose polymerization is carried out by cationic polymerization is an epoxide, oxetane, vinyl ether, lactide, lactone or caprolactone monomer.

12. Use according to any one of claims 7 to 11 for the preparation of an interpenetrating network of at least two polymers produced by concomitant free radical and/or cationic polymerization.

13. A process for radical and/or cationic photopolymerization under red to near-infrared irradiation conditions, comprising the step of polymerizing at least one polymerizable component selected from:

(i) ethylenically unsaturated monomers, the polymerization of which can be carried out by free radical polymerization; and/or

(ii) Ethylenically unsaturated monomers or epoxy-containing monomers or oxetane monomers or vinyl ether-containing monomers or lactide monomers or lactone monomers or caprolactone monomers; the polymerization thereof may be carried out by cationic polymerization.

14. The method of claim 13, wherein at least one polymerizable monomer is an acrylate or methacrylate whose polymerization is carried out by free radical polymerization.

15. The method according to claim 13 or 14, wherein at least one polymerizable monomer is a vinyl ester or an epoxide whose polymerization is carried out by cationic polymerization.

16. The method according to any one of claims 13 to 15, wherein the interpenetrating network of at least two polymers produced by concomitant free radical and/or cationic polymerization is prepared by carrying out free radical and/or cationic photopolymerization.

17. A polymer obtained by the process according to any one of claims 13 to 16.

Technical Field

The present invention relates to novel photoinitiating compositions for red and near infrared induced photopolymerization, methods of using them in photopolymerization reactions and polymers obtained by such methods.

In the following, the number of brackets ([ ]) refers to the list of references provided at the end of the document.

Background

Photopolymerization has many advantages over conventional thermal polymerization, namely: (i) the space and time control of the polymerization reaction is better; (ii) (ii) the polymerization can be carried out in the absence of a solvent, and (iii) the conditions are milder (light rather than heat); thereby being advantageous in terms of economy and energy costs. For these reasons, photoinduced radical polymerization using Photoinitiators (PI) or Photoinitiating Systems (PIs) has been extensively studied in the past few years. Furthermore, they have applications in many industrial fields such as coatings, paints, dentistry, medicine and 3D printing.

Most compositions used in photopolymerization have so far required high or low intensity UV lamps. Currently, UV curing is mainly used for photopolymerization of methacrylate monomers. Since UV wavelengths are known to cause skin and eye damage, a great challenge is to develop new free radical initiation systems that can work under longer (safer) wavelength illumination. Other disadvantages of UV-induced or visible light-induced photopolymerization include: limitation of the thickness of the sample to be polymerized (polymerization of only thin layers), high use levels if photoinitiator systems are used, and/or photopolymerization under inert Conditions (CO)₂，N₂…).

Thus, there remains a need to develop new photoinitiator systems that efficiently initiate photopolymerization under mild light exposure and allow polymerization to proceed throughout the depth of thick samples/materials.

Drawings

In the figures appearing, the symbolsIndicating the start of irradiation.

Also, in all of the following figures and related legends, "Ar₂I⁺/PF₆ ^-"refers to the following iodonium salts:

FIG. 1 calculated transmittance of selected photons and UV-vis light diffusion of polystyrene latex (mean diameter 112 nm).

FIG. 2 RT-FTIR spectra of methacrylate monomers (1) before polymerization (2) after polymerization between 4500 and 7500 nm. Circled are peaks representing the double bond C ═ C conversion used to calculate the photopolymerization curve (methacrylate functionality conversion versus irradiation time).

FIG. 3 shows the results of the reactions of Mix-MA on (1) IR 140-borate (0.1 w%), (2) IR 140-borate/Ar₂I⁺/PF₆ ^-(0.1 w%/3 w%), (3) IR 140-Borate/Ar₂I⁺/PF₆ ^-4-dppba (0.1 w%/3 w%/2 w%); (4) exposure to laser @785nm, 400mW/cm²The following individual monomers; (5) IR 140-Borate/Ar₂I⁺/PF₆ ^-In the presence of/4-dppba (0.1 w%/3 w%/2 w%); laser @785nm, 2.55W/cm²(ii) a Thickness 1.4mm, photopolymerisation curve in air (methacrylate functionality conversion versus irradiation time). Irradiation starts at t-17 s.

FIG. 4.Mix-MA in IR140 Borate (0.1 w%), Ar₂I⁺/PF₆ ^-(3 w%) and 4-dppba (2 w%); laser @785 nm; the thickness is 1.4 mm; (1)0.4W/cm²，(2)1.37W/cm²，(3)1.82W/cm²，(4)2.08W/cm²，(5)2.34W/cm²，(6)2.55W/cm²Photopolymerisation curve under air (methacrylate functionality conversion versus irradiation time). Irradiation starts at t-17 s.

FIG. 5 Mix-MA at IR 140-Borate/Ar₂I⁺/PF₆ ^-Photopolymerization in air in the presence of 0.1 w%/3 w%/2 w% of a/4-dppba (0.1 w%/3 w%/2 w%) and different filler contents (conversion of methacrylate functionality versus irradiation time); laser @785nm, 2,55W/cm²(ii) a (A) Curves using (1)0 w% filler, (2)25 w% filler, (3)50 w% filler, (4)75 w% filler thickness ═ 1.4 mm; photograph of composite (C) 1.4mm thick with 75 w% filler (B) 1cm thick. Irradiation starts at t-17 s.

FIG. 6.Mix-MA at 3 w% Ar₂I⁺/PF₆ ^-2 w% 4dppba and 0.1 w% (1) IR 140-borate, (2) indocyanine green, (3) IR813 p-toluenesulfonate, (4) IR 780-borate, (5) manganese (II) phthalocyanine (Mn-Ph), (6) sodium copper chlorophyllin and (7) nickel dithiolene 1 exposure to (A) LED @660nm, (B) laser @785nm, 400mW/cm²(C) laser @785nm, 2.55W/cm²(ii) a Thickness 1.4mm, photopolymerisation curve in air (methacrylate functionality conversion versus irradiation time). Irradiation starts at t-17 s.

FIG. 7.Mix-MA in Ar₂I⁺/PF₆ ^-(3 w%), 4-dppba (2 w%) and IR-140(0.1 w%); (1) is sold on the market; (2) a borate; exposure to laser @785nm, 2.55W/cm²(ii) a Thickness 1.4mm, photopolymerisation curve under air (methacrylate functionality conversion versus irradiation time). Irradiation starts at t-17 s.

FIG. 8.Mix-MA in Ar₂I⁺/PF₆ ^-(3W%), 4-dppba (2W%) and (1) IR-140 borate (0.1W%) (2) S2265 (0.1W%) were exposed to a laser @785nm, 2.55W/cm²(ii) a Thickness 1.4mm, photopolymerisation curve under air (methacrylate functionality conversion versus irradiation time). Irradiation starts at t-17 s.

FIG. 9A. mix-MA in Ar₂I⁺/PF₆ ^-(3W%), NPG (2W%) and (1) IR 783 (0.1W%), (2) IR 783 (0.1W%), (3) IR813 (0.1W%), (4) indocyanine green (0.1W%), (5) IR780 (0.1W%) and (6) IR-140 borate (0.1W%) exposure to laser light @785nm with an I of 2.5W/cm²(ii) a Thickness 1.4mm, photopolymerisation curve under air (methacrylate functionality conversion versus irradiation time). Irradiation starts at t-15 s.

