WO1999054363A1

WO1999054363A1 - Novel photoinitiators and applications therefor

Info

Publication number: WO1999054363A1
Application number: PCT/US1999/008527
Authority: WO
Inventors: Ronald Sinclair Nohr; John Gavin Macdonald
Original assignee: Kimberly Clark Worldwide Inc; Kimberly Clark Corp
Current assignee: Kimberly Clark Worldwide Inc; Kimberly Clark Corp
Priority date: 1998-04-17
Filing date: 1999-04-16
Publication date: 1999-10-28
Anticipated expiration: 2000-10-17
Also published as: EP1080118A1; AU3496199A; JP2002512273A

Abstract

The present invention is directed to new, energy-efficient photoinitiators in the form of organic sulfur-containing compounds. The present invention is also directed to a method of generating reactive species which includes exposing one or more photoinitiators to radiation to form one or more reactive species. Also described are methods of polymerizing unsaturated monomers, methods of curing an unsaturated oligomer/monomer mixture, and methods of laminating using the photoinitiators of the present invention.

Description

NOVEL PHOTOINITIATORS AND APPLICATIONS THEREFOR

Technical Field

The present invention relates to a novel photoinitiators and methods for generating a reactive species using the photoinitiators. The present invention further relates to methods of polymerizing or photocuring polymerizable unsaturated material using the above- mentioned photoinitiators.

Background of the Invention

Polymers have served essential needs in society. For many years, these needs were filled by natural polymers. More recently, synthetic polymers have played an increasingly greater role, particularly since the beginning of the 20th century. Especially useful polymers are those prepared by an addition polymerization mechanism, i.e., free radical chain polymerization of unsaturated monomers, and include, by way of example only, coatings and adhesives. In fact, the majority of commercially significant processes is based on free-radical chemistry. That is, chain polymerization is initiated by a reactive species which often is a free radical. The source of the free radicals is termed an initiator or photoinitiator. Improvements in free radical chain polymerization have focused both on the polymer being produced and the photoinitiator. Whether a particular unsaturated monomer can be converted to a polymer requires structural, thermodynamic, and kinetic feasibility. Even when all three exist, kinetic feasibility is achieved in many cases only with a specific type of photoinitiator. Moreover, the photoinitiator can have a significant effect on reaction rate which, in turn, may determine the commercial success or failure of a particular polymerization process or product.

A free radical-generating photoinitiator may generate free radicals in several different ways. For example, the thermal, homolytic dissociation of an initiator typically directly yields two free radicals per initiator molecule. A photoinitiator, i.e., an initiator which absorbs light energy, may produce free radicals by either of two pathways:

(1) the photoinitiator undergoes excitation by energy absorption with subsequent decomposition into one or more radicals; or

(2) the photoinitiator undergoes excitation and the excited species interacts with a second compound (by either energy transfer or a redox reaction) to form free radicals from the latter and/or former compound(s).

While any free radical chain polymerization process should avoid the presence of species which may prematurely terminate the polymerization reaction, prior photoinitiators present special problems. For example, absorption of the light by the reaction medium may limit the amount of energy available for absorption by the photoinitiator. Also, the often competitive and complex kinetics involved may have an adverse effect on the reaction rate. Moreover, commercially available radiation sources, such as medium and high pressure mercury and xenon lamps, emit over a wide wavelength range, thus producing individual emission bands of relatively low intensity. Most photoinitiators only absorb over a small portion of the emission spectra and, as a consequence, most of the lamps' radiation remains unused. In addition, most known photoinitiators have only moderate "quantum yields" (generally less than 0.4) at these wavelengths, indicating that the conversion of light radiation to radical formation can be more efficient.

Thus, there are continuing opportunities for improvements in free radical polymerization photoinitiators. Moreover, there is a need in the art for new, energy-efficient photoinitiators for use in a variety of polymerization and photocuring processes.

Summary of the Invention

The present invention addresses some of the difficulties and problems discussed above by the discovery of energy-efficient photoinitiators having the following general formula:

wherein x is an integer from 1 to 4, and R and R2 each independently

O N— represent H- ; ^ ' ; (R)2N- where R is an alkyl group having from one to six carbon atoms; a chalcone; HSO3-; and NaSC»3- . In a further embodiment, the present invention is directed to photoinitiators having the following formula:

O O C(S)_X C CH₂

wherein x is an integer from 1 to 4.

The present invention is directed to the above-described photoinitiators, compositions containing the same, and methods for generating a reactive species which includes providing one or more of the photoinitiators and irradiating the one or more photoinitiators. One of the main advantages of the photoinitiators of the present invention is that they efficiently generate one or more reactive species under extremely low energy lamps, such as excimer lamps, as compared to prior art photoinitiators.

