Polymers for use in centrifugal separation of liquids

This application claims the priority of the US provisional application of reference number 60/707299 filed on August 10, 2005, of reference number 11/499436 filed on August 4, 2006. This is a partially continuing simultaneous pending US application. This application further asserts the convenience of a co-pending provisional application of reference number 61/028426 filed on February 13, 2008.

The field of the present invention relates to photopolymers, and in particular to photopolymers for separating cell-containing components from cell-deficient biological fluids.

Analysis of blood samples often requires the separation of whole blood into serum and cell-containing components. It is well known in the art that whole blood separation can be performed through centrifugation by placing the whole blood in a blood collection tube, placing the tube in a centrifuge, and centrifuging the blood. There is.

Unfortunately, after the blood is separated, the whole blood components are remixed, resulting in contamination of the components by diffusion, agitation, sampling, or other undesired interactions. Ideally, the two components should remain isolated so that contamination does not occur when accessing the desired component. In addition, the analyte should maintain stability over an extended period of time after separation in preparation for storage, transport, or subsequent analysis.

Any system for isolating whole blood components must contain a separating substance with the appropriate concentration in the tube. Suitable concentration is about 1.04 g / cm³It is between the concentration of the heavy cell-containing layer and the concentration of the light serum-containing phase. When whole blood is added to the tube, when the tube is centrifuged, the separating material moves between the components and separates the two components from each other. An exemplary collection tube using gel as a separating material that is fluid with whole blood can be found in Feeler's US Pat. No. 4,946,601. These and all other foreign references are incorporated herein by reference as is. If the definitions or uses of terms in the incorporated references contradict or contradict the definitions of the terms given herein, the definitions of the terms given herein apply and the terms in the references. Does not apply. Illustrative isolates that are fluid with whole blood can be found in US Pat. No. 6,248,844 and US Pat. No. 6,361,700 of Gate et al. In these patents, the substance is a polyester that is curable to the desired viscosity.

By providing a fluid substance, it is possible to separate the components of whole blood, but the fluid substance has some disadvantages. Fluids remain fluid after centrifugation and are at risk of contaminating the sample if proper care is not taken to keep the sample in place and protect it from agitation. For example, it is known to use a shake-denatured gel in which the gel can flow after centrifugation in a blood collection tube. In addition, well-known materials lack the ability to retain analytes (eg, potassium and glucose) at acceptable levels over extended time periods (eg, at least 3 days).

Sounders US Pat. No. 4,818,418 discloses the use of rock-denatured gels in blood collection tubes. However, the problem with rock-denatured gels is that the gels do not form a sufficiently permanent separation barrier between whole blood components. When a sample is extracted from a tube using a pipette, the substance can contaminate or block the pipette when it comes into contact with the substance due to the fluidity of the substance. If the substance is prepared or constructed to have a high viscosity that is hard enough to overcome the previous disadvantages or provides a barrier of permanence, the substance no longer adequately flows with whole blood. It is no longer sex and the centrifugation time is extremely long. Short centrifugation times have important implications for life-threatening situations where blood analysis results are needed immediately.

An alternative approach taken by the blood collection tube manufacturer is to provide a mobile solid barrier. Examples of suitable solid materials include intermediate density polymers found in US Pat. No. 3,647,070, in which polymer spheres form a barrier layer. U.S. Pat. No. 5,266,199 describes tubes and ball valves that control the separation of serum from the cell-containing layer. However, such physical barriers do not provide sufficient sealing between the components and are often incomplete and leaky, or infeasible for a variety of other reasons.

These and other solutions to whole blood isolation ensure that the isolated components of whole blood are effectively protected from contamination by unwanted sample interactions while responding to short centrifugation times. It lacks the characteristics necessary to do so. Moreover, all or almost all well-known separation techniques have failed to maintain a stable and permanent barrier to separate the cell-containing phase from the cell-deficient phase. Therefore, there is still a need for liquid separation techniques that can be formed simply and effectively.