FIG. 9B.Mix-MA at Ar₂I⁺/PF₆ ^-(3W%), DABA (2W%) and (1) IR 783 (0.1W%), (2) IR 783 (0.1W%), (3) IR813 (0.1W%), (4) indocyanine green (0.1W%), (5) IR780 (0.1W%) and (6) IR-140 borate (0.1W%) exposure to laser light @785nm with an I of 2.5W/cm²(ii) a Thickness 1.4mm, photopolymerisation curve under air (methacrylate functionality conversion versus irradiation time). Irradiation starts at t-15 s.

Detailed Description

Definition of

To facilitate an understanding of the invention, a number of terms and expressions are defined below:

as used herein and in addition to the claims, the terms "a", "an", "the" and/or "said" mean one or more. As used in the claims herein, the terms "a," an, "" the, "and/or" said "can mean one or more when used in conjunction with the terms" comprising, "" containing, "and/or" including. As used herein and in the claims, the terms "having," being, "" having, "" containing, "" including, "and/or" containing "have the same meaning as" consisting of …, "" consisting of …, "and" containing. As used herein and in the claims, "another" may mean at least one more.

The expression "a mixture thereof, etc., following a list, using" and/or "as part of a list, a list in a table, using" etc "as part of a list, the expressions" such as, "e.g.," and/or a list with "e.g.," or "i.e.," in parentheses, referring to any combination (e.g., any subset) of a set of listed members, as well as combinations and/or mixtures of related species and/or embodiments described herein, although not directly placed in such a list, are also contemplated. Such related and/or similar genera, sub-genera, species, and/or embodiments described herein are contemplated as single members of the group that may be claimed, as well as mixtures and/or combinations that may be described in the claims as "at least one selected from …," mixtures thereof, "and/or" combinations thereof.

In general, the term "substituted", whether or not after the term "optionally" and the substituents contained in the formulae of the present invention, means that the hydrogen radical in a given structure is substituted with the radical of the indicated substituent. When more than one position in any given structure may be substituted with more than one substituent selected from a specified group, then the substituents may be the same or different at each position. As used herein, the term "substituted" is intended to include all permissible substituents of organic compounds.

As used herein, the term "aliphatic" includes both saturated and unsaturated, straight-chain (i.e., unbranched) or branched aliphatic hydrocarbons, which are optionally substituted with one or more functional groups. As will be understood by those of ordinary skill in the art, "aliphatic" is intended herein to include, but is not limited to, alkyl, alkenyl, alkynyl moieties.

As used herein, the term "alkyl" refers to both straight and branched chain alkyl groups. Similar convention applies to other general terms such as "alkenyl", "alkynyl", and the like. As used herein, "lower alkyl" is used to denote those alkyl groups (substituted, unsubstituted, branched or straight chain) having from about 1 to 6 carbon atoms. Exemplary alkyl groups include, but are not limited to, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, n-hexyl, sec-hexyl, moieties, and the like, which may also bear one or more substituents. Alkenyl groups include, but are not limited to, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, and the like. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.

As used herein, the term "cycloaliphatic" refers to compounds that combine the properties of aliphatic and cyclic compounds and include, but are not limited to, cyclic or polycyclic aliphatic hydrocarbons and bridged cycloalkyl compounds, which are optionally substituted with one or more functional groups. As will be understood by those of ordinary skill in the art, "alicyclic" is intended herein to include, but is not limited to, cycloalkyl, cycloalkenyl and cycloalkynyl moieties, which are optionally substituted with one or more functional groups. Thus, exemplary cycloaliphatic radicals include, but are not limited to, for example, cyclopropyl, -CH₂-cyclopropyl, cyclobutyl, -CH₂-cyclobutyl, cyclopentyl, -CH₂-cyclopentyl-n, cyclohexyl, -CH₂Cyclohexyl, cyclohexenylethyl, cyclohexylethyl, norbornyl, which may once again bear one or more substituents.

As used herein, the term "heteroaliphatic" refers to an aliphatic moiety in which one or more carbon atoms in the backbone have been replaced with a heteroatom. Thus, heteroaliphatic refers to aliphatic chains containing one or more oxygen, sulfur, nitrogen, phosphorus, or silicon atoms, i.e., in place of carbon atoms. The heteroaliphatic moiety may be branched or linear unbranched. Similar convention applies to other general terms such as "heteroalkyl," "heteroalkenyl," "heteroalkynyl," and the like.

As used herein, the term "heterocyclic" or "heterocycle" refers to compounds that combine the properties of heteroaliphatic and cyclic compounds and include, but are not limited to, saturated and unsaturated monocyclic or polycyclic heterocycles such as morpholinyl, pyrrolidinyl, furanyl, thiofuranyl, pyrrolyl and the like, which are optionally substituted with one or more functional groups as defined herein. In certain embodiments, the term "heterocyclic" refers to a non-aromatic 5-, 6-, or 7-membered ring or polycyclic group, including but not limited to bicyclic or tricyclic groups comprising a fused six-membered ring having 1-3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein (i) each 5-membered ring has 0 to 2 double bonds and each 6-membered ring has 0 to 2 double bonds, (ii) the nitrogen and sulfur heteroatoms may optionally be oxidized, (iii) the nitrogen heteroatom may optionally be quaternized, and (iv) any of the above heterocycles can be fused to an aryl or heteroaryl ring. Representative heterocycles include, but are not limited to, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, and tetrahydrofuranyl.

Generally, the term "aromatic" or "aryl" as used herein refers to a stable substituted or unsubstituted unsaturated monocyclic or polycyclic hydrocarbyl moiety having preferably 3 to 14 carbon atoms, which comprises at least one ring satisfying the houckel's law of aromaticity. Examples of aromatic moieties include, but are not limited to, phenyl, indanyl, indenyl, naphthyl, phenanthryl, and anthracyl.

As used herein, the term "heteroaryl" refers to an unsaturated mono-or poly-heterocyclic moiety having preferably 3 to 14 carbon atoms and at least one ring atom selected from S, O and N, which contains at least one ring satisfying the huckel rule of aromaticity. The term "heteroaryl" refers to a compound having from about 5 to about 10 ring atoms and wherein one ring atom is selected from S, O and N; zero, one, or two ring atoms are additional heteroatoms independently selected from S, O and N; and the remaining ring atoms are cyclic unsaturated groups of carbon, which radical is attached to the rest of the molecule through any ring atom, such as, for example, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, thienyl, furyl, quinolinyl, isoquinolinyl, and the like. Examples of heteroaryl moieties include, but are not limited to, pyridyl, quinolinyl, dihydroquinolinyl, isoquinolinyl, quinazolinyl, dihydroquinazolinyl, and tetrahydroquinazolinyl.

As used herein, the expression "C_x-C_yPreferably C_x1-C_y1An alkylaryl, arylalkyl, or aryl group, "wherein x, y, x1, and y1 represent integers representing the number of carbon atoms in the chemical moiety to which they are referred (e.g.," alkylaryl, "" arylalkyl, "" aryl ")) means" C_x-C_yAlkylaryl group, C_x-C_yAralkyl or C_x-C_yAryl, preferably C_x1-C_y1Alkylaryl group, C_x1-C_y1Aralkyl or C_x1-C_y1Aryl ". Likewise, the expression "C_x-C_yAlkylaryl, arylalkyl or aryl "means" C_x-C_yAlkylaryl group, C_x-C_yAralkyl or C_x-C_yAryl ".

As used herein, the term "halogen" refers to an atom selected from fluorine, chlorine, bromine, and iodine.

The term "amine" refers to a compound having the structure-N (R)₂Wherein each occurrence of R is independently hydrogen, or a moiety of an aliphatic, heteroaliphatic, aryl, or heteroaryl, or R taken together with the nitrogen atom to which they are attached may form a heterocyclic moiety.