The present invention is further directed to methods of using the above-described photoinitiators to polymerize and/or photocure a polymerizable material. The photoinitiators of the present invention result in rapid curing times in comparison to the curing times of prior art photoinitiators, even with relatively low output lamps. The present invention includes a method of polymerizing an unsaturated monomer by exposing the unsaturated monomer to radiation in the presence of the efficacious wavelength specific photoinitiator composition described above. When an unsaturated oligomer/ monomer mixture is employed in place of the unsaturated monomer, curing is accomplished. The present invention further includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition. The admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer-coated nonwoven web or fiber, and a method for producing the same. The present invention is also directed to an adhesive composition comprising an unsaturated polymerizable material admixed with one or more photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above- described adhesive composition, in which at least one layer is a nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition. These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.

Detailed Description of the Invention

The present invention is directed to energy-efficient reactive photoinitiators and methods for utilizing the same. More particularly, the present invention is directed to new photoinitiators having the following general formula:

^"X )>— C(S)_X - (

R₂^= ^■ v =^R₂

wherein x is an integer from 1 to 4, and Ri and R2 each independently

represent H- ; ; (R)2N- where R is an alkyl group having from one to six carbon atoms; a chalcone; HSO3-; and NaSθ3- . In a further embodiment of the present invention, the photoinitiator comprises bis-phthaloylglycine sulfide compounds having the following formula: O O C(S)_X C CH₂

O

wherein x is an integer from 1 to 4.

The present invention also includes a method of polymerizing an unsaturated polymerizable material by exposing the unsaturated material to radiation in the presence of one or more of the photoinitiators described above. Further, the present invention is directed to a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more of the photoinitiators described above, into a film and irradiating the film with an amount of radiation sufficient to polymerize the admixture.

The present invention is further directed to an adhesive composition comprising an unsaturated polymerizable material admixed and one or more photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above- described adhesive composition. The present invention further provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition.

After the following definitions, the photoinitiators of the present invention will be described in detail, followed by a detailed description of the method of generating reactive species, and the various representative applications of the method.

Definitions

As used herein, the term "reactive species" is used herein to mean any chemically reactive species including, but not limited to, free-radicals, cations, anions, nitrenes, and carbenes. Illustrated below are examples of several of such species. Examples of carbenes include, for example, methylene or carbene, dichlorocarbene, diphenylcarbene, alkylcarbonylcarbenes, siloxycarbenes, and dicarbenes. Examples of nitrenes include, also by way of example, nitrene, alkyl nitrenes, and aryl nitrenes. Cations (sometimes referred to as carbocations or

5 carbonium ions) include, by way of illustration, primary, secondary, and tertiary alkyl carbocations, such as methyl cation, ethyl cation, propyl cation, /--butyl cation, f-pentyl cation, £-hexyl cation; allylic cations; benzylic cations; aryl cations, such as triphenyl cation; cyclopropylmethyl cations; methoxymethyl cation; triarylsulphonium cations; and acyl cations. Cations also include those formed from various metal salts, such as tetra-n-butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) triflates. Examples of anions (sometimes referred to as carbanions) include, by way of example, alkyl anions, such as ethyl anion, npropyl anion, isobutyl anion, and neopentyl anion; cycloalkyl anions, such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion; allylic anions; benzylic anions; aryl cations; and sulfur- or phosphorus-containing alkyl anions. Finally, examples of organometallic photoinitiators include titanocenes, fluorinated diaryltitanocenes, iron arene complexes, manganese decacarbonyl, and methyl cyclopentadienyl manganese tricarbonyl. Organometallic photoinitiators generally produce free radicals or cations. As used herein, the term "quantum yield" is used herein to indicate the efficiency of a photochemical process. More particularly quantum yield is a measure of the probability that a particular molecule will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1.

As used herein, the term "polymerization" is used herein to mean the combining, e.g. covalent bonding, of large numbers of smaller molecules, such as monomers, to form very large molecules, i.e., macromolecules or polymers. The monomers may be combined to form only linear macromolecules or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.

As used herein, the term "curing" means the polymerization of functional oligomers and monomers, or even polymers, into a crosslinked polymer network. Thus, curing is the polymerization of unsaturated monomers or oligomers in the presence of crosslinking agents. As used herein, the terms "unsaturated monomer," "functional oligomer," and "crosslinking agent" are used herein with their usual meanings and are well understood by those having ordinary skill in the art. The singular form of each is intended to include both the singular and the plural, i.e., one or more of each respective material.

