TW200835700A - Polymerization inhibitor compositions, their preparation, and their use - Google Patents

Abstract

This invention provides a liquid polymerization inhibitor composition formed from ingredients comprised of tris(N-nitroso-N-phenylhydroxylamine)aluminum salt and (a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4' -(2-hydroxyethoxy)-2-methylpropiophenone, α, α -diethoxyacetophenone, or 1-benzoylcyclohexanol, or a combination of any two or more of these; or (b) benzophenone, at least one ester having a benzoylphenyl group therein, or at least one acrylate having a benzoylphenyl group therein, or a combination of any two or more of these; or c both (a) and (b). When (a) is 1-benzoylcyclohexanol, then at least one ingredient from (b) is also present in said composition.

Description

200835700 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel stable liquid polymerization inhibitor composition comprising a ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt, and a method of forming the same And the use of the composition in a photohardenable formulation. [Prior Art] Sodium (N-nitroso-N-phenylhydroxylamine) aluminum salt CAS No. 1 5 3 0 5 - 0 7 - 4 is a photohardenable formulation (also known as radiation hardenable) Formulations) very effective polymerization inhibitors. This compound was obtained from FIRSTCURE® NPAL polymerization inhibitor from Albemarle Corporation. The ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt itself is an agglomerated solid. In order to enhance its use as a polymerization inhibitor, it is desirable to provide a compound in liquid form. To date, the (N-nitroso-N-phenylhydroxylamine) aluminum salt has been marketed as a liquid polymerization inhibitor blend having 2-phenoxyethanol acrylate. Unfortunately, this blend has a strong off-taste. There is therefore a need for a way to provide a stability solution of the ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt which is used to form a photohardenable formulation without incurring a strong off-taste. It is particularly desirable to provide these properties regardless of how they provide good storage stability, inhibit premature polymerization of the photohardenable formulation in which the blend is used to high efficiency, and not adversely affect the hardened photohardenable formulation. A stable blend in the form of a clear solution of the nature of the hardened product. SUMMARY OF THE INVENTION The present invention provides a liquid poly 200835700 combined inhibitor composition having most, if not all, of the above attributes. In other words, this composition is highly suitable as an additive in the formation of photohardenable formulations. Surprisingly, these compositions may contain about 10% by weight or more of the ginseng (nitroso-N-phenylhydroxylamine) aluminum salt. These liquid polymerization inhibitor compositions are composed of the ginseng (N-nitroso-N-phenylhydroxyl) salt and the following components: a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy- 4,-(2-hydroxyethoxy)-2-methylpropiophenone, α,α-diethoxyacetophenone, or 1-benzylidenecyclohexanol, or any two or more thereof a combination; or Φ b) diphenyl ketone, at least one ester having a benzhydryl phenyl group therein, or at least one acrylate having a benzhydryl phenyl group therein, or a combination of two or more thereof Or c) both a) and b), provided that if a) is 1-bensylcyclohexanol, at least one component from b) is also present in the composition. As described above, the polymerization inhibitor composition of the present invention is a liquid. When a) is 1-bensylcyclohexanol, the component derived from b) is also present in the composition ^ to make the composition liquid. See U.S. Patent No. 4,5 63,43 8 for this. The invention also provides a process for the manufacture of a liquid polymerization inhibitor composition which comprises mixing a ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt and the following: a) 2-hydroxy-2- Methylpropiophenone, 2-hydroxy-4,-(2-hydroxyethoxy)-2-methylpropiophenone, α,α-diethoxyacetophenone, or 1-benzylidenecyclohexanol Or a combination of two or more thereof; or -6- 200835700 b) diphenyl ketone, at least one ester having a benzylidene phenyl group therein, or at least one acrylic acid having a benzylidene phenyl group therein An ester, or a combination of two or more thereof; or c) both a) and b), provided that if a) is 1-benzylidenecyclohexanol, at least one component derived from b) It is also present in the composition to form a liquid composition. The storage of this liquid composition caused the solution to remain solid-free over a longer period of time than the storage of pure ginseng (N-nitroso-N-benzamide) under salt storage conditions. • The present invention also provides the preparation of a photohardenable formulation containing a polymerization inhibitor. The formulation comprises at least one photohardenable monomer, oligomer and/or