As used herein, the term "independently" refers to the fact that: the substituents, atoms or moieties to which these terms refer are independently selected from the list of variables (i.e., they may be the same or identical).

As used herein, the term "mild light irradiation conditions" or "mild irradiationThe "irradiation conditions" mean that several W/cm are used in the near infrared region, for example, λ 625-²Even at mW/cm²Within the range ofLow strengthThe irradiation conditions of (1). For example, the intensity of near infrared radiation may be 50mW/cm²To 10W/cm²Advantageously 100mW/cm²To 7W/cm²More advantageously 200mW/cm²To 5W/cm²More advantageously 300mW/cm²To 3W/cm²The range of (1).

As used herein, "about" refers to any inherent measurement error or rounding of values (e.g., measured values, calculated values, such as ratios), and thus the term "about" may be used with any value and/or range. As used herein, the term "about" can refer to a variation of ± 5% of the specified value. For example, in some embodiments, "about 50%" may have a variation of 45% to 55%. For a range of integers, the term "about" can include one or two integers greater than and/or less than the recited integer. Unless otherwise indicated herein, the term "about" is intended to include values near the recited ranges that are equivalent in terms of functionality for the respective ingredient, composition, or embodiment, e.g., wt%, temperature.

As used herein, the term "and/or" refers to any one of, any combination of, or all of the items associated with the term.

As will be understood by those skilled in the art, all numbers, including those expressing quantities of ingredients such as molecular weights, reaction conditions, and so forth, are approximations and in all instances will be understood as being modified by the term "about". These values may vary depending on the desired properties sought to be obtained by those skilled in the art using the teachings described herein. It will also be understood that these values inherently contain variability necessarily resulting from the standard deviation found in their respective test measurements.

As will be understood by those skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges recited herein also encompass any and all possible subranges and combinations of subranges thereof, as well as individual values, particularly integer values, that make up the range. A recited range (e.g., weight percent or carbon groups) includes each particular value, integer, decimal, or identity within the range. Any listed range can be easily identified as fully descriptive and the same range can be broken down into at least equal halves, thirds, quarters, fifths, or tenths. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, a middle third, and an upper third, etc.

As those skilled in the art will also appreciate, all languages such as "up to," "at least," "greater than," "less than," "exceeding," "or more," and the like, including the recited number, are intended to encompass the ranges subsumed therein as well as ranges into which such terms may be subsequently subdivided. In the same manner, all ratios recited herein also include all sub-ratios falling within the broader ratio. Thus, the specific values recited for the groups, substituents, and ranges are for illustration only; they do not exclude other defined values or other values within the definition of radicals and substituents.

Those skilled in the art will also readily recognize that where members are grouped together in a common manner, such as in a Markush (Markush) group, the present invention encompasses not only the entire group as a whole, but also each member of the group and all possible subgroups of the main group. In addition, for all purposes, the present invention includes not only the master group, but also the master group lacking one or more team members of the group. Thus, the present invention contemplates the explicit exclusion of any one or more members of an enumerated group. Thus, the conditions may apply to any of the disclosed categories or embodiments, whereby, for example, any one or more of the listed elements, categories or embodiments may be excluded from the categories or embodiments as used in an explicit negative limitation.

Detailed description of certain preferred embodiments of the invention

As mentioned above, in recent years there has been increasing interest in the development of new photoinitiator systems that effectively trigger photopolymerization processes under mild light irradiation, e.g., in the red to near infrared region. To date, only a few studies have reported near-infrared induced ("NIR induced") photopolymerization. However, to date, only a few studies have been reported. [1,2,3] for example, curing of NIR photoinitiated systems using cyanine-based dyes has been reported. [3] However, the use of NIR photoinitiating systems (e.g., cyanines) is generally associated with low reactivity (low conversion and/or reaction rate) and requires high light intensity. Such NIR-photoinitiator systems are therefore generally not suitable for most practical/industrial applications, especially applications requiring mild intensity irradiation.

The present inventors have found that an appropriately selected three-component photoinitiator system can overcome the above-mentioned disadvantages in the art.

In this context, provided herein is a photoinitiating composition comprising:

(a) an absorbing dye that is an electron donor when exposed to a 625-;

(b) an oxidizing agent suitable for polymerization and capable of generating radicals and/or cations by electron transfer from the dye upon exposure to a light source of 625-.

(c) A reducing agent suitable for regeneration of the dye; and

(d) an optional oxygen scavenger.

Briefly, the present invention relates to a combination of three components as a photoinitiator system for red to Near Infrared (NIR) photopolymerization, preferably NIR-induced photopolymerization. The three-component combination is based on: 1) an absorbing dye which acts as a photosensitizer in the red to NIR range, preferably the NIR range, 2) an oxidizing agent capable of generating free radicals and/or cations by transfer of electrons from the absorbing dye upon exposure to a 625-; and 3) a reducing agent suitable for the regeneration of the absorption dye.

Advantageously, the photoinitiator system may additionally comprise an oxygen scavenger suitable for reducing and/or preventing oxygen inhibition during free radical polymerization.

a)Absorbing dye

Advantageously, the absorbing dye may be any suitable dye that is an electron donor when exposed to a 625-.

Advantageously, the absorbing dye may comprise a conjugated system, cyclic or acyclic, containing 2 or 4 heteroatoms selected from N or S whose lone pair of electrons may participate in the conjugated system; wherein the absorbing dye is an electron donor when exposed to a 625-2500nm light source, for example, 625-1500nm light irradiation. Advantageously, the absorbing dye may comprise:

an open conjugated system containing two N or S atoms, preferably two N atoms, whose lone pair of electrons can participate in the conjugated system;

-a conjugated macrocyclic system containing four N or S atoms, preferably four N atoms, complexed to a single metal atom; preferably in the red to near infrared region of 625-;

-a metal complex containing two bidentate conjugated ligands; each bidentate ligand contains two N or S atoms, preferably two S atoms, complexed to a single metal atom; preferably in the red to near infrared region of 625-.

Advantageously, the absorbing dye may be chosen from cyanine, phthalocyanine, dithiolene or porphyrin dyes.

As used herein, the term "cyanine dye" does not deviate from the conventional meaning of the term, and refers to a dye having an open conjugated system, in which part thereofAnd sectionCovalently linked through a conjugated system of two or more double bonds, some of which may belong to aromatic radicals. The expression "open conjugated system" refers to the fact that:do not form a ring with a conjugated double bond (i.e., do not piggyback together in their entirety to form a ring). However, the entire system may comprise one or more mono-or polycyclic cycloaliphatic, heterocyclic, aromatic or heteroaromatic groups.

Examples of such cyanine dyes include:

wherein X^-Represent suitable counterions. For example, X^-May represent Cl^-、I^-、ClO₄ ^-P-toluenesulfonate, p-dodecylbenzenesulfonate or borate anions, such as triphenylbutylborate.

Advantageously, the counterion X^-May represent a borate anion. For example, X^-May represent triphenylbutylborate.

For example, any one or more of the following cyanine dyes may be used as the absorbing dye:

as used herein, the term "phthalocyanine dye" does not depart from the conventional meaning of the terms in the art, and refers to a conjugated macrocycle containing different metallic or metalloid inclusions depending on how it is synthesized. Advantageously, the phthalocyanine dyes which can be used in the context of the present invention may have a cyclic conjugated system of the following structure:

wherein M represents a metal center, e.g., Mn, and L₁And L₂Independently represents a propionyl (acyloyl) ligand or may be absent depending on the valence of the metal atom.