As used herein, the term "unsaturated polymerizable material" is meant to include any unsaturated material capable of undergoing polymerization. The term encompasses unsaturated monomers, oligomers, and crosslinking agents. Again, the singular form of the term is intended to include both the singular and the plural.

As used herein, the term "fiber" as used herein denotes a threadlike structure. The fibers used in the present invention may be any fibers known in the art. As used herein, the term "nonwoven web" as used herein denotes a web-like matter comprised of one or more overlapping or interconnected fibers in a nonwoven manner. It is to be understood that any nonwoven fibers known in the art may be used in the present invention.

Photoinitiators of the Present Invention The present invention is directed to new photoinitiators having the following general formula:

C(S)_X "-^gζ

wherein x is an integer from 1 to 4, and Ri and R2 each independently

O N— represent H- ; ^ ' ; (R)2N- where R is an alkyl group having from one to six carbon atoms; a chalcone; HSO3-; and NaSθ3- . In a further embodiment of the present, the photoinitiator comprises bis- m-morpholinobenzoyl trisulfide having the following formula:

or bis-p-morpholinobenzoyl trisulfide having the following formula:

O N-

ty

In another embodiment of the present invention, the photoinitiator comprises a bis-dialkylaminobenzoyl trisulfide having the following formula:

O

'R,N C -s ,

wherein R is an alkyl group having from 1 to 6 carbon atoms. Desirably, the photoinitiator comprises bis-m-dimethylaminobenzoyl trisulfide having the following formula:

(CH₃ )_>N. cs-j-s

or bis-p-dimethylaminobenzoyl trisulfide having the following formula:

(CH₃ ^-N— ( \- ffc-

In yet another embodiment of the present invention, the photoinitiator comprises a water-soluble photoinitiator having the following structure:

8

In a further embodiment of the present invention, the photoinitiator comprises bis-phthaloylglycine trisulfide having the following formula:

One method of producing the photoinitiators of the present invention is discussed below. However, it should be noted that the photoinitiators of the present invention may be prepared by any reaction mechanism known to those of ordinary skill in the art. In one embodiment of the present invention, special reagents, used to prepare the photoinitiators of the present invention, are produced by reacting sulfur with a desired amount of lithium triethylborohydride to produce lithium sulfide compounds. The above-described reaction is shown by the following mechanism:

2Li(CH3)3BH + _yS → Li2S_y

Various lithium sulfide compounds may be produced by the above- described reaction including, but not limited to, Li2S, Li2S2, and U2S3.

Preferably y is an integer from 1 to 4. The above-described reaction results in a variety of lithium sulfide compounds wherein y varies from 1 to 3. However, these compounds may be separated using separation techniques known to those of ordinary skill in the art if desired.

The lithium sulfide compounds may be further reacted with a substituted benzoyl chloride, a phthaloylglycine chloride or other carbonyl chloride compounds to produce one or more photoinitiators of the present invention. In one embodiment of the present

9 invention, a morpholinobenzoyl chloride is reacted with one or more lithium sulfide compounds to produce one or more morpholinobenzoyl sulfide compounds. In a further embodiment of the present invention, phthaloylglycine chloride is reacted with one or more lithium sulfide compounds to produce one or more phthaloylglycine sulfide compounds.

The resulting photoinitiators are stable at room temperature (from about 15 C to 25°C) and normal room humidity (from about 30% to 60%). However, upon exposure to radiation, the photoinitiators efficiently produce one or more free radicals. The photoinitiators of the present invention have a high intensity of absorption. For example, the photoinitiators of the present invention may have a molar extinction coefficient greater than about 2,000 liters per mole per cm (1 mole^"lcm^"l) at an absorption maximum. As another example, the photoinitiators of the present invention may have a molar extinction coefficient (absorptivity) greater than about 5,000 1 mole^'lcm^'l. As another example, the photoinitiators of the present invention may have a molar extinction coefficient (absorptivity) greater than about 10,000 l mole^'lcm^"1. As a further example, the photoinitiators of the present invention will have a molar extinction coefficient greater than about 20,000 1 mole^" 1¹ cm -1.

Method of Generating a Reactive Species and Applications Therefor

The present invention is also directed to a method of generating a reactive species. The method of generating a reactive species involves generating a reactive species by exposing one or more of the above-described photoinitiators to radiation. The exposure of the photoinitiators to a radiation source triggers a photochemical process. As stated above, the term "quantum yield" is used herein to indicate the efficiency of a photochemical process. More particularly, quantum yield is a measure of the probability that a particular molecule (photoinitiator) will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1.