polymer, wherein the polymerization inhibitor is modified to include a ginseng (N-nitroso-N-phenylhydroxylamine) Aluminium salt and a liquid formed by the following components: a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4,-(2-hydroxyethoxy)-2-methylpropiophenone, α,α- Diethoxyacetophenone, or 1-benzylidenecyclohexanol, or a combination of any two or more thereof; or b) a ketone, at least one ester having a benzhydrylphenyl group therein Or at least one acrylate having a benzhydrylphenyl group, or a combination of two or more thereof; or c) both a) and b), provided that a) is 1-benzene For mercaptocyclohexanol, at least one component derived from b) is also present in the composition. Other specific embodiments and features of the present invention will be apparent from the following description and the appended claims. 200835700 [Embodiment] Throughout this document, all ratios and percentages are by weight unless otherwise indicated. Diphenyl ketone is referred to as a benzyl phenyl phenyl group when it becomes a substituent moiety. It should also be understood that the term "benzimidyl" as used throughout this document, unless otherwise indicated, includes substituted and unsubstituted benzhydrylphenyl. When a compound containing a substituted benzhydrylphenyl group is used to form a liquid polymerization inhibitor composition, the substituent on the benzhydrylphenyl group may be any substituent which does not hinder the formation of the liquid polymerization inhibitor composition. A feature of the present invention is that a relatively large amount of the ginseng (N-nitroso-N-phenylcarbylamine) aluminum salt can be used in a liquid form for the polymerization inhibitor composition. At least about 1%, often from about 5% to about 1% by weight, based on the total weight of the composition, and up to about 12% of the ginseng (nitroso-indolyl-phenylhydroxylamine) aluminum salt Successfully included in the liquid polymerization inhibitor composition of the present invention. 1) Polymerization inhibitor composition As apparent from the above, various polymerization inhibitor compositions are available in the present invention. One type of novel polymerization inhibitor composition is composed of ruthenium (nitroso-nitro-p-phenylhydroxylamine) aluminum salt and 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2 a liquid form formed by the component of ethoxylated)-2-methylphenyl acetonide, α,α-diethoxy phenyl hexahydrate, or a combination of any two or more thereof. A preferred component for mixing the aluminum salt of ginseng (nitroso-quinone-phenylhydroxylamine) is 2-hydroxy-2-methylpropiophenone. Another novel polymerization inhibitor composition obtainable by the present invention is an ester comprising stilbene (nitrosophenylphenylhydroxylamine) aluminum salt and diphenyl ketone, at least one ester having benzhydryl phenyl group therein, Or a liquid form formed by at least one acrylate having a benzamidine 200835700-phenyl group, or a combination of two or more thereof. A preferred component for mixing the ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt is diphenyl ketone and at least one ester having a benzhydryl phenyl group; more preferably diphenyl ketone . The benzepidine phenyl ester used to form the composition of the present invention can be represented by the following structure:

〇 〇

Preferably, R contains up to about 12 atoms; more preferably r has from about i to about 6

atom. It should be understood that these structures are not considered to limit the inclusion of benzhydryl phenyl ester. It may be present in more than one ester group and this ester group may be on the same ring or on separate rings. The substituent may be present on one or both of the benzhydrylphenyl groups. Suitable substituents include alkyl groups (preferably Ci to C6), alkoxy groups (preferably having up to about 12 carbon atoms), ethers, esters, amine groups, and/or acid amine groups. Examples of the substituent of the present formate phenyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, pentyl, cyclopentyl, hexyl , cyclohexyl, heptyl, octyl, decyl, hydroxy, methoxy, ethoxy, trifluoromethyl, amine, methylamino, diethylamino, dibutylamino, nitro, and fluorine base. R, which may be, but not limited to, an alkyl group, an ether group, an amine group, or a guanamine group. Preferably, R contains up to about 12 atoms; more preferably V has from about 1 to about 6 atoms. Suitable R, including methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, tert-butyl 'pentyl 200835700, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl Base, fluorenyl, trifluoromethyl, amine, methylamino, diethylamino, dibutylamine, fluorine, and the like. Esters having benzhydrylphenyl groups suitable for use in the present invention include, but are not limited to, methyl phthalate, ethyl m-benzoyl benzoate, n-propyl p-benzoyl benzoate. , 2-(3-benzylidenylphenyl)propionic acid isopropyl