Examples of such phthalocyanine dyes include:

most phthalocyanines (Pc) have a high molar absorption coefficient and absorb light in the red and Near Infrared (NIR) regions (. apprxeq.650-700 nm [4, 6 ]).

Incidentally, NIR dyes, and more specifically borate dyes, have also been used for information recording, such as xerography, dry photographic printing techniques.

When the cyanine borate dye is subjected to light irradiation, electron transfer between the dye and the counter ion causes radical recombination of the dye to give a leuco dye. This process facilitates bleaching and ultimately, multiple recycling of the paper. This bleaching property may also be of no interest for photopolymerization. Changing from green to colorless upon polymerization, light can penetrate deeper into the sample and thus thicker samples can be polymerized.

As used herein, the term "dithiolene dye" does not deviate from the conventional meaning of the term in the art, and refers to a metal complex comprising an unsaturated bidentate ligand containing two sulfur donor atoms. They may also be referred to as "metal disulfide dyes". Advantageously, the dithiolene dyes useful in the context of the present invention may have the following structure:

wherein M represents a metal center that absorbs in the red to near infrared region of 625-; and Ar₁、Ar₂、Ar₃And Ar₄Independently represent C_6～10An aryl group; wherein each aryl moiety may each be further substituted by one OR more substituents such as-OH, -OR, halogen atoms, -NO₂、-CN、-NR^A ₁R^A ₂、-NHC(＝O)R^A ₃、-OC(＝O)R^A ₃Vinyl or straight or branched C_1-10Alkyl or C_6-10Aryl moiety substituted; wherein R and R^A ₃Independently represents a straight or branched chain C_1-10Alkyl or C_6-10An aryl moiety; and R is^A ₁And R^A ₂Independently represent H or straight or branched C_1-6Alkyl or C_6-10Aryl moiety, wherein R^A ₁And R^A ₂Together with the nitrogen atom to which they are attached may form a 5-or 6-membered heterocyclic moiety; wherein each of the above aryl moieties may each be further substituted by one or more straight or branched chain C_1-6Alkyl or C_6-10Aryl moieties. Advantageously, Ar₁、Ar₂、Ar₃And Ar₄May independently represent a phenyl moiety; wherein each phenyl moiety may each be further substituted by one or more substituents such as those described above, preferably straight or branched C_1-6Alkyl moieties including methyl, propyl, butyl, isopropyl substituted.

Examples of such dithiolene dyes include:

as used herein, the term "porphyrin dye" does not deviate from the conventional meaning of this term in the art, and refers to conjugated heterocyclic macrocyclic metal complexes comprising four modified pyrrole subunits interconnected at their alpha carbon atoms by methine bridges (═ CH-).

Advantageously, the porphyrin dyes that can be used in the context of the present invention may have a heterocyclic conjugated system of the following structure:

wherein M represents a metal center that absorbs in the red to near infrared region of 625-2500nm, e.g., in625-; and R is₁、R₂、R₃And R₄May independently represent H, -C (═ O) OR₅Vinyl, straight or branched C_1-10Alkyl or C_6-10An aryl moiety; wherein R is₅Each occurrence of (A) may independently represent H or an alkali metal cation such as Na⁺(ii) a And wherein each of the foregoing alkyl or aryl moieties may each be further substituted with one or more straight or branched chain C_1-6Alkyl or C_6-10Aryl moieties.

Examples of such porphyrin dyes include copper salts of sodium chlorophyllin:

advantageously, the absorbing dye may be present in a quantity based on the total weight of the composition to be polymerized; i.e., the total weight of the aforementioned polymerizable components + the total weight of components a), b) and c) is about 0.01 wt.% to 0.5 wt.%, preferably 0.01 to 0.4 wt.%, preferably 0.01 wt.% to 0.3 wt.%, more preferably 0.25 wt.% or less, still more preferably 0.20 wt.% or less, and most preferably 0.15 wt.% or less. For example, the absorbing dye may be present in an amount based on the total weight of the composition to be polymerized; that is, the total weight of the above polymerizable components + the total weight of components a), b) and c) is about 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.10 wt%, 0.11 wt%, 0.12 wt%, 0.13 wt%, 0.14 wt%, 0.15 wt%, 0.16 wt%, 0.17 wt%, 0.18 wt%, 0.19 wt%, 0.20 wt% is used.

b)Oxidizing agent

The oxidizing agent may be selected from any suitable oxidizing agent known in the art of polymerization. For example, the oxidizing agent may be selected from onium salts (e.g., of formula (R)_A)₂I⁺X_A ^-Or (R)_A)₃S⁺X_A ^-Iodonium salt or sulfonium salt of (a); wherein R is_AEach occurrence of (A) independently represents C_6-10Aryl or C_1-10An alkyl moiety; wherein each aryl moiety may each be further substituted by one or more straight or branched chain C_1-6Alkyl orC_6-10Aryl moiety substituted; and X_A ^-Representing a suitable counterion). For example, each occurrence of R_AMay independently represent phenyl or C_1-10An alkyl moiety; wherein each phenyl moiety may be further substituted with one or more straight or branched C_1-6Alkyl or C_6-10Aryl moieties. For example, the phenyl moiety may preferably bear one or more methyl, ethyl, n-propyl, isopropyl, tert-butyl groups in the para position relative to the iodine atom. In an exemplary embodiment, X_A ^-Can represent B (PhF)₆)₄ ^-、PF₆ ^-、SbF₆ ^-Or Cl^-. Preferably X_A ^-Can represent B (PhF)₆)₄ ^-Or PF₆ ^-Most preferably B (PhF)₆)₄ ^-。

Advantageously, the oxidizing agent may be of the formula (R) as defined and described above and in any of the variants herein_A)₂I⁺X_A ^-The iodonium salt of (1). Advantageously, the oxidizing agent may be:

advantageously, the oxidizing agent may be present in an amount based on the total weight of the composition to be polymerized; i.e., the total weight of the aforementioned polymerizable components + the total weight of components a), b) and c) is about 0.1 to 5.0 wt%, preferably 0.5 to 4.0 wt%, more preferably 1 to 4.0 wt%, still more preferably 2.0 to 4.0 wt%, and most preferably about 3 wt%. For example, the oxidizing agent may be based on the total weight of the composition to be polymerized; i.e., the total weight of the polymerizable components + the total weight of components a), b), and c), is used at about 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, 5.0 wt%.

c)Reducing agent

Advantageously, the reducing agent (c) may be any reducing agent suitable for the regeneration of the absorbing dye (a). In the initial stage of the photoinitiation process, the dye (when exposed to625-2500nm light sources, e.g., electron donors when exposed to 625-1500nm light irradiation) absorb light in the red-NIR range to release electrons and form free radical dyes^·+. The expression "regenerating the absorbing dye (a)" used in the context of the present invention means that the dye is intended to be applied^·+The process of radical reduction to the original neutral dye molecule.

Thus, advantageously, the Reducing Agent (RA) is preferably capable of reacting the dye^·+The free radicals are reduced to the original neutral dye molecule as follows:

dye material^·++ RA → dye + RA^·+

Examples of suitable reducing agents include phosphine compounds/phosphine-based reducing agents (e.g., 4- (diphenylphosphine) benzoic acid (4-dppba), 2-diphenylphosphinobenzoic acid (2-dppba), bis (2-diphenylphosphinophenyl) -ether (2-dpppe), trimethoxyphenylphosphine (triompp), DPBP bidentate phosphine (DPBP), 4-dimethylaminophenyldiphenylphosphine (4-dmapp), (R, R) -dach-phenyl-test (test), triphenylphosphine (tpp)); and amine compounds/amine based reducing agents (e.g., ethyl 4-dimethylaminobenzoate (EDB), 4- (dimethylamino) phenylacetic Acid (ADP), Triphenylamine (TPA), N-Dibutylaniline (DBA), N-ethyl-N-isopropylaniline (EIPA), 3- (dimethylamino) benzyl alcohol (3-dmaba or "DABA"). other suitable amine based reducing agents include N-phenylglycine or other aromatic amines.