<p num="0010"> The content of the present invention allows the rapid formation of a hard barrier layer between the cell deficient phase and the cell enrichment phase in the blood collection tube, the barrier layer being preferably polymerizable by UV (UV) irradiation. Various compositions and methods formed from the compositions are described.</p><p num="0011"> In a preferred embodiment of the content of the invention, the polymerizable composition allows sterilization prior to use, allowing the composition to settle to a position between the cell depletion layer and the cell enrichment layer under centrifugal force. Has effective density and / or fluidity to enable. In particular, suitable polymers are 1.02 to 1.06 g / cm³Has a density of, and can be cured to form acrylate polymers, methacrylate polymers, epoxy polymers, polyurethanes, and / or thiol-ene polymers. Further, it is generally preferred that the composition comprises a photoinitiator and optionally a light inhibitor. If desired, various components can be utilized to further adjust the density of the composition, suitable components include silica, alumina, and other organic or inorganic fillers.</p><p num="0012"> In yet another preferred embodiment, the polymerizable component is (a) substantial capture of cells, (b) substantial contraction, (c) excessive heat generation, (d) one or more blood analyzed. Allows reaction with the components and / or (e) hardening without interference with analytical tests performed in the cell-deficient and / or cell-enriched phases. Moreover, it is generally preferred that the cured polymer has a hardness of shore 00, more generally shore A, most commonly at least 10 on shore D scale, and the polymer is 60 seconds. Less than, and more generally, less than 20 seconds to cure to its hardness. Preferred curable polymers will form a fluid resistant barrier between the cured polymer and the inner wall of the collection tube, but not limited to the content of the present invention.</p><p num="0013"> Therefore, from a different point of view, a method of assisting the separation of whole blood in a blood collection tube into a cell-deficient phase and a cell-enriched phase is considered, and a polymerizable composition is added to the tube. The composition has a predetermined density and fluidity that is effective in allowing the composition to settle to a position between the cell depleted phase and the cell enriched phase under centrifugal force. The tube is then sterilized (eg, using γ irradiation and / or heating) and transferred to the desired location. In another step of the method considered, it is then instructed to cure the composition which can be polymerized to a hardness of at least 10 on a Shore A hardness scale using UV irradiation for a period of less than 30 seconds after centrifugation. Given. The same considerations given above are used with respect to the appropriate composition in the manner considered.</p><p num="0014"> The various objectives, properties, aspects and advantages of the content of the present invention will become apparent from the following detailed description of preferred embodiments.</p>

The present invention has discovered various compositions and methods that allow the formation of a hard barrier layer in blood collection tubes from polymerizable compositions after the initialization or acceleration of the polymerization reaction. In a preferred embodiment, the polymerizable composition has density and fluidity in mammalian blood that allows it to settle to a position between the cell depleted phase and the cell enriched phase under centrifugal force.

One such exemplary composition was previously published as Reference No. 11/933839 (published as US 2008/0132874A1), 11/933871 (published as US 2008/0108493A1), and No. It is described in our co-pending US patent application on 12/27610 (filed November 14, 2008), all of which are incorporated herein by reference. Here, the composition is a polyfunctional acrylic monomer (trimethylolpropane propylate triacrylate), an aliphatic urethane acrylate, and 2,2-dimethoxy-1,2-diphenyl-ethane-1-one (as a photoinitiator). It was a combination of (used). As a rocking agent, fumes silica, about 1.04 g / cm³Was added to the composition to obtain the density of. As used herein, the term "about" in combination with numbers refers collectively to a range of numbers defined by an absolute deviation of 10%. For example, the term "about 10g" comprehensively refers to the range 9-11. Generally preferred is a polymerizable composition of about 1.01 to 1.09 g / cm.³, Most preferably 1.03 ~ 1.05g / cm³To have the density of. If the opposite intent is not clear from the context, the full range referred to herein should be construed to include their end points and the open end range should be construed to include only commercial practical values. Such polymer compositions exceed 10 on the Shore A scale after less than 10 seconds of UV irradiation without producing extra heat dissipation (eg, without raising the temperature of the fluid in the tube above 5 ° C). It exhibited a number of desirable properties, including hardening to hardness. In addition, such compositions were rock-denaturing, fluid, and formed a fluid-resistant seal on the inner wall of the tube to separate the cell-containing phase from the cell-deficient phase. Thus, preferred compositions generally have flow characteristics and concentrations that allow the suitable placement of polymerizable compositions between the cell depleted phase and the cell enriched phase, which allows cell capture and contraction. Indicates low and low or no heat dissipation. In addition, preferred compositions allow sterilization (eg, gamma rays or bundles) without significantly curing the composition (eg, over 30% or over 40%). ..