ester, 2-(p-chlorobenzopyridyl)phenylpropionic acid n-butyl ester, (3-benzoyl-2-yloxy) Phenyl)acetic acid second butyl ester, (2-amino-3-benzhydrylphenyl)acetic acid tert-butyl ester, 4-benzylidene-α-methylphenylacetic acid amyl ester, 2-(# Cyclopropenylphenoxy)acetic acid cyclopentyl ester, 2-amino-(4'-chlorobenzylidene)phenylhexyl acetate, 4-(2-methyl-3-(4-chlorobenzene) Mercapto)phenyl)butyric acid cyclohexyl ester, 2-amino-3-(4-bromobenzylidene)p-butyl acetate, heptyl 5-(2,4-dichlorobenzylidene)-2 -hydroxy- 5-(4-fluorobenzhydryl)>-2-hydroxy-α-methylphenylacetate, methyl 2-(4-methylbenzimidyl)benzoate, 4-methyl Ethyl diphenyl ketone-2-carboxylate, n-propyl 2-(4-ethylbenzylidene)benzoate, ethyl 4-ethyldiphenyl ketone-2-carboxylate, 4,4' -Dimethoxydiphenyl ketone-2,2'-dicarboxylic acid methyl ester, diphenyl ketone-4 , 4'-dicarboxylic acid second butyl ester ^, diphenyl ketone-2,2',4-tricarboxylic acid tert-butyl ester, diphenyl ketone-3,3',4,4'-tetracarboxylic acid N-butyl acrylate, diphenyl ketone - 2,2',5,5'-tetracarboxylic acid amyl ester, phthalyl benzoyl benzoate, cyclopentyl m-benzoyl benzoate, p-phenylene Cyclohexyl benzoate, heptyl 2-(3,4-dimethylbenzylidene)benzoate, octyl 2-(2-hydroxy-5-methylbenzylidene)benzoate, 2 - (2,3-difluorobenzhydryl)benzoic acid oxime ester, methyl 2-(4-fluoro-3-methylbenzylidene)benzoate, 2-(2,3,4,5, Methyl 6-pentamethylbenzhydryl)benzoate, ethyl 2-(4-hydroxy-3,5-dimethylbenzimidyl)benzoate, 2-(2-aminophenyl-10- 200835700 Methyl isopropyl benzoate, 2-(3,5-indole (trifluoromethyl)benzyl)benzoic acid tert-butyl ester, 2-[4-(dibutylamino)-2 -hydroxybenzylidene] methyl benzoate, methyl 2-(4-fluorobenzhydryl)benzoate, ethyl octabenzoate, 2-(4-methylbenzene) Methyl benzoate isopropyl benzoate, 2-butyl 3-(3-aminobenzylidene) benzoate, Ethyl-2-hydroxybenzamide acyl amino) benzoate, 2-benzoyl-yl - nitrophenyl acid hexyl ester, 2 - nitro-benzoyl _3_ amyl group and the like.

Preferably, the benzhydryl phenyl ester has only one ester group; and is preferably an unsubstituted benzyl phenyl phenyl ester. More preferred are benzamidine basic orthoesters (also known as diphenyl ketone phthalate). Still more preferred is the benzylidene benzoate (i.e., o-benzimidyl benzoate, m-benzoyl benzoate, and p-benzoyl benzoate). A highly preferred benzhydrylphenyl ester is methyl orthobenzoylbenzoate. The acrylate having a benzamidine phenyl group for forming the composition of the present invention can be represented by the following structure:

Wherein R" can be, but is not limited to, hydrogen, alkyl, ether, ester, amine, or guanamine. Preferably, R" contains up to about 12 atoms; more preferably R" has from about i to about 6 atoms. It should be understood that this structure is not to be construed as limiting the acrylate having a benzhydrylphenyl group. The substituent may be present on the benzoylphenyl group or on both rings. Suitable for the benzhydrylphenyl group. Substituents include alkyl groups (preferably <^ to (:6), alkoxy groups (preferably having up to about 12 carbon atoms) -11-200835700, ethers, esters, amine groups, and/or guanamines Examples of the substituents on the benzhydrylphenyl ring include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, pentyl , cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, decyl, hydroxy, methoxy, ethoxy, trifluoromethyl, amine, methylamino, diethylamino, dibutylamino And a nitro group, and a fluoro group. R" may be, but not limited to, an alkyl group, an ether group, an amine group, or a guanamine group. Preferably, R" contains up to about 12 atoms; more preferably R" has from about 1 to about 6 atoms. Suitably R" includes hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl II, t-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl , octyl, decyl, amine, methylamino, diethylamino, dibutylamine, etc. There are several ways in which acrylic acid having a benzhydrylphenyl group can be used as a component of the composition of the present invention. The ester nomenclature. For example, in the above structure, the ring is unsubstituted, and when R is hydrogen, the compound may be referred to as benzhydrylphenyl acrylate or benzepidine phenyl 2-propionate; similarly, at R" The methyl group compound may be referred to as methyl benzhydryl phenyl acrylate or 4-benzylidene phenyl 2-methyl -2-propionate. Suitable for use in the present invention having benzhydryl benzene Acrylates include o-benzimidyl phenyl acrylate, m-benzoyl phenyl acrylate, p-benzoyl phenyl acrylate, 2-methoxy-m-benzoyl phenyl propyl acrylate Acid ester, methyl phthalyl phenyl acrylate, m-benzyl phenyl propyl acrylate, isopropyl p-benzoyl phenyl acrylate, 2-methoxy- N-butyl benzhydryl phenyl acrylate, 4-benzylidene-3-hydroxyphenyl methacrylate, etc. -12- 200835700 Preferably, acrylate having a benzhydryl phenyl group is benzophenone Nonylphenyl acrylate. More preferably, the acrylate is an unsubstituted benzhydryl phenyl acrylate of c. The novel