Advantageously, the reducing agent (c) may be P (R)_B1)₃Class of phosphine-based reducing agents, wherein each occurrence of R_B1Independently represent C_6-10An aryl group; wherein any of the above aryl moieties may be further independently substituted with one OR more-C (═ O) OH, -C (═ O) OR_B2Or straight or branched C_1-6Alkyl or C_6-10Aryl moiety substituted; wherein R is_B2Independently represent C_6-10Aryl or C_1-10An alkyl moiety. Advantageously, the reducing agent (c) may come from (Ph)₂PR_B1Class I, wherein R_B1Independently represent optionally further substituted by one OR more-C (═ O) OH, -C (═ O) OR_B2Or straight or branched C_1-6Alkyl or C_6-10Aryl partially substituted C_6-10An aryl moiety; wherein R is_B2Independently represent C_6-10Aryl or C_1-10An alkyl moiety. Preferably, the reducing agent (c) may be derived from (Ph)₂PR_B1Class I, wherein R_B1Represents a compound having one OR more C (═ O) OH OR-C (═ O) OR_B2Part C₆Aryl moiety, wherein R_B2Independently represent C_6-10Aryl or C_1-10An alkyl moiety. For example, the reducing agent (c) may be 4- (diphenylphosphino) benzoic acid (4-dppba).

Advantageously, the reducing agent (c) may be an aromatic amine compound having the following structure:

wherein

n represents an integer from 0 to 3, preferably from 0 to 2, most preferably 0 or 1;

R₆and R₇Can independently represent H, C_1-6Alkyl or-C_1-6Alkyl C (═ O) OR₉Wherein R is₉Represents H or C_1-6An alkyl group; and is

R₈May independently represent-C_1-6alkyl-OH or-C_1-6Alkyl C (═ O) OR₁₀Wherein R is₁₀Represents H or C_1-6An alkyl group.

Advantageously, R₆Or R₇At least one is not H.

Advantageously, n may represent 0, R₆May represent H and R₇Can represent-C_1-6Alkyl C (═ O) OR₉Wherein R is₉Represents H or C_1-6An alkyl group.

Advantageously, n may represent 1, R₈Can represent-C_1-6alkyl-OH, and R₆And R₇May independently represent C_1-6An alkyl group.

Advantageously, the reducing agent (c) may be NPG or DABA:

advantageously, the reducing agent may be present in an amount based on the total weight of the composition to be polymerized; i.e., the total weight of the aforementioned polymerizable components + the total weight of components a), b) and c is about 0.1 to 5.0 wt%, preferably 0.5 to 4.0 wt%, more preferably 1.0 to 4.0 wt%, still more preferably 1.0 to 3.0 wt%, and most preferably about 2 wt% is used. For example, the oxidizing agent may be present in an amount based on the total weight of the composition to be polymerized; i.e.the total weight of the aforementioned polymerizable components + the total weight of components a), b) and c) is about 0.5 wt.%, 1.0 wt.%, 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt.%, 4.0 wt.%, 4.5 wt.%, 5.0 wt.% is used.

d)Oxygen scavenger

Advantageously, oxygen scavengers may be used in the photoinitiating compositions according to the present invention to promote polymerization in the event that undesirable peroxide radicals are formed during polymerization (e.g., when the polymerization is conducted in the presence of oxygen (e.g., in air or ambient atmosphere)). Advantageously, when an oxygen scavenger is used, it should be compatible with the intended photopolymerization (radical, cationic or radical/cationic dual photopolymerization): the oxygen scavenger preferably does not interfere with the active species that promote the type of polymerization reaction that is being carried out. For example, the oxygen scavenger preferably does not interfere with free radical formation and/or cation formation.

For example, when the polymerization is carried out under air, certain monomers (such as methacrylates) may be sensitive to the presence of oxygen in air. In this case, peroxy radicals may be generated during the polymerization, which are too stable to polymerize (in other words, polymerization is inhibited). Oxygen scavengers help to overcome the inhibition of oxygen by reacting with peroxy radicals to produce less stable radicals, which in turn can allow the polymerization reaction to proceed/continue. Any conventional oxygen scavenger used to promote polymerization may further be used as part of the photoinitiating composition of the present invention. Examples of such oxygen scavengers include potassium sulfite, unsaturated hydrocarbons, and ascorbic acid derivatives.

Advantageously, the reducing agent (c) and the oxygen scavenger (d) may be one compound (in other words, one and the same compound)Can be used both as reducing agent (c) and as oxygen scavenger (d)). For example, any of the phosphine reducing agents described in section c) above may also act as an oxygen scavenger. Advantageously, therefore, the oxygen scavenger (d) may be a compound derived from P (R)_B1)₃Phosphine-based compounds of the class in which each occurrence of R_B1Independently represent C_6-10An aryl group; wherein any of the above aryl moieties may be further independently substituted with one OR more-C (═ O) OH, -C (═ O) OR_B2Or straight or branched C_1-6Alkyl or C_6-10Aryl moiety substituted; wherein R is_B2Independently represent C_6-10Aryl or C_1-10An alkyl moiety. Advantageously, the oxygen scavenger (d) may come from (Ph)₂PR_B1Class I, wherein R_B1Independently represent optionally further substituted by one OR more-C (═ O) OH, -C (═ O) OR_B2Or C being straight-chain or branched_1-6Alkyl or C_6-10Aryl partially substituted C_6-10An aryl moiety; wherein R is_B2Independently represent C_6-10Aryl or C_1-10An alkyl moiety. Preferably, the oxygen scavenger (d) may be derived from (Ph)₂PR_B1Class I, wherein R_B1Represents a compound having one OR more C (═ O) OH OR-C (═ O) OR_B2Part C₆Aryl moiety, wherein R_B2Independently represent C_6-10Aryl or C_1-10An alkyl moiety. For example, the oxygen scavenger (d) may be 4- (diphenylphosphinobenzoic acid (4-dppba).

e)Irradiation light source

The light source may be any light source known in the art capable of generating light in the range of 625-. For example, light from LED bulbs, lasers, laser diodes, low pressure mercury and argon lamps, fluorescent lamp systems, arc sources, high intensity light sources may be used. Advantageously, the light source may generate light in the red region of the spectrum (i.e., 625-750 nm). For example, light sources that may be used to achieve this include LED bulbs, lasers, laser diodes, fluorescent lamp systems, arc sources, high intensity (3000K metal halide, high pressure sodium lamp), xenon lamps, mercury-xenon lamps. Advantageously, the light source can generate light in the near infrared region of the spectrum (i.e., 700 f)2500nm, e.g., 700 and 1500 nm). Light sources that may be used for this purpose include, for example, NIR LEDs, NIR lasers, low-pressure mercury and argon lamps (696-₄、Nd:CidVO₄、Nd:LuVO₄、CO₂A laser.

An important advantage of the present invention is that photopolymerization can be carried out under long wavelength irradiation conditions (e.g., lower and safer energy than UV-type irradiation).