Of course, it should be understood that a number of alternative polymerization compositions are also considered suitable for use herein. More preferably, the polymerizable composition may include a composition that typically requires a cure time of less than 5 minutes and allows rapid photopolymerization to a hardness of at least 10 on a Shore A scale. Such polymerizable compositions may be of the same type (ie, may contain a single class of substances [eg, acrylates, methacrylates, etc.]) or of different types (ie, of multiple classes). Substances [eg, acrylates and epoxies] may be included). For example, particularly preferred polymerizable compositions can be polymerized (most preferably by UV irradiation / curing) to acrylate polymers, methacrylate polymers, epoxy polymers, polyurethanes, thiol-ene polymers, and all reasonable combinations thereof. Can include compositions that are.

For example, when a polymerizable composition is utilized to form an acrylate polymer and / or a methacrylate polymer, the suitable composition may preferably contain one or more, usually at least two functional acrylic groups. Included are aliphatic and aromatic acrylates and methacrylates (most preferably all substances are at least somewhat soluble). It should be noted that in the following enumeration of suitable substances, the term acrylate can also be replaced with the term methacrylate in order to display additional methyl groups within each acrylate. Among other suitable choices, suitable acrylates may include monofunctional acrylates, bifunctional acrylates, trifunctional acrylates, tetrafunctional acrylates and higher order acrylates.

Suitable monofunctional acrylates include oxyethylated phenol acrylates, monofunctional epoxy acrylates, phenoxyethyl acrylates, urethane monoacrylates, isobutyl acrylates (tricyclic acrylates), trimethyl propane acrylates, octyl / decyl acrylates, hydroxypropyl methacrylates, phenoxys. Included are ethyl acrylates (or other aryloxyalkyl acrylates), substituted cycloalkyl (meth) acrylates (eg, 3,3,5 trimethylcyclohexyl methacrylate), alkoxylated phenol acrylates, and alkyl methacrylates.

Bifunctional acrylates considered herein include alpha-omega-alkanediol diacrylates, alkoxylated aliphatic diacrylates, alkoxylated hexanediol diacrylates, di / tri / polyalkylene glycol diacrylates, and diacrylates. / Tri / Polyalkylene glycol diacrylates, alkoxylated bisphenol A diacrylates, tricyclodecanediol diacrylates, propoxylated neopentyl glycol diacrylates, bisphenol A derivatized diacrylates, dipropylene glycol diacrylates, 1,6 -Hexanediol diacrylate and tripropylene glycol diacrylate can be mentioned. On the other hand, suitable trifunctional acrylates include trimethylolpropane ethoxytriacrylates, glycerol acrylics, trimethylolpropane triacrylates, alkoxylated (and especially ethoxylated or propoxylated) trimethylolpropane triacrylates, and trimethylolpropane. Propanetriacrylate can be mentioned.

Examples of the tetrafunctional and higher-order acrylates generally include polyether tetraacrylates, polyester acrylates, dipentaerythritol penta / hexaacrylates, pentaacrylate esters, and ethoxylated pentaerythritol tetraacrylates. In particular, suitable oligomeric and polymeric acrylates include epoxy acrylates, acrylic acrylates, aliphatic urethane acrylates, polyether acrylates, polyester acrylates, acrylic acid esters, and aliphatic urethane acrylates. ..

In another example of using a polymerizable composition to form an epoxy polymer, the suitable composition is usually a combination of epichlorohydrin and a polyvalent compound (eg, bisphenol) and / or one. Epoxy groups, more generally one or more compounds containing at least two epoxy groups. Therefore, suitable compounds include monomeric, dimeric, oligomeric or polymeric epoxy materials containing one or more epoxy groups. In addition to these compounds, one or more reactive diluents may be included to further alter the properties of the desired polymeric material. For example, from the reaction of bisphenol-A (4,4'-isopropyridene diphenol) with epichlorohydrin, those resins produced by the reaction of epichlorohydrin with low molecular weight phenol-formaldehyde resins are used alone. Alternatively, it can be used in combination with an epoxy-containing compound as a reactive diluent. Suitable diluents include phenol glycidyl ether, 4-vinylchlorohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, aryl glycidyl ether and the like.