The photoinitiators of the present invention absorb photons having a specific wavelength and transfers the absorbed energy to one or more excitable portions of the molecule. The excitable portion of the molecule absorbs enough energy to cause a bond breakage, which

10 generates one or more reactive species. The efficiency with which a reactive species is generated with the photoinitiators of the present invention is significantly greater than that experienced with photoinitiators of the prior art as indicated by faster cure times. For example, the photoinitiators of the present invention desirably will have a quantum yield greater than about 0.5. More desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.6. Even more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.7. Still more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.8, with the most desirable quantum yield being greater than about 0.9.

Exposing the photoinitiators of the present invention to radiation results in the generation of one or more reactive species. Thus, the photoinitiators may be employed in any situation where reactive species are required, such as for the polymerization of an unsaturated monomer and the curing of an unsaturated oligomer/ monomer mixture. The unsaturated monomers and oligomers may be any of those known to one having ordinary skill in the art. In addition, the polymerization and curing media also may contain other materials as desired, such as pigments, extenders, amine synergists, and such other additives as are well known to those having ordinary skill in the art.

By way of illustration only, examples of unsaturated monomers and oligomers include ethylene, propylene, vinyl chloride, isobutylene, styrene, isoprene, acrylonitrile, acrylic acid, methacylic acid, ethyl acrylate, methyl methacrylate, vinyl acrylate, allyl methacrylate, tripropylene glycol diacrylate, trimethylol propane ethoxylate acrylate, epoxy acrylates, such as the reaction product of a bisphenol A epoxide with acrylic acid; polyester acrylates, such as the reaction product of acrylic acid with an adipic acid/ hexanediol-based polyester, urethane acrylates, such as the reaction product of hydroxypropyl acrylate with diphenylmethane-4,4'-diisocyanate, and polybutadiene diacrylate oligomer. The types of reactions that various reactive species enter into include, but are not limited to, addition reactions, including polymerization reactions; abstraction reactions; rearrangement reactions; elimination reactions, including decarboxylation reactions;

11 oxidation-reduction (redox) reactions; substitution reactions; and conjugation/deconjugation reactions.

Accordingly, the present invention also comprehends a method of polymerizing an unsaturated monomer by exposing the unsaturated monomer to radiation in the presence of the efficacious photoinitiators of the present invention described above. When an unsaturated oligomer /monomer mixture is employed in place of the unsaturated monomer, curing is accomplished. It is to be understood that the polymerizable material admixed with the photoinitiators of the present invention is to be admixed by means known in the art, and that the mixture will be irradiated with an amount of radiation sufficient to polymerize the material. The amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiators, the identity and amount of the polymerizable material, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.

It is believed that radiation exposure results in the generation of free radicals from the photoinitiators of the present invention by one or more of the following: cleavage of a sulfur-sulfur bond resulting in two sulfur-terminated free radicals; and cleavage of a carbon-sulfur bond resulting in a carbon-terminated free radical and a sulfur- terminated free radical.

Polymer Films, Coated Fibers and Webs, and Adhesive Compositions

The present invention further includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition. When the unsaturated polymerizable material is an unsaturated oligomer /monomer mixture, curing is accomplished. Any film thickness may be produced, as per the thickness of the admixture formed, so long as the admixture sufficiently polymerizes upon exposure to radiation. The admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer-coated nonwoven web or fiber, and a method for producing the same. Any method known in the art of drawing the admixture into a film may be used in the present invention. The amount of radiation sufficient to

12 polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the intensity and wavelength of the radiation, and duration of exposure to the radiation.

The present invention also includes an adhesive composition comprising an unsaturated polymerizable material admixed with one or more photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition. In one embodiment of the present invention, a laminate is produced wherein at least one layer is a cellulosic or polyolefin nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition. When the unsaturated polymerizable material in the adhesive is an unsaturated oligomer/monomer mixture, the adhesive is irradiated to cure the composition. It is to be understood that any layers may be used in the laminates of the present invention, on the condition that at least one of the layers allows sufficient radiation to penetrate through the layer to enable the admixture to polymerize sufficiently. Accordingly, any cellulosic or polyolefin nonwoven web or film known in the art may be used as one of the layers so long as they allow radiation to pass through. Again, the amount of radiation sufficient to polymerize the admixture is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the identity and thickness of the layer, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.