Advantageously, the light source is preferably chosen according to the absorbing dye used: most advantageously, the light source may be the dye that absorbs light most readily at the dye to initiate the polymerization process^·+A light source emitting light in the wavelength range of the radicals. The absorption curve of a dye that is known to absorb in the red or near infrared range of the spectrum is known or can be readily determined by using a plot of absorbance versus wavelength. It is evident throughout the teachings of this document that if a particular dye exhibits low/moderate absorbance at a given wavelength, it can still be employed at the same given wavelength by increasing the intensity of the light irradiation. This can be achieved, for example, by usingAdjustable powerLight sources such as commercially available red to near infrared light sources of tunable power.

Dye material	Red or NIR absorption range
		IR 140	600-900nm
IR 780	>670nm
		Indocyanine green	600-900nm
IR 813	>670nm
		S 2265	600-850nm
S 0991	>650nm
		Mn-Ph	600-800nm
Dithiolene nickel 1	>750nm
		Sodium copper chlorophyllin	550-700nm

For illustration purposes, if IR780 is used as the heat-generating dye, an NIR laser @785nm may be used.

As mentioned above, it should be understood that the light source may be a variable power light source; this is a light source equipped with adjustable power so that the power of red to near infrared radiation can be adjusted as desired. Such a power-adjustable light source can also be used to determine the threshold light intensity at which a particular dye begins to absorb at any given wavelength, and thus fine tune the wavelength/irradiation intensity that can be used to obtain optimal polymerization conditions.

f)Polymerizable component

Advantageously, the photoinitiating composition according to the invention may be used in polymerization reactions involving at least one polymerizable component selected from:

(i) ethylenically unsaturated monomers, the polymerization of which can be carried out by free radical polymerization; and/or

(ii) Ethylenically unsaturated monomers or epoxy-containing monomers or oxetane monomers or vinyl ether-containing monomers or lactide monomers or lactone monomers or caprolactone monomers; the polymerization thereof may be carried out by cationic polymerization.

Advantageously, the at least one polymerizable component may be an ethylenically unsaturated monomer, the polymerization of which may be carried out by free radical polymerization. As used herein, the term "ethylenically unsaturated monomer" refers to a polymerizable component that includes at least one carbon-carbon double bond. Preferably, the ethylenically unsaturated monomer whose polymerization can be carried out by free radical polymerization contains at least one carbon-carbon double bond conjugated with an aryl moiety (e.g., phenyl), a carboxyl group (C ═ O), or another double bond. Monomers of this class include, for example, acrylate- [ (ROCO) CHCH₂]… - (acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, etc.), and (meth) acrylic acid esters- [ (ROCO) C (Me) CH₂]- (methacrylic acid, methyl methacrylate, etc. …), styrene, ethylene, propylene, N-vinylacrylamide, N-vinylpyrrolidone. For example, the at least one polymerizable component may be an acrylate or methacrylate monomer. For example, the at least one polymerizable component may be a methacrylate monomer such as (hydroxypropyl) methacrylate (HPMA), 1, 4-butanediol dimethacrylate (1,4-BDDMA), 1, 6-dimethacryloxy-2-ethoxycarbonylamino-2, 4, 4-trimethylhexane (BMATMH), or a methacrylate functionalized prepolymer such as UDMA

Advantageously, the at least one polymerizable component may be an ethylenically unsaturated monomer or an epoxy-containing monomer or an oxetane monomer or a vinyl ether-containing monomer or a lactide monomer or a lactone monomer or a caprolactone monomer. The polymerization thereof may be carried out by cationic polymerization. Examples of such monomers include vinyl ether- [ ROCHCH₂]Such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; and an epoxy monomer. As used herein, the term "epoxy-containing monomer" refers to a monomer having an oxirane ring having the structurePartial monomers of (a):for exampleOrWherein "-" denotes the point of attachment of the ethylene oxide moiety to the remainder of the monomer; and R is₁And R₂Independently represents H or straight or branched C_1-10Alkyl or C_6-10An aryl moiety; wherein each of the above aryl moieties may each be further substituted by one or more straight or branched chain C_1-6Alkyl or C_6-10Aryl moieties. For example,

the polymerizable component may be an epoxy-containing monomer (EPOX) having the structure:

also, as used herein, the term "oxetane-containing monomer" refers to a monomer with a moiety comprising an oxetane ring having the structure:for exampleWherein "-" represents the point of attachment of the oxetane moiety to the remainder of the monomer; r₁And R₂Independently represent H or straight chain or branched C_1-10Alkyl or C_6-10An aryl moiety; wherein each of the above aryl moieties may each be further substituted by one or more straight or branched chain C_1-6Alkyl or C_6-10Aryl moieties. For example, the at least one polymerizable component may be one of the following oxetane-containing monomers:

the vinyl ether-containing monomers that may be used in the context of the present invention may be any known vinyl ether-containing monomers, including commercially available vinyl ether monomers such as: bis [4- (vinyloxy) butyl]1,6^-Adipylbicarbamate, bis [4- (vinyloxy) butyl ]]Isophthalate, bis [4- (vinyloxy) butyl ]](methylenebis-4, 1-phenylene) biscarbamate, bis [4- (vinyloxy) butyl]Succinate ester, bis [4- (vinyloxy) butyl]Terephthalic acid ester, glutaric acid bis [4- (vinyloxymethyl) cyclohexylmethyl]Esters, 1, 4-butanediol divinyl ether, 1, 4-butanediol vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, 2-chloroethyl vinyl ether, cis-1, 4-cyclohexanedimethanol divinyl ether, trans-1, 4-cyclohexanedimethanol divinyl ether, cyclohexyl vinyl ether, di (ethylene glycol) divinyl ether, di (ethylene glycol) vinyl ether, diethylvinyl orthoformate, dodecyl vinyl ether, ethylene glycol vinyl ether, 2-ethylhexyl vinyl ether, ethyl-1-propenyl ether (cis, trans or mixtures thereof), ethyl vinyl ether, isobutyl vinyl ether, phenyl vinyl ether, propyl vinyl ether tris [4- (vinyloxy) butyl.]Trimellitic esters of trimellitic acid.

It is to be understood that the photoinitiating compositions of the present invention may be used to performAt least one kind ofFree radical polymerization and/or cationic polymerization of a polymerizable component selected from the group consisting of:

(i) ethylenically unsaturated monomers, the polymerization of which can be carried out by free radical polymerization; and/or

(ii) Ethylenically unsaturated monomers or epoxy-containing monomers or oxetane-containing monomers or vinyl ether-containing monomers or lactide monomers or lactone monomers or caprolactone monomers; the polymerization thereof may be carried out by cationic polymerization;

or a mixture of two or more thereof.

Thus, the polymerizable component may be a mixture of two or more ethylenically unsaturated monomers (i), as generally and as defined and described in the variants herein. For example, the polymerizable component may be a mixture of:

the polymerizable component may be a mixture of two or more monomers (ii), as generally and as defined and described in the variants herein. For example, a mixture of vinyl ether monomers and ethylenically unsaturated monomers that can be polymerized by cationic polymerization can be used.

The polymerizable component may also be a mixture of at least one monomer (i) and at least one monomer (ii), as generally and as defined and described in the variants herein. In other words, the polymerizable component may be a polymerizable compound that can pass throughIs differentThe polymerization mechanism: a mixture of two or more components polymerized separately by free radical polymerization or cationic polymerization. For example, the polymerizable component may be a mixture of HPMA and EPOX. Other examples include mixtures of vinyl ether/acrylates and vinyl ether/epoxies.