In addition, it should be recognized that the compositions considered may further comprise a polymeric material containing terminal and / or suspended epoxy groups. Examples of these materials are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the copolymers. Other classes of epoxies, including polymers suitable for curing (preferably utilizing UV), are usually epoxy siloxane resins, epoxy polyurethanes and epoxy polyesters that contain an epoxy functional group at the end. More specifically, epoxy siloxane resins and preparation methods are shown by EP Proudemann and G. Flanger, Journal of the American Chemical Society, Vol. 8, pp. 632-5 (1959). As described in the literature, epoxy resins are also described in US Pat. Nos. 2,935,488, 3,235,620, 3,369,055, 3,379,653, 3,398,211, 3,403,199, 3,563,850, 3,567,797, It can be modified by a plurality of standard methods such as reaction with amines, carboxylic acids, thiols, alcohols and the like as shown in No. 3,677,995 and the like. Other examples of epoxy resins available are set forth in the Dictionary of Polymer Chemistry and Technology, Vol. 6, 1967, Interscience Publishing, New York, pp. 209-271.

In another example of using a polymerizable composition to form a urethane polymer (polyurethane), a suitable composition is usually, for example, in the presence of a catalyst, at least two compounds containing at least two isocyanate groups. Compositions may be included that allow the formation of urethane bonds by reacting with another compound containing one alcohol group (eg, by the reaction of polyisocyanates with hydroxyl group-containing polyesters).

With respect to suitable isocyanates, it is generally preferred that the isocyanates contain at least two isocyanate groups and such compounds are utilized to form polymeric isocyanates having three or more isocyanate functional groups. It is possible. Most preferably, the isocyanates are aromatic isocyanates (eg, diphenylmethane diisocyanate, toluene diisocyanate, etc.), but aliphatic isocyanates (eg, hexamethylene diisocyanate, isophorone diisocyanate, etc.) are also described herein. Clearly considered in the book. It should be noted that aliphatic and cycloaliphatic isocyanates are less preferred due to the reduction reactivity of the aliphatic isocyanate group compared to the aromatic-bonded isocyanate group. Yet another consideration of isocyanates includes polymeric isocyanates (eg, diphenylmethane diisocyanate). Isocyanates are prepolymers (ie, the ratio of hydroxyl and isocyanate groups is equal to 2: 1) or quasi-prepolymers (ie, the ratio of hydroxyl and isocyanate groups is 2: 1). It should be noted that it can also be prepared by a partial reaction with a polyol to form a larger).

With respect to suitable polyols, polyols are considered to be at least diols, more generally triols, and most commonly polyols. Short-chain or low molecular weight multivalent compounds include ethylene glycol, 1,4-butanediol, diethylene glycol, glycerol, and trimethylolpropane. Examples of long-chain or high-molecular-weight multivalent compounds include polyethylene polyols and polyester polyols. For example, soft polyols have a molecular weight of 2,000 to 10,000, whereas hard polymers have a molecular weight of 250 to 700. Polycarbonates having a molecular weight of 700 to 2,000 are often suitable for adding rigidity or flexibility to the polymer system. Among other suitable polyols, particularly preferred polyols include polyether polyols and polyester polyols.

Suitable polyether polyols may preferably include dipropylene glycol or glycerol for less rigid barrier layers and Mannich bases for harder barrier layers. Propylene oxide can then be added to obtain the desired molecular weight. Polyols extended with propylene oxide end with a secondary hydroxy group. Ethylene oxide is utilized as a co-reactant to produce random or mixed block heterogeneous polymers to alter the compatibility, rheological properties, and reactivity of the polyols. Suitable polyester polyols are usually made from a variety of glycols (eg, by direct transesterification of diacids and glycols (eg, adipic acid and 1,4-butanediol) or by utilizing recycled untreated materials (eg, by utilizing recycled untreated materials). It can be made through a transesterification reaction of diethylene glycol) with regenerated poly (ethylene terephthalate) or dimethyl terephthalate. Still other considerations of polyols include polycarbonate polyols, polycaprolactone polyols, polybutadiene polyols and polysulfide polyols.