The radiation to which the photoinitiators of the present invention may be exposed generally will have a wavelength of from about 4 to about 1,000 nanometers. Thus, the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation; visible radiation; and near infrared radiation. Desirably, the radiation will have a wavelength of from about 100 to about 900 nanometers. More desirably, the radiation will have a

13 wavelength of from about 100 to 700 nanometers. Desirably, the radiation will be ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. More desirably, the radiation will have a wavelength of from about 100 to about 390 nanometers, and even more desirably will have a wavelength of from 200 to about 380 nanometers. For example, the radiation may have a wavelength of from about 222 to about 370 nanometers. The radiation desirably will be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp or radiation from a mercury lamp. Excimers are unstable excited-state molecular complexes which occur only under extreme conditions, such as those temporarily existing in special types of gas discharge. Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom. Excimer complexes dissociate within less than a microsecond and, while they are dissociating, release their binding energy in the form of ultraviolet radiation. The dielectric barrier excimers in general emit in the range of from about 125 nm to about 500 nm, depending upon the excimer gas mixture.

Dielectric barrier discharge excimer lamps (also referred to hereinafter as "excimer lamp") are described, for example, by U.

Kogelschatz, "Silent discharges for the generation of ultraviolet and vacuum ultraviolet excimer radiation." Pure & Appl. Chem., 62, No. 9, pp. 16671674 (1990); and E. Eliasson and U. Kogelschatz, "UN Excimer Radiation from Dielectric- Barrier Discharges." Appl. Phys. B. 46, pp. 299-303 (1988). Excimer lamps were developed by ABB Infocom Ltd.,

Lenzburg, Switzerland, and at the present time are available from Heraeus Νoblelight GmbH, Kleinostheim, Germany.

The excimer lamp emits incoherent, pulsed ultraviolet radiation. Such radiation has a relatively narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers.

Desirably, the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers. Most desirably, the half width will be of the order of approximately 5 to 15 nanometers. The ultraviolet radiation emitted from an excimer lamp can be emitted in a plurality of wavelengths, wherein one or more of the wavelengths within the band are emitted at a maximum intensity. Accordingly, a plot of the wavelengths in the band against the intensity for each wavelength in the band produces a bell curve. The "half

14 width" of the range of ultraviolet radiation emitted by an excimer lamp is defined as the width of the bell curve at 50% of the maximum height of the bell curve.

The emitted radiation of an excimer lamp is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the alternating current power supply which typically is in the range of from about 20 to about 300 kHz. An excimer lamp typically is identified or referred to by the wavelength at which the maximum intensity of the radiation occurs, which convention is followed throughout this specification and the claims. Thus, in comparison with most other commercially useful sources of ultraviolet radiation which typically emit over the entire ultraviolet spectrum and even into the visible region, excimer lamp radiation is essentially monochromatic. The source of radiation used with the photoinitiators of the present invention may be any radiation source known to those of ordinary skill in the art. In one embodiment of the present invention, a mercury lamp with a D-bulb, which produces radiation having an emission peak of 350 nm is used to produce free radicals from the above-described photoinitiators. This radiation source is particularly useful when matched with one or more photoinitiators of the present invention having an absorption maximum of 350 nanometers, corresponding to the emission peak of the mercury lamp.

As a result of the photoinitiators of the present invention absorbing radiation in the range of about 250 to about 350 nanometers, the photoinitiators of the present invention will generate one or more reactive species upon exposure to sunlight. Accordingly, these photoinitiators of the present invention provides a method for the generation of reactive species that does not require the presence of a special light source.

The photoinitiators of the present invention enable the production of adhesive and coating compositions that consumers can apply to a desired object and polymerize or cure upon exposure to sunlight. These photoinitiators also enable numerous industry applications wherein unsaturated polymerizable materials may be polymerized merely upon exposure to sunlight. Therefore, depending upon how the photoinitiator is designed, the photoinitiator of the present invention can eliminate the cost of purchasing and maintaining light sources in numerous industries wherein such light

15 sources are necessary without the photoinitiators of the present invention.

The effective tuning of the photoinitiators of the present invention for a specific wavelength band permits the photoinitiators of the present invention to more efficiently utilize the target radiation in the emission spectrum of the radiating source corresponding to the "tuned" wavelength band, even though the intensity of such radiation may be much lower than, for example, radiation from a narrow band emitter, such as an excimer lamp. For example, it may be desirable to utilize an excimer lamp, or other radiation emission source, that emits radiation having a wavelength of approximately 222 nm with the phthaloylglycine-containing photoinitiators of the present invention. Similarly, it may be desirable to utilize a mercury lamp that emits radiation having a wavelength of approximately 350 nm with the substituted benzoyl-containing photoinitiators of the present invention. However, the effectiveness of the photoinitiators of the present invention is not necessarily dependent upon the availability or use of a narrow wavelength band radiation source.