An important advantage of the three-component photoinitiator compositions described herein is at least two-fold:

(i) they are irradiated under very mild irradiation conditions (i.e., at several W/cm)²Or even mW/cm²Generates radicals in the near-infrared region, e.g., λ 625-

(ii) When ethylenically unsaturated monomers or epoxy-containing monomers or oxetane-containing monomers or vinyl ether-containing monomers or lactide monomers or lactone monomers or caprolactone monomers are present, the polymerization of which can be carried out by cationic polymerization, they can initiate a free radical-promoted cationic photopolymerization.

Thus, when using monomer mixtures with these unique polymerization mechanisms, the use of the three-component photoinitiator composition of the present invention under mild light irradiation conditions allows for concomitant free radical and cationic polymerization. This allows the preparation of interpenetrating networks of polymers with different polymerization mechanisms (free radical and cationic) using a single photoinitiator. This is a significant advantage over prior methods that required the use of two different polymerization initiators, a photoinitiator for free radical polymerization and a cationic initiator for cationic polymerization. It is inevitable that the use of two different initiators would imply different initiation times and therefore the polymerization reaction may proceed at different rates and/or with different efficiencies, resulting in interpenetrating polymer networks of far lower homogeneity than those obtainable by the photopolymerization process of the invention.

The adsorbing dye a), the oxidizing agent b), the reducing agent c), the polymerizable component f) and the irradiation light source may be as defined above and in any of the variants described herein.

Advantageously, the following proportions of a), b) and c) may be used:

the absorbing dye may be used in an amount of about 0.01 to 0.5 wt%, preferably 0.01 to 0.4 wt%, preferably 0.01 to 0.3 wt%, more preferably 0.25 wt% or less, even more preferably 0.20 wt% or less, most preferably 0.15 wt% or less. For example, the absorptive dye may be used at about 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.10 wt%, 0.11 wt%, 0.12 wt%, 0.13 wt%, 0.14 wt%, 0.15 wt%, 0.16 wt%, 0.17 wt%, 0.18 wt%, 0.19 wt%, 0.20 wt%;

the oxidizing agent may be used at about 0.1 to 5.0 wt%, preferably 0.5 to 4.0 wt%, more preferably 1 to 4.0 wt%, even more preferably 2.0 to 4.0 wt%, most preferably about 3 wt%. For example, the oxidizing agent may be used at about 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, 5.0 wt%;

the reducing agent may be used in an amount of about 0.1-5.0 t%, preferably 0.5-5.0 wt%, preferably 0.5-4.0 wt%, more preferably 1.0-4.0 wt%, even more preferably 1.0-3.0 wt%, most preferably about 2 wt%. For example, the oxidizing agent may be used at about 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, 5.0 wt%;

all wt% are based on the total weight of the composition to be polymerized; i.e.the total weight of the aforementioned polymerizable component f) + the total weight of components a), b) and c).

The oxygen scavenger, if different from the reducing agent, may be used in an appropriate amount conventionally used in photopolymerization processes to exert its oxygen scavenging function.

Polymerization process

In another aspect, there is provided a process for free radical and/or cationic photopolymerization under irradiation with 625-:

(i) ethylenically unsaturated monomers, the polymerization of which can be carried out by free radical polymerization; and/or

(ii) Ethylenically unsaturated monomers or epoxy-containing monomers or oxetane-containing monomers or vinyl ether-containing monomers or lactide monomers or lactone monomers or caprolactone monomers; the polymerization thereof may be carried out by cationic polymerization;

or a mixture of two or more thereof.

The variants described above, in particular the variants for the various components of the photoinitiating composition according to the invention, are applicable variations in this section and will be understood to apply to the polymerization process defined in this section. This includes all the variations described in the "detailed description of certain preferred embodiments" section of this document, including any and all variations relating to a) absorbing dyes, b) oxidizing agents, c) reducing agents, d) oxygen scavengers, e) irradiation light sources, and f) polymerizable components described above and in the following exemplary sections and figures in this document.

For example, the at least one polymerizable monomer is an acrylate or methacrylate whose polymerization is carried out by free radical polymerization.

For example, the at least one polymerizable monomer is a vinyl ester or an epoxide whose polymerization is carried out by cationic polymerization.

Advantageously, the interpenetrating network of at least two polymers resulting from the concomitant polymerization of free radicals and/or cations is prepared by carrying out the free radical and/or cationic photopolymerization according to the invention (see discussion above in "f) polymerizable component", referring to variants in which the polymerizable component may be a mixture of two or more components that can be polymerized by different polymerization mechanisms).

Polymer and method of making same

In another aspect, a polymeric material obtainable by the photopolymerization method according to the invention is provided. Likewise, the above-described variants, in particular variants for the various components of the photoinitiating composition according to the invention, are applicable variations in this section and should be understood to apply to the polymeric materials defined in this section. This includes all the variants described in the "detailed description of certain preferred embodiments" section of this document, including any and all variants relating to a) absorbing dyes, b) oxidizing agents, c) reducing agents, d) oxygen scavengers, e) irradiation light sources, f) polymerizable components and polymerization methods described above and in the following exemplary sections and drawings in this document.

Advantageously, the polymeric material may be obtained by photopolymerizing at least a portion of the ethylenically unsaturated monomers polymerized by free radical polymerization and the ethylenically unsaturated monomers or epoxy-containing monomers polymerized by cationic polymerization to form an interpenetrating network of polymer resulting from the free radical and cationic polymerization reactions, in accordance with the mild light-induced polymerization according to the invention.

Method and use

In another aspect, there is provided the use of a photoinitiating composition as defined and described herein generally and in variants in a polymerization reaction. For example, the polymerization reaction may be a radical and/or cationic polymerization.

Likewise, the above-described variants, in particular variants for the various components of the photoinitiating composition according to the invention, are applicable variations in this section and will be understood to apply to the methods and uses defined in this section. This includes all the variants described in the "detailed description of certain preferred embodiments" section of this document, including any and all variants relating to a) absorbing dyes, b) oxidizing agents, c) reducing agents, d) oxygen scavengers, e) irradiation light sources, f) polymerizable components, polymerization processes and polymers described hereinabove and in the following exemplary sections and figures of this document.

For example, there is provided the use of a photoinitiating composition as defined and described generally and in variants herein, wherein the polymerization reaction comprises at least one polymerizable component selected from the group consisting of:

(i) ethylenically unsaturated monomers, the polymerization of which can be carried out by free radical polymerization; and/or

(ii) Ethylenically unsaturated monomers or epoxy-containing monomers or oxetane-containing monomers or vinyl ether-containing monomers or lactide monomers or lactone monomers or caprolactone monomers; the polymerization thereof may be carried out by cationic polymerization.

Advantageously, the ethylenically unsaturated monomer which is polymerized by free radical polymerization may be an acrylate or methacrylate.

Advantageously, the monomer polymerized by cationic polymerization may be an epoxide, oxetane, vinyl ether, lactide, lactone or caprolactone monomer.

In addition, there is provided the use of a photoinitiating composition according to the invention as defined and described herein generally and in variants for the preparation of an interpenetrating network of at least two polymers resulting from the concomitant polymerization of free radicals and/or cations.

Synthesis method

Practitioners have a mature literature of synthetic organic and inorganic chemistry, as well as polymer chemistry, incorporating the information contained herein, to summarize guidelines for synthetic strategies, protecting groups, and other materials and methods suitable for use in photoinitiating compositions and polymer synthesis according to the present invention. For example, the reader is referred to the "exemplary" section below, and references therein that are applicable to synthetic methods for preparing certain compositions and polymeric materials described herein. The reader is referred to the references [4] and [5] relating to phthalocyanine dyes. These are generally simple to synthesize in relatively high yields and have been used as commercial pigments and dyes for decades.