Additional components that alter polyurethane include chain secondary and higher order polyols that can be used as extenders, and are generally alkylene glycols (eg, diethylene, methylene, etc.), alpha-omega-alkanediol. (For example, 1,3-propanediol, 1,4-butanediol, etc.), dimethanolamine, phenyldiethanolamine and the like can be mentioned. Yet another consideration compound for polyurethanes is found in US Pat. No. 6,747,088 .

In addition, all catalysts suitable for polyurethane formation may be utilized and all well-known catalysts are considered suitable for use herein. Among other categories, preferred catalysts include amine compounds and organometallic complexes. For example, amine catalysts may include tertiary amines (eg, triethylenediamine, dimethylcyclohexylamine, and dimethylethanolamine). Organometallic catalysts can be based on mercury, lead, tin (dibutyltin dilaurate), bismuth (bismuth octanate), and zinc.

In yet another diacrylate that utilizes a polymerizable composition to form a thiol-ene polymer, the suitable compositions are generally polythiol compounds and polyvinyl (-ene) for forming curable mixtures. Compounds can be mentioned. In addition to thiols and vinyl functional groups, other functional groups may be provided to condition and / or provide additional desired properties. Therefore, suitable thiol compounds include aliphatic (poly) thiols, aromatic (poly) thiols, and polymeric (thiols).

For example, suitable examples of aliphatic and cyclodithiothiones include 1,2-ethanedithiole, butanedithiol, 1,3-propanedithiol, 1,5-pentanedithiol, 2,3-dimercapto-1-propanol. , Dithioerythitol, 3,6-dioxa-1,8-octanedithiol, 1,8-octanedithiolhexanedithiol, dithiodiglycol, pentandithiol, decandiothione, 2-methyl-1,4-butanedithiol, bis-mercapto Ethanephenylmethane, 1,9-nonandithiol (1,9-dimercaptononan), glycoldimercaptoacetate, 3-mercapto-β,4-dimethyl-cyclohexaneethanethioe, cyclohexanedimethanedithiol, and 3,7-dithia. -1,9-nonandithiol can be mentioned.

Suitable examples of aromatic dithiols include 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 2,4,6-trimethyl-1,3-benzenedimethanethiol, durene. -α1, α2-dithiol, 3,4-dimercaptotoluene, 4-methyl-1,2-benzenedithiol, 2,5-dimercapto-1,3,4-thiadiazol, 4,4'-thiobisbenzene Dithiol, bis (4-mercaptophenyl) -2,2'-propane (bisphenoldithiol) (Meng. YZ, Hi. AS, Journal of Applied Polymer Science, Vol. 74, pp. 3069-307, prepared according to the 1999 method. ), [1,1'-biphenyl] -4,4'-dithiol, and p-xylene-α, α-dithiol. On the other hand, suitable examples of oligomeric dithiols include hydroxyethyl mercaptones, hydroxypropyl mercaptones, dimercaptopropane, and bifunctional mercaptofunctional urethane oligomers derived from the sealed portion of dimercaptoethane.

Examples of suitable trithiol functional compounds include trimethylolethanetris-mercaptopropinate, trimethylolpropane, tris-mercaptopropinate, trimethylolethanetris mercaptoacetate, and trimethylolpropane tris mercaptoacetate glyceroltri (11-mercapto). Undecate), trimethylolpropane tri (11-mercaptoundecate). The preferred trithiol is trimethylolpropane tris (2-mercaptoundecate), and examples of suitable tetrafunctional thiols are pentaerythritol tetramercaptopropinate, pentaerythritol tetramercaptoacetate, and pentaerythritol tetra (11-mercapto). Undecate).