polymerization inhibitor composition of the present invention of the third type is N-nitroso-N-phenyl Hydroxylamine) aluminum salt and c) (a) 2-hydroxy-2-one, 2-hydroxy-4,-(2-hydroxyethoxy)-2-methylpropiophenone, oxyacetophenone, or 1 - benzothyridylcyclohexanol, or any two or combination of 'and b) diphenyl ketone, at least one of which has benzamidine ester' or at least one of which has a benzhydryl phenyl group or two or more A combination of a plurality of combinations) formed into a solution form. Preferred 2-hydroxy-2-methylpropiophenone and diphenyl ketone, 2-hydroxy-2-methylphthalic acid oxime of the component of the N-nitroso-N-phenylhydroxylamine aluminum salt Methyl benzoate, and 1-benzylidenecyclohexanol; more preferably 2-hydroxy-2-methylpropiophenone and diphenyl ketone. a) Pairs can be any, such as 0 · 1 ·· 9 9.9 to 9 9.9 : 0.1, which limits the liquid. For combinations involving 1-benzimidylcyclohexanol, the amount of 1-phenylhexanol is such that the composition is liquid and is typically in the range of about 80%; more preferably 1-benzylidenecyclohexanol It is a combination to about 70%; even more preferably from about 40% to about 60% of the cyclohexanol. For at least one acrylic acid having a benzoyl group and/or at least one having a benzhydryl phenyl group therein, when the ester or acrylate is a solid, the solid ester or acrylate is combined with b) by about 80% or more. less. a) a preferred ratio of b) to a range of about 80:20, more preferably a) a preferred ratio of b), no substituent P" is a hydrogen-containing ginseng (meth) , the α-diethyl phenyl ester of a greater variety, or a mixture thereof comprising a ratio of propiophenone to diphenyl ketone b) is from about 5 to about 30% of the formazan ring. The combination of the phenyl phenyl ester ester is usually a) | about 2 0 : 8 0 I from about 30:70 -13 to 200835700 to about 70:30. Still better a) to b) The ratio is from about 40:60 to about 60:40. The liquid polymerization inhibitor composition of the present invention has good solubility in common organic solvents and media, good stability, and can be used with high effective inhibition. Early maturing polymerization of various photohardenable formulations. Further, the components of these blends may be dispensed to provide little, if any, odor. The liquid polymerization inhibitor composition of the present invention contains at least about the total weight of the composition. 1. 1% by weight, generally at least about 1% by weight, preferably less than about 5% by weight, and more preferably at least about 6% by weight of ginseng Nitro-indole-phenylhydroxylamine) aluminum salt. The amount of cerium (non-nitroso-indolyl-phenylhydroxylamine) aluminum salt in an amount of up to about 8% by weight, 10% by weight and 12% by weight may be present in the present invention. The liquid composition of the invention. The composition of the blend is such that it does not exceed the room temperature of the cerium (nitroso-nitro-indolyl-hydroxyhydroxylamine) aluminum salt in the particular component used to form the liquid composition (eg 2 3 ° C) solubility limit. However, in the case where the appearance of the product is not an important factor, the composition may even be a concentrated turbid liquid • ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt preparation in this technique It is known and described, for example, in U.S. Patent No. 6,0,8,078. For example, the ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt can be reacted with an aluminum salt (such as aluminum sulfate). Salts are prepared with N-nitroso-N-phenylhydroxylamine ammonium salts, although other metal salts such as halide salts, phosphates, nitrates, carbonates, and organic acid salts can also be used. a polymerization inhibitor composition which uses a typical mixing apparatus such as a blending tank or a vessel equipped with a suitable agitation or agitation means, -14-200 835700 The ingredients are mixed together in any suitable manner.Additional ingredients may be included in the liquid polymerization inhibitor composition of the present invention, with the proviso that the ingredient does not actually detract from the beneficial properties of the composition in which it is used. Non-limiting examples of additional ingredients of the inventive blend include dyes, acrylate and/or methacrylate monomers and/or methacrylate oligomers, common organic solvents, oxidation inhibitors, viscosity modifiers, dips , photoinitiators, and tertiary amines. Non-limiting examples of such additional ingredients include acetone, isopropanol, acetonitrile, waxes, polymer powders, N,N-diethyl-4-aminobenzene (DEAB) , oxidized (2,4,6-trimethylbenzylidene) diphenylphosphine (TPO, Albemarle Corporation), 2-methyl-1-[4-(methylthio)phenyl]-2-? Oral propyl-1-one (Irgacure® 907, Ciba Chemical Specialties), phenyl phthalate (2,4,6-trimethylbenzoate) phosphine (Irgacure® 819, Ciba Chemical Specialties), liquid