The composite material comprises the following components:

advantageously, the process according to the invention can be carried out generally by conventional methods for preparing the above-mentioned polymers according to the invention in suitable mixing equipment such as, but not limited to, stirred tanks, dissolvers, homogenizers, microfluidizers, extruders or other equipment conventionally used in the art.

When the polymerization process of the present invention is used in the preparation of composites and/or laminates, the process may further comprise the step of adding materials/reinforcements designed for this purpose using known methods.

Advantageously, the polymerization process further comprises the steps of: in a mold, such as a silicone mold, the composite reinforcement is impregnated with a mixture of the light inducing composition and at least one polymerizable component according to the present invention prior to application of the light source.

Advantageously, the composite reinforcement may be any reinforcement conventionally used in the manufacture and implementation of composite materials. For example, the composite reinforcement material may be selected from:

-glass fibres

-carbon fibres

-aramid fibres

Basalt fiber

-silica fibres

-silicon carbide fibres

-polymer fibres

-vegetable fibres (hemp, flax.)

Mineral, metallic or organic fillers (for example, gravel, sand, glass beads, carbonate powder, hydrated alumina powder, steel powder, aluminum powder, polymer particles, titanium oxide, aluminum oxide, etc.)

Advantageously, the composite reinforcement material may be selected from glass fibers, carbon fibers, aramid fibers, basalt fibers, silica fibers, polymer fibers (e.g., polyester, poly (p-phenylene-2, 6-benzodioxazole), aliphatic and aromatic polyamides, polyethylene, polymethylmethacrylate, polytetrafluoroethylene), natural fibers (e.g., nettle, flax or hemp fibers).

Advantageously, the composite reinforcing material may be placed in the mould beforehand before the application of the light irradiation (step (ii)) and subsequently impregnated with the mixture of the photoinitiating composition according to the invention and of at least one polymerizable component (step (i)).

Alternatively, the composite reinforcement material may be pre-impregnated with a mixture of the photoinitiating composition according to the invention and at least one polymerizable component. Then, in the case of mass production, the resulting mixture may be uniformly deposited/spread on a mold manually or using an automatic robot.

The method may further comprise the step of adding resins, composites and any other additives conventionally used in the application field. Examples of suitable additives include:

pigments, such as colour pigments, fluorescent pigments, conductive pigments, magnetic shielding pigments, metal powders, scratch-resistant pigments, organic dyes or mixtures thereof;

light stabilizers, such as benzotriazole or oxalanilide;

crosslinking catalysts, such as dibutyltin dilaurate or lithium decanoate;

-a slip additive;

-an antifoaming agent;

emulsifiers, especially nonionic emulsifiers, such as alkoxylated alkanols and polyols, phenols and alkylphenols, or anionic emulsifiers, such as alkali metal or ammonium salts of alkanecarboxylic acids, alkanesulfonic acids or alkoxylated polyols, phenols or alkylphenols;

wetting agents, such as siloxanes, fluorinated compounds, carboxylic monoesters, phosphoric esters, polyacrylic acids or copolymers thereof, polyurethanes or acrylate copolymers, which are known under the trade markOrThe following are commercially available;

adhesion promoters, such as tricyclodecane-dimethanol;

-a leveling agent;

film-forming aids, such as cellulose derivatives;

-a flame retardant;

sag control agents (sag control agents), such as urea, modified urea and/or silica,

rheology control additives, such as those described in patent documents WO 94/22968[3], EP0276501A1[4], EP0249201A1[5] and WO 97/12945[6 ];

crosslinked polymeric microparticles, for example as described in EP0008127A1[7 ];

phyllosilicates (phyllosilicates), such as magnesium aluminum silicate, magnesium sodium silicate or magnesium fluoride of the montmorillonite type, lithium sodium phyllosilicate;

silica, e.g.Silicon dioxide;

matting agents, such as magnesium stearate; and/or

-a tackifier.

Mixtures of at least two of these additives are also suitable in the context of the present invention.

As used herein, the term "tackifier" refers to polymers that increase the tack properties, i.e., intrinsic viscosity or self-adhesion, of a composition such that they adhere strongly to a surface after a short period of light pressure.

In another aspect, the present invention provides an article obtainable by a polymerization process according to any one of the variants of the process of the present invention, as defined and described herein in general and in the variants.

The present invention has many advantages, including:

red to near infrared wavelengths lead to deeper penetration in the material to be polymerized. As shown in fig. 1, the larger the wavelength: the less light is diffused by the filler in the material. Thus, curing of the filler material with NIR light sources is enhanced compared to curing using UV or visible light; this allows for the polymerization of thicker sample/polymer materials than conventional UV-induced or visible light-induced photopolymerization.

This method is safer than the widely used UV curing method;

the red-based and NIR-based photoinitiator-based systems according to the invention are more efficient (higher conversion and/or photopolymerization rate);

cost-efficiency (the process can be carried out at room temperature and under milder lighting conditions of visible light guided photoinitiator systems than traditional UV-based photoinitiator systems);

-environmentally friendly (solvent not necessary);

the possibility of application in the medical field, in particular due to the use of red to near infrared wavelengths (much safer than UV wavelengths). Existing laser sources in the dermatological field can be used for this purpose.

Further advantages will become apparent to those skilled in the art upon reading the following embodiments, with reference to the following drawings, which are provided by way of non-limiting illustration.

Equivalents of the formula

The following representative examples are intended to help illustrate the invention, and are not intended to, and should not be construed as, limiting the scope of the invention. Indeed, various modifications of the invention and many further embodiments thereof, in addition to those shown and described herein, will become apparent to those skilled in the art from the entire contents of this document, including the following examples, and by reference to the scientific and patent literature cited herein. It should be further understood that the contents of those cited references are incorporated herein by reference to help illustrate the state of the art.

The following examples contain important additional information, exemplification and guidance which can be adapted to the practice of this invention in its various embodiments and equivalents thereof.

Examples of the invention

The polymeric materials and compositions of the present invention and their preparation may be further understood by reference to the following examples which illustrate some of the processes for making or using these polymeric materials and compositions. It should be understood, however, that these examples do not limit the present invention. Variations of the invention, now known or further developed, are considered to fall within the scope of the invention as described herein and claimed hereinafter.

To summarize:

the use of the three-component photoinitiating compositions of the present invention for the NIR photopolymerization of methacrylates is illustrated in the examples below. Specifically, an exemplary photoinitiating composition comprises: 1) dyes for use as photosensitizers absorbing in the NIR range, 2) iodonium salts as oxidizing agents, and 3) phosphine compounds as reducing agents and concomitant oxygen scavengers to prevent polymerization inhibition due to the presence of oxygen. Phosphines are shown to reduce oxygen inhibition, however, they are reported to have this capability only for polymerization with visible light rather than NIR light sources. Thus, to our knowledge, this is the first report of the use of phosphine compounds in NIR-induced photopolymerization and photoinitiator systems.

In addition, Near Infrared (NIR) photoinitiation systems for the photopolymerization of methacrylate monomers are still relatively rare in the literature. Photopolymerization under near infrared light is challenging due to the low energy, but has several advantages if successful. For example, such lower energy wavelengths may be safer than the primary light source UV light currently represented in the photocuring literature. Second, NIR allows deeper light penetration, and thus more complete curing can be achieved, especially for polymerization reactions in the presence of fillers.

Several NIR absorbing dyes, such as borates and phthalocyanines, are set forth and studied in the examples below. Notably, systems using borate dyes result in methacrylate monomer conversions of over 80% under air.

Three types of irradiation systems are proposed: low power LEDs @660nm and 780nm and high power lasers @785 nm.