Polyfunctional thiols can be obtained by reacting a highly functional alcohol with a thioalkylcarboxylic acid (for example, thioglycolic acid, mercaptopropionic acid, etc.). Further, polyfunctional thiols can be obtained by reacting silanols, which can be polymeric or silica-based silanols, with mercaptoalkyltrialkoxysilanes. Yet another considered polyfunctional thiol can be obtained by utilizing thiolcarboxylic acids in which a carboxylic acid group reacts with the polyfunctional reactive enes, alcohols, thiols or amines. Considerable examples of polyfunctional thiols are described in PCT Application No. 88/02902. Therefore, among other suitable choices, examples of polythiols include ethylene glycol bis (thioglycolate), ethylene glycol bis (β-mercaptopropinate), trimethylolpropane tris (thioglycolate), trimethylol Propantris (β-mercaptopropinate), pentaerythritol tetrakis (β-mercaptopropinate), all of which are commercially available. Further, as polythiols to be considered, polypropylene ether glycol bis (β-mercaptopropionate) prepared by esterification from polypropylene-ether glycol and β-mercaptopropionic acid can be mentioned.

With respect to polyvinyl or vinyl compounds, it should be understood that all compounds having one or more vinyl functional groups are suitable for combination with the teachings presented herein. Therefore, it is generally preferred that the polyvinyl or vinyl compound have at least two, more preferably at least three vinyl groups. Examples of suitable compounds include trimethylolpropane trivinyl ether, pentaerythritol triaryl ether, and 1,3,5-triaryl-1,3,5-triazine-2,4,6-trione, as well as simple compounds. Included are cycloalkenyls having a ring, polycyclic, or fused polycyclic structure (optionally containing one or more heteroatoms). Examples of polycyclic enes are described in PCT Application No. 88/02902.

Regardless of the type of polymer formed during the curing reaction, additional reactive groups may be included to crosslink and / or provide the desired functionality, with acidic groups (and, of particular consideration) being particularly considered reactive groups. Most preferably, it should be understood that monocarboxyl groups and dicarboxyl groups), basic groups (eg, tetraammonia group, ammonium group, etc.), conjugated diene groups, aromatic vinyl groups and the like can be mentioned. Furthermore, it should be understood that such additional bases can be attached to the ends of the polymer and / or as suspension groups. Furthermore, it is believed that the polymerizable composition may comprise a variety of materials and / or agents to achieve the desired biological reaction objectives. For example, the polymerizable compositions represented herein may include EDTA, heparin, citric acid, glucose, optionally a solid phase covered with a lectin or antibody, and the like.

Further, generally preferred, the composition considered comprises, optionally, one or more denaturants to impart fluidity to the composition while the composition is exposed to centrifugation. That is, on the other hand, all well-known rock-modifying additives are considered suitable for use herein. However, particularly preferred rocking additives include fumigant silica, micronized calcium silicate hydrate crystals and related compounds, as described in US Pat. No. 5,120,775, and US Pat. No. 4,190,535. Examples include compositions and precipitated methylated silica prepared from diethylpolysiloxane, and gels formed from silicone oil, butadiene resin, polyester resin, or butanol resin, as described in US Pat. No. 4,957,638. .. If desired, the surface properties can be adjusted to adapt to the particular requirements of the polymerizable composition. For example, one or more agents may be utilized (eg, lipophilic or hydrophilic organic silanes or organic siloxanes) to increase or decrease the hydrophobicity of the additive and / or One or more types of reactive groups may be introduced to allow covalent attachment of the additive polymer component. In addition, it should be noted that the shake-denaturing additive advantageously allows the polymerizable composition to remain in a gel state prior to combining with a fluid sample (usually blood) and / or centrifuging. .. Thus, the polymerizable composition considered can remain at the bottom of the collection tube and will not flow out of the tube or near the top of the tube, even if the tube is in an inverted or tilted position. The polymerizable composition is then centrifuged and then flowed to the appropriate location.

As a result, it should be recognized that the mechanism of polymerization to the final separated polymer can vary considerably depending on the particular polymerizable composition. Therefore, all well-known mechanisms of polymerization are considered suitable for use herein. For example, the polymerization mechanism considered includes radical and cationic polymerization (using, for example, photosensitive compounds, radical initiators, etc.), condensation polymerization, esterification, amide formation, and the like.