aliphatic amine Synergist (FIRSTCURE® AS-5 Amine, Albemarle Corporation), 4-(dimethylamino) Ethyl benzoate (ED AB), 2-ethylhexyl 4-(dimethylamino)benzoate (ODAB, Albemarle Corporation), N-methyl^-N,N-diethanolamine, ginseng (2, 4-di-t-butylphenyl)phosphite (ETHAPH0STM 3 6 8,A1 bem ar 1 e C orpor at i ο η), and 3- (3,5-di-t-butyl-4-hydroxyl) Phenyl) octadecyl propionate (ETHANOX® 376, Albemarle Corporation) 所得 When additional ingredients are used to form the polymerization inhibitor composition of the present invention, the resulting liquid polymerization inhibitor composition should contain at least about 1% by weight Nitrite (N-nitroso-N-phenylhydroxylamine) aluminum salt with a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2- Methylpropiophenone, a, oc-diethoxy-15-200835700 acetophenone, or 1-benzylidenecyclohexanol, or a combination of any two or more thereof; or b) diphenyl ketone , at least one ester having a benzhydrylphenyl group therein, or at least one acrylate having a benzhydrylphenyl group therein, or a combination of any two or more thereof; or c) both a) and b) a combination of conditions if a) is a 1-benzylidene ring Alcohols, derived from the at least one b) of the component is also present in the composition.

Preferred polymerization inhibitor compositions of the present invention are comprised of (for example at least about 9% by weight, and preferably at least about 20% by weight) of ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt and a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4,-(2-hydroxyethoxy)-2-methylpropiophenone, α,α-diethoxyacetophenone, or 1 - benzhydrylcyclohexanol, or a combination of any two or more thereof; or b) diphenyl ketone, at least one ester having a benzhydryl phenyl group therein, or at least one having a benzamidine group therein a phenyl acrylate, or a combination of any two or more thereof; or a component consisting of c), a) and b), except that it is or may be present in the residue itself of the component itself, or Contacting a residual amount of impurities obtained from the container for preparing, transporting and/or storing the component or the polymerization inhibitor composition itself, the agitating blades and/or the shaft, the conduit or the pipeline, or the like, provided that a) is 1-Benzyldecylcyclohexanol, at least one component derived from b) is also present in the composition. 2) Photohardenable formulation The liquid polymerization inhibitor composition of the present invention may comprise a polymerization inhibitor as a preparation for any photohardenable formulation. For example, a photohardenable formulation formed using a polymerization inhibitor composition may additionally comprise one or more photohardenable monomers, one or more photohardenable oligomers or polymers, or one or more photoinitiated-16-200835700 agents (free radical or cationic). Among the additional ingredients, one or more of them may be, for example, a co-initiator (also known as a synergist), a modifier, a pigment, a dye, a photostabilizer, a radical scavenger, and an admixture. The use of the compositions and their materials is well known to those skilled in the art and is described in the literature as well as many commercially available products which exhibit these functions in photorepensibles. The photocatalyst produced using the liquid polymerization inhibitor composition of the present invention can be formed by mixing the blend of the present invention with a component generally used to form a ® hardening formulation. Mixing equipment, such as blending tanks or vessels suitable for agitation or agitation, can be used to form the radiation formulations of the present invention. The formulation prepared using the polymerization inhibitor composition of the present invention generally comprises a range of from about 〇5 to about 1% by weight based on the total weight of the formulation, and preferably from about 0. 1 to about 4% by weight. The compound. Several non-limiting examples of photohardenable monomers, and/or polymers that can be used to form photohardenable formulations include monomeric, oligomeric, poly(meth) methacrylate, methyl methacrylate, acrylic Ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl Isodecyl cyclohexenoate, isodecyl methacrylate, hydroxyethyl acrylate hydroxyethyl acrylate, dimethylaminopropyl acrylate, methyl propyl propyl propyl ester, diethyl propyl acrylate An ester, diethyl methacrylate or the like, and a mixture of two or more thereof. Formulation of logistics modification adhesion promotes known hardening and hardenable radiation can be equipped with condensing hard light hardening 5 10 invention invention oligopolymer, or ethyl ester, acrylate, methyl ester, propyl, methyl acid Methylaminopropane-17-200835700 Preferred photohardenable monomers, oligomers and/or polymers useful in this formulation include monomeric, oligomeric, polymeric, or copolymeric forms of tripropylene