Accordingly, a major advantage of the photoinitiators of the present invention is that they have rapid curing times in comparison to the curing times of the prior art. Another advantage of the present invention is that the photoinitiators of the present invention are highly sensitive photoinitiators and are beneficially used in situations having lower light levels.

The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or the scope of the present invention. In the examples, all parts are by weight, unless stated otherwise.

EXAMPLE 1 Preparation of 3-morpholinobenzoic acid This example describes a method of synthesizing the following compound, 3-morpholinobenzoic acid, which is used in the reaction mechanism for preparing bis-m-morpholinobenzoyl trisulfide:

16 O^

-N COOH

The reaction proceeded as shown below:

0

Et0₂C N + KOH ^Et0H/H2° > HOOC ^

4.3 g of KOH was dissolved in 200 milliliters of ethanol and 100 milliliters of water. Then 5.0 g of 3-morpholinobenzoic acid ester was added and the mixture stirred while heated at reflux for about 2 hours. The mixture was neutralized with dilute HCL and subsequently filtered to give a white solid. The white solid was dried by a Dean & Stark apparatus using toluene to remove the water. The reaction yielded 4.4 g of a white powder, 3-morpholinobenzoic acid.

EXAMPLE 2

Preparation of 3-morpholinobenzoyl chloride This example describes a method of synthesizing the following compound, 3-morpholinobenzoyl chloride, which is used as a reactant to form bis-m-morpholinobenzoyl trisulfide:

O

.N COC1

The reaction proceeded as shown below:

17 O

O

N COOH O O N COC1

II II Dioxane Cl — c-c-ci

The above reagents, including 25 g of 3-morpholinobenzoic acid and 15.2 g of oxalyl chloride, were mixed in dioxane at 0°C under argon gas. The reaction proceeded for about 2 hours, one hour at 0°C and one hour at room temperature. The solvent was then removed under reduced pressure to yield 22.1 g of 3-morpholinobenzoyl chloride, which was used without further purification.

EXAMPLE 3 Preparation of bis-m-morpholinobenzoyl trisulfide This example describes a method of synthesizing the following compound, bis-m-morpholinobenzoyl trisulfide:

O o

II

CS IS

The reaction proceeded as shown below:

0 0 0^'

0

II

THF N S + LiEt-Bh -^→> Li S c N r

2-^3 ^C1 THF CS

XT

In the first step of the above reaction, 0.1 g of sulfur was added to a 100 ml three-neck flask with magnetic stirrer bar and flushed with argon. 20 ml of 1M lithium triethylborohydride was slowly added to the flask. The reactants were mixed at room temperature in tetrahydrofuran (THF) for about 30 minutes resulting in a pale yellow solution. To this

18 solution was added 50 ml of THF followed by 4.4 g of 3- morpholinobenzoyl chloride. The solution turned a deep yellow/red color and was allowed to stir at room temperature for about one hour. After about one hour, the mixture had become a thick paste with a yellow color.

The reaction product was filtered to yield a yellow solid which was washed with water, benzene, and subsequently dried under vacuum. The reaction yielded 3.4 g of bis-m-morpholinobenzoyl trisulfide. The reaction HPLC showed complete reaction after about 30 minutes, yielding two products with retention times respectively of about 10 and about 15 minutes in a ratio of about 25:75. The 75% peak was the bis-m-morpholinobenzoyl trisulfide solid while the 25% peak was in the filtrated liquid.

EXAMPLE 4 Photocuring of bis-m-morpholinobenzoyl trisulfide in Red Flexo Resin A 2 % wt/wt mixture of bis-m-morpholinobenzoyl trisulfide powder was added to a 1 g sample of red flexo ink (Gamma Graphics). The solubility was poor at room temperature; however, the solubility improved upon heating the mixture on a hot plate. A drop of the mixture was placed on a metal plate and drawn down with a zero bar. The thin film was exposed to a brief flash of a D-bulb lamp (Fusion Systems). The thin film was instantly cured. Another thin film sample was cured using a medium pressure mercury lamp. The mercury lamp has a good emission at a wavelength of 350 nm. Exposure of less than one second resulted in full curing of the thin film.

EXAMPLE 5

Preparation of p-morpholinobenzoyl ester The formation of p-morpholinobenzoyl ester was conducted by the following reaction:

^v-®^**^*0 ^ -ϋr^ ^ ;-ϋr-

19 The above reagents, including 100 g of ethyl 4-aminobenzoic acid ester and 114 g of oxalyl chloride, were placed in a three liter round- bottom flask with condenser and mechanical stirrer. The reaction mixture was stirred at reflux for 15 hours. The hot solution was filtered to remove the solvent and yield a white solid. The white solid was recrystallized in benzene to yield 100 g of a white crystalline solid, p-morpholinobenzoyl ester.