With respect to a suitable energy source, it is generally preferred that the energy source provide non-particulate energy, more preferably electromagnetic radiation, most preferably UV irradiation (eg, in the 250 nm to 400 nm range). However, it should be noted that other irradiations, including microwave irradiation, visible light irradiation, infrared irradiation, radio frequency irradiation, and ion (eg, beta or gamma ray) irradiation are also considered appropriate. Irradiation is usually delivered through the wall of the tube, but direct fiber optic delivery to the polymerizable composition is also suitable. For example, the blood collection tube can be irradiated after centrifugation in a rotor or in a dedicated rack.

It should be noted that all well-known photoinitiators are considered suitable, depending on the polymerizable composition and the type of reaction. However, it is classified as a particularly preferable photoinitiator, as an organic onium salt, and particularly as an aromatic sulfonium salt (for example, a phenacyl sulfonium salt, a hydroxyphenyl sulfonium salt, a sulfonium salt, and / or a salt activated by a sensitizer). Examples of drugs that can be used. Still other preferred photoinitiators include organosilicon-containing compounds that produce silanol by UV irradiation in the presence of organoaluminum-containing compounds. In addition, the photoinitiators considered are: (a) phosphine oxide photoinitiators (eg, 2,4,6-trimethylbenzyl-diphenyl-phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine). Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide), (b) Ketone-based photoinitiators (eg, hydroxy and alkoxyalkylphenyl ketone, 2-benzyl-2-(eg) Dimethylamino) -4'-morpholinobtyrophenone, 1-phenyl-2-hydroxy-2-methylpropanone, 2-hydroxy-2-methylpropiophenone, benzophenone, trimethylbenzophenone, methylbenzophenone, 1-hydroshikicyclohexylphenylketone , Isopropylthioxanthone, 2,2-dimethyl-2-hydroxy-acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- On and thioalkyl phenylmorpholinoalkyl ketones), and benzoin ether photoinitiators (eg, benzoin isopropyl ether, etc.).

With respect to cure time, it should be understood that the cure time depends on the particular composition of the polymerizable composition, the reaction conditions, and the amount of photoinitiator and / or photoinhibitor. However, it is generally preferred that the curing time be adjusted to less than 10 minutes, more preferably less than 5 minutes, most preferably less than 1 minute (eg, less than 30 seconds, less than 20 seconds, etc.). .. As used herein, the term "curing time" is the time required to obtain a hardness of at least 85%, measured 60 minutes after irradiation (or vice versa, at the start or acceleration of polymerization). Point to. Of course, it should be understood that in order to obtain the polymer with the desired hardness, the desired curing time can be adjusted by including the appropriate photoinitiator, irradiation conditions, and optionally a light inhibitor.

Hardness was measured using any suitable hardness scale, including one of the shore hardness scales. The hardness of soft substances including gels or foams was measured using the Shore 00 hardness scale. The Shore A hardness scale is used to measure the hardness of substances with intermediate hardness, including rubbers. The hardness of hard substances including plastics is measured using the Shore D hardness scale. It is used for various materials with different shore hardness scales, but the scales all overlap at the low end of their range. Therefore, the value of 10 on the shore D is harder than the value of 10 on the shore A, and the value of 10 on the shore A is harder than the value of 10 on the shore 00 scale. The separating material formed by the polymerization of the polymerizable composition is preferably at least 1 on the Shore 00 hardness scale, more preferably at least 10 on the Shore A scale, and most preferably on the Shore D scale. Formulated to harden to at least 10. With respect to the hardness of the cured polymer, it is generally preferred that the cured polymer has a hardness of at least 10 on Shore 00, more generally on Shore A, and most commonly on Shore D scale. is there.

It should be apparent to those skilled in the art that many further modifications beyond those already described are possible without departing from the concept of the invention herein. Therefore, the content of this issue is not restricted except in the spirit of the attached claims. Moreover, in interpreting both the specification and the claims, all terms should be construed as broadly as possible, consistent with the context. In particular, the terms "contains" and "contains" should be construed to refer to an element, component, or process, without exception, and the referenced element, component, or process is a table. Indicates that it may exist, be utilized, or be combined with other elements, components, or processes not mentioned above. If the claims of the specification refer to at least one selected from the group consisting of A, B, C ... and N, the text is not from the group A plus N or B plus N etc. Should be interpreted as requiring only one element of.