glycol diacrylate, three Hydroxymethylpropane tetraacrylate, ethoxylated trimethylolpropane tetraacrylate, propoxy neopentyl glycol diacrylate, hexanediol diacrylate, and the like, and a mixture of two or more thereof. In general, in order to provide improved adhesion to a particular substrate, the α,β-ethylenically unsaturated carboxylic acid may be used in combination with acrylate and/or methacrylate monomers, oligomers and/or polymers, if desired. Examples of the acid include methyl ® acrylic acid, acrylic acid, itaconic acid, maleic acid, β-carboxyethyl acrylate, β-carboxyethyl methacrylate, and the like, and a mixture of any two or more thereof. Other photohardenable monomers, oligomers and/or polymers useful in the formulations include thiols, ethyl ethers, vinyl esters, oxime-vinyl compounds, in monomeric, oligomeric, polymeric, or copolymeric forms, Unsaturated polyester, styrene, divinylbenzene, acrylonitrile, polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, polyoxy acrylate, fluoroacetic acid Ester, and amine acrylate. The photohardenable formulation typically comprises from about 5 to about 85 percent by weight of one or more of the above photohardenable monomers, oligomers or polymers. Preferred formulations contain from about 20 to about 75% by weight of one or more of such photohardenable materials. It is selected within these ranges in order to generally adjust the viscosity to suit the particular coating method used. For example, photohardenable formulations suitable for use in forming low viscosity web coatings generally comprise one or more of the range from about 50 to about 70 weight percent based on the weight of all of the compositions that receive photohardening (radiation hardening) -18-200835700 This monomer, oligomer or polymer. The free radical photoinitiator which can be used to form a photohardenable formulation using the liquid polymerization inhibitor of the present invention has two general types I, which are photo-separated to generate free radicals, and type II, which produces free radicals. . The Type I photoinitiator passes through a single molecule of free radicals. Examples thereof include aromatic carbonyl compounds such as derivatives of benzoin ketal and acetophenone. Type II (extracted) is generally an aromatic ketone such as a 9-oxo-sulfonium- and diphenyl ketone derivative. In the system, a co-initiator must be present to make the initiation of free radicals. Hair sprays can include amines, alcohols, thiols, or ethers. The co-initiator that produces free radicals is subjected to a hydrogen extraction or electron transfer mechanism. A non-limiting type I (single molecule fragment) initiator that can be used as a photoinitiator for radiation hardenable formulations, such as alpha-diketone monoketal derivatives (eg, diethylidene, diphenylacetamone, Benzyl ketal derivatives); oxime (such as benzoin, 4-hydroxy^tetramethylhex-3-one (Pivaloin), etc.); oxime ether (such as benzoic acid, benzoin ethyl ether, benzoin, etc.) The fluorenylphosphine oxide, and the Type I initiator, including any two or more of such initiators, may employ a Di-type (extracted) initiator. Non-limiting examples of type initiators include ketone, 9-oxo-sulfonium, benzoin, diphenyl ketone, 4,4,-fluorene (ν, fluorene, -dimethylamino), polynuclear hydrazine (eg 9, 1 0 -蒽醌, 9,1 〇-phenanthrenequinone, 2-ethyl 1,4-naphthoquinone), and the like, and a mixture of two or more thereof. Suitable initiators include ketals such as benzoin dimethyl ketal. The preferred form of formation: the first extraction of the fragment, the diphenylethyl initiator - in these systems, the co-introduction method is based on the example inclusion compound or its dimethyl; -2, 2, 5, 5 - Other similar mixtures of fragrant methyl ether. Suitable II 2 -chloroindolone Diphenyl ketone oxime, and preferred I type II -19- 200835700 initiators include hydroquinones such as benzoquinone and 2-ethyl hydrazine. Mixtures of Type I and Type II initiators can also be used. The initiator or the mixture of initiators is generally from about 0. 01 to about 10 parts by weight, preferably from about 0. to about 5 parts by weight, per 1 part by weight of the monomer, oligomer or polymer to be photohardened. It is added in an amount of about 5 parts by weight. Among the various co-initiators which can be used in the formulation, it is generally advantageous to use tertiary amines. Several non-limiting examples of amine initiators that can be used in the formulation include >1-[3-(dimethylamino)propyl]->1,:^', 1^'-trimethyl-1, 3-propanediamine _ (Polycat 77; Air Products, Inc.), 2,2'-oxydene [N,N-dimethylethylamine] (DABCO BL-19; Air Products, Inc.), N , N-dimethyl-4-morpholine ethylamine (DABCO XDM; Air Products, Inc.); methyl diethanolamine; acrylate amine; 4-(dimethylamino)benzoic acid 2-ethylhexyl ester ( 〇DAB); 4-(dimethylamino)benzoic acid ethyl ester (EDAB); morpholine derivative; and one or more molecules each