EXAMPLE 6 Hydrolysis of p-morpholinobenzoyl ester

The hydrolysis of p-morpholinobenzoyl ester proceeded as shown in the following reaction:

°0^N^0^~c°^{2Et + KOH iϊδϊm}^ °O^N~ H^OH

15.2 g of KOH was dissolved in 200 milliliters of ethanol and 100 milliliters of water. To the mixture was added 80 g of p- morpholinobenzoyl ester. The mixture was stirred at room temperature overnight. The mixture was neutralized with dilute HCL and subsequently filtered to give a white solid. The white solid was dried by a Dean and Stark apparatus using toluene to remove the water. The reaction yielded 65 g of 4-morpholinobenzoic acid.

EXAMPLE 7 Preparation of ^-morpholinobenzoyl chloride

The preparation of 4-morpholinobenzoyl chloride was conducted using the following reaction:

o o

I \ fr II I "I / / \ \ , , ,-.

0 N— (( )) C :OOOOHH + α Cl—— c " C--cC--c THHFF. Ci T l -►> O0 N— <( )>— COC1 -/ \_^

A solution was formed with 60 g of 4-morpholinobenzoic acid in toluene at 0°C. To the solution was added 28.5 g of oxalyl chloride in

50 milliliters of THF over a period of about 10 minutes. The reaction mixture was stirred at 0°C for about 1 hour followed by stirring at room temperature for about 2 hours. The solution was filtered and the

20 solvent removed under reduced pressure to yield a white solid. The reaction yielded 58.2 g of 4-morpholinobenzoyl chloride, which was used in subsequent reactions without further purification.

EXAMPLE 8 Preparation of bis-p-morphobenzoyl trisulfide The preparation of bis-p-morphobenzoyl trisulfide proceeded as shown in the following reaction:

+ L-BEt₃h THF, Lb 2S°3

In a 250 milliliter round bottom flask fitted with a condenser and a magnetic stir bar, and flushed with argon gas was added 1 g of sulfur. To the sulfur was added 20 ml of lithium triethylborohydride by using a syringe over a period of about 3 minutes. The mixture was stirred at room temperature for 30 minutes, after which time, the mixture had stopped bubbling (H2 evolution). The color of the solution turned from red to pale yellow. To the mixture was added 4.4 g of 4- morpholinobenzoyl chloride over a period about 5 minutes. The reaction mixture was stirred for about 1 hour. The reaction mixture was filtered to separate a yellow filtrate, which was subsequently washed with toluene and dried under vacuum. The yellow solid was recrystallized from acetonitrile to yield 2.1 g of bis-p- morpholinobenzoyl trisulfide.

EXAMPLE 9 Photocuring bis-p -morpholinobenzoyl trisulfide in red βexo resin A 2% wt/wt mixture of bis-p-morpholinobenzoyl trisulfide and 1.0 g of red flexo resin (Gamma Graphics) was mixed for about 5 minutes while stirring at a temperature of about 30 to 40°C. A drop of the mixture was placed on a metal plate and drawn down with a 0 bar. The resulting film was exposed to radiation from a medium pressure mercury lamp for approximately 0.1 seconds to fully cure the film.

21 EXAMPLE 10 Preparation of bis-p-dimethylaminobenzoyl chloride The preparation of bis-p-dimethylaminobenzoyl chloride proceeded as shown in the following reaction:

l — , 0 o o i — , p

Me₂N— /QV-COH + Cl— C— C-Cl - *> Me₂N— Q\— C— Cl

To a solution of 60 g of p-dimethylaminobenzoic acid in toluene at 0°C was slowly added 46.1 g of oxalyl chloride and 50 milliliters of THF for a period of about 10 minutes. The mixture was stirred at 0°C for about 1 hour followed by stirring at room temperature for about 2 hours. The mixture was filtered to remove the solvent and yield 62 g of a solid, bis-p-dimethylaminobenzoyl chloride. The solid was used in the following examples without further purification.

EXAMPLE 11 Preparation of bis-p-dimethylaminobenzoyl trisulfide The preparation of bis-p-dimethylaminobenzoyl trisulfide proceeded as shown in the following reaction:

O

S + LiEt₃BH ^THF > Li₂S₂ + Me₂ »:-® -° -MM& o "-

In a 250 ml round-bottom flask fitted with condenser and magnetic stir bar, and flushed with argon gas, was added 1 g of sulfur. To the sulfur was added 20 ml of a 1M solution of lithium triethylborohydride over a period of about 3 minutes by syringe. The mixture was stirred at room temperature for about 30 minutes. To the mixture was added 3.7 g of p-dimethylaminobenzoyl chloride over a period of about 5 minutes. The mixture was stirred for about 1 hour and subsequently filtered to remove a yellow solid. The yellow solid was washed with toluene and subsequently dried to yield 2.1 g of bis-p- dimethylaminobenzoyl trisulfide. HPLC of the reaction showed one product having a retention time of about 15 minutes at a maximum wavelength of 360 nm.