having a total of 1 (V to about 36 carbon atoms, and at least one of which is at least one alkane a trialkylamine having a chain length of at least 8 carbon atoms, such as (A) - or a plurality of molecules each having a total of 10 to about 24 carbon atoms, and # and wherein the alkyl group is a methyl or ethyl group Or one (more preferably all methyl), the remaining pendant group containing at least 8 carbon atoms (and more preferably a linear alkyl group having from 8 to about 22 carbon atoms), or (B) ) or a plurality of molecules each having a total of 17 to about 38 carbon atoms, and wherein the alkane Is a methyl or ethyl group (preferably a methyl group), and the other two alkyl groups are the same or different trialkylamines each of which is a primary alkyl group. Dodecyl dimethylamine, tetradecyldiyl An example of methylamine, hexadecyldimethylamine, octadecyldimethylamine, dimercaptomethylamine, and dodecylmethylamine being a tertiary amine of (A) or (B). Mixture of di-20-200835700 or more tertiary amine co-initiators. The amount of amine is generally in the range of from about 〇·5 to about 40% by weight based on the total weight of the formulation. Rheology modifiers which can be used to form formulations Non-limiting examples include materials such as organopolyoxo compounds, organofluorine compounds, polyethers, and organic ionic compounds. In general, rheology modifiers are formulated to about 〇1 to about 5% by weight. Amounts can be used. Pigments and dyes can be used and are often preferred for photohardening formulations. Examples and typical amounts of pigments for formulations include indigo blue (about 5 to about 20% by weight), titanium dioxide (about 1 〇 to about 3 〇% by weight), or other organic or inorganic pigments used in this art. Depending on the situation It may use a dye such as aniline black or methylene blue to enhance color or hue (for example, from about 1 to about 5 wt%). The tanning stabilizer is another type which can be used for the photohardenable formulation in which the liquid polymerization inhibitor composition of the present invention is used. Additives. Non-limiting examples of such light stabilizers include 2-hydroxydiphenyl ketones such as 2,2'-dihydroxy-4,4'-dimethoxydiphenyl ketone, 2-(2-hydroxybenzene). Benzotriazole, such as 2-(2'-hydroxyphenyl)benzotriazole, a sterically hindered amine such as anthracene (2,2,6,6-tetramethyl-4-piperidinyl)anthracene Diester or hydrazine (2,2,6,6-tetramethyl-4-piperidinyl) succinate, physic amine, such as 4,4'-dioctyloxybenzophenone, acrylate, Such as α-cyano-β, β-diphenylacrylate or methyl α-carbonylmethoxycinnamate, and nickel complexes such as 2,2′-thiopurine (1,1,3,3 a nickel complex of tetramethylbutyl phenol. Generally, the amount employed will range from about 0.02 to about 5 weight percent, depending on the particular type of light stabilizer used. Another type of additive that can be used to form the radiation hardenable composition is one or -21 - 200835700 various free radical scavengers. Non-limiting examples of suitable free radical scavengers for this use include hydroquinone, hydroquinone methyl ether, p-tert-butylcatechol, anthraquinone compounds (such as benzoquinone and alkyl-substituted benzoquinone), and other such techniques Known free radical scavengers. Generally, these ingredients are used in amounts ranging from about 1 〇 〇 p p m to about 2% by weight of the composition. The adhesion promoter composition can be used to form an additive component in which the photohardenable composition of the liquid polymerization inhibitor composition of the present invention is used. This component is generally a decane derivative such as γ-aminopropyltriethoxydecane (DOW A-11 00) and an equivalent substituted decane product; an acid functional group-substituted resin; with or without acrylic acid or methacrylic acid a saturated oligomer or monomer, such as a partial ester of phosphoric acid, maleic anhydride or phthalic anhydride; and a dimer and trimer of acrylic acid/methacrylic acid. If an adhesion promoter is used, the preferred form is other than α,β-ethylenically unsaturated carboxylic acid. If and when used, the concentration is determined experimentally by the adhesion test. Usually, however, this amount will often range from about 0.5 to about 20% by weight of the total weight of the composition, and more preferably from about 2 to about 10% by weight. Coherent or non-coherent radiation can be used for photohardening. It can use various sources of this radiation, such as ionic gas lasers (such as argon ion laser, krypton laser, chlorine: cadmium laser, etc.), solid state laser (such as frequency doubling Nd: YAG laser), semiconductor diode Radiation sources such as body lasers, arc lamps (eg medium pressure mercury lamps, xenon lamps or carbon arc lamps). Exposure sources that provide ultraviolet and visible wavelength radiation (typically in the range of 200-700 nm) can also be used for prior hardening. Preferred wavelengths are those corresponding to the spectral sensitivity of the initiator used. Preferred sources of radiation are vapors using mercury, argon, gallium, or iron salts and Li--22-200835700 gas discharge lamps using magnetic, microwave or electronic rectifiers; this lamp is often recorded, or a lamp manufactured by Fusion Systems (ie, 〇 , Η and V 4 exposure time can be applied at high speed depending on the source of radiation and the photoinitiator used, such as forming a thin coating or paper that passes at a high linear velocity. It is desirable to be about 〇. 