22 EXAMPLE 12 Photocuring of bis-p-dimethylaminobenzoyl trisulfide in Red

Flexo Resin A 2% wt/wt. mixture of p-dimethylaminobenzoyl trisulfide and 1.0 g of red flexo resin (Gamma Graphics) was mixed for about 5 minutes while stirring at a temperature of about 30 to 40°C. A drop of the mixture was placed on a metal plate and drawn down with a 0 bar. The resulting film was exposed to radiation from a medium pressure mercury lamp for approximately 0.1 seconds to fully cure the film.

While the specification has been described in detail with respect to specific embodiments thereof, it will be appreciated that those skilled in the art, upon attaining an understanding of the foregoing, may readily conceive of alterations to, variations of, and equivalents to these embodiments. Accordingly, the scope of the present invention should be assessed as that of the appended claims and any equivalents thereto.

23

Claims

Claims What is claimed is:

1. A photoinitiator having the following formula:

^" RX ^"))— C(S)_X " — ( ^ - 3 =^f₂

wherein x is an integer from 1 to 4, and Ri and R2 each independently

O N— represent H- ; ^ ' ; (R)2N- where R is an alkyl group having from one to six carbon atoms; a chalcone; HSO3- or NaSθ3~ .

2. A photoinitiator having the following formula:

O

O O C(S)_X C CH₂ N

O wherein x is an integer from 1 to 4.

3. A method of generating a reactive species, comprising irradiating the photoinitiator of Claim 1 with radiation.

4. A method of generating a reactive species, comprising irradiating the photoinitiator of Claim 2 with radiation.

5. A method of polymerizing an unsaturated polymerizable material, comprising irradiating an admixture of an unsaturated polymerizable material and the photoinitiator of Claim 1.

6. A method of polymerizing an unsaturated polymerizable material, comprising irradiating an admixture of an unsaturated polymerizable material and the photoinitiator of Claim 2.

24

7. A polymer film, produced by the process of: providing an admixture of an unsaturated polymerizable material and the photoinitiator of Claim 1 that has been drawn into a film; and irradiating the film with an amount of radiation sufficient to polymerize the admixture.

8. A polymer film, produced by the process of: providing an admixture of an unsaturated polymerizable material and the photoinitiator of Claim 2 that has been drawn into a film; and irradiating the film with an amount of radiation sufficient to polymerize the admixture.

9. A method of coating a nonwoven web comprising: providing a nonwoven web coated with an admixture of unsaturated polymerizable material and the photoinitiator of Claim 1; and irradiating the coating on the web with an amount of radiation sufficient to polymerize the admixture.

10. A method of coating a nonwoven web comprising: providing a nonwoven web coated with an admixture of unsaturated polymerizable material and the photoinitiator of Claim 2; and irradiating the coating on the web with an amount of radiation sufficient to polymerize the admixture.

11. A method of coating a fiber comprising: providing a fiber coated with an admixture of unsaturated polymerizable material and the photoinitiator of Claim 1; and irradiating the coating on the fiber with an amount of radiation sufficient to polymerize the admixture.

25

12. A method of coating a fiber comprising: providing a fiber coated with an admixture of unsaturated polymerizable material and the photoinitiator of Claim 2; and irradiating the coating on the fiber with an amount of radiation sufficient to polymerize the admixture.

13. The photoinitiator of Claim 1, wherein the photoinitiator has the following formula:

14. The photoinitiator of Claim 1, wherein the photoinitiator has the following formula:

15. The photoinitiator of Claim 1, wherein the photoinitiator has the following formula:

O ^f R,N ¹¹— s \-s

wherein R is an alkyl group having from 1 to 6 carbon atoms.

26

16. The photoinitiator of Claim 15, wherein the photoinitiator has the following formula:

O

(CH₃ II CS IS

17. The photoinitiator of Claim 1, wherein the photoinitiator has the following formula:

R₂N

O

II cs- -s \SO₃Na

wherein R is an alkyl group having from 1 to 6 carbon atoms.

18. The photoinitiator of Claim 2, wherein the photoinitiator has the following formula:

/ °

NCH, C— S S

O

27