〇〇5 to about 〇· 〇1 5 seconds. Radiation hardening in which the polymer is stationary or moving slowly on the conveyor belt (light operation can use a longer exposure time (for example, in the range of about 0.2 to 2 seconds). There are various known ways of performing photohardening operations, such as photopolymerization of a hardenable formulation into a thin coating or through a web. Alternatively, a cocoa hardening formulation can be photopolymerized or photohardened onto a substrate to form a coating or coating. The radiation hardenable formulation is condensed into the article or shape in the mold. In these and other modes of operation, exposure to hardening or photopolymerization can be continuous or intermittent. Various radiation hardening articles and shapes can be The radiation hardening is produced by using a photopolymerizable composition formed by a polymerization inhibitor. Therefore, the final product (photopolymerization) can be a printed matter on a substrate, such as a plate or a plastic film; and an article such as a handle or a handle , ink bottle trays, rulers, etc.; and coatings or laminates on the substrate, such as plywood sheets, polymer composite sheets, etc. As shown above, thin coated paper having a coating thickness of up to about 10 mils and The following examples illustrate the practice of the invention and some of its advantages. The examples are intended to be limiting and should not be construed as limiting the general scope of the invention. For the web, mixed polymerization) about 0.4 light can be used to synthesize the radiation laminate into radiation. The radiation hard paper, paper holder, small, metal of the present invention is composed of about 0.0 2 by not intending -23-200835700 Example 1 Preparation of 10% by weight of ginseng (N-nitroso-N-phenylcarbylamine) salt (FIRSTCURE® NPAL polymerization inhibitor; Albemarle Corporation), and 90% by weight of 2-hydroxy-2-methylbenzene Acetone and diphenyl ketone Compound mixture liquid 'form a polymerization inhibitor composition of the present invention. The ratio of 2-hydroxy-2-methylpropiophenone to diphenyl ketone was 40:60 by weight. This liquid composition is stabilized at 50 °F (about 10 ° C). Example 2 # By preparing 8% by weight of ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt (FIRSTCURE® NPAL polymerization inhibitor; Albemarle Corporation), and 92% by weight of 1-benzamide A liquid mixture of a mixture of a base S alcohol and a diphenyl ketone to form a polymerization inhibitor composition of the present invention. b benzhydrylcyclohexanol and diphenyl ketone are 40:60 by weight. This liquid composition is stable at room temperature. Example 3 Preparation of 7.5% by weight of ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt (FIRSTCURE® NPAL polymerization inhibitor; Albemarle Corporation), and 92.5% by weight of 2-hydroxy-2 a liquid mixture of methyl phenylacetone to form a polymerization inhibitor composition of the present invention. This liquid composition is stable at room temperature. Example 4 By preparing 7% by weight of ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt (FIRSTCURE® NPAL polymerization inhibitor; Albemarle Corporation), and 93% by weight of 2-hydroxy-2- A liquid mixture of a mixture of methyl propiophenone and o-phenyl-24-200835700 methylmercaptobenzoic acid to form a polymerization inhibitor composition of the present invention. 2-Hydroxy-2-methylpropiophenone and o-benzimidylbenzoic acid methyl ester were in a 60:40 weight ratio. Example 5 Preparation of 12% by weight of ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt (FIRSTCURE 8 NPAL polymerization inhibitor; Albemarle Corporation), and 88% by weight of 2-amino group-2- A liquid mixture of a mixture of methotrexate and diphenyl ketone forms the composition of the polymerization inhibitor # of the present invention. The ratio of 2-hydroxy-2-methylpropiophenone to diphenyl ketone was 50:50 by weight. It should be understood that the chemical name or chemical formula referred to anywhere in the specification or its patent application, whether singular or plural, refers to other substances referred to by chemical name or chemical type (such as other reactants, solvents). , thinner, etc.) exist before verification. The chemical changes, transitions, and/or reactions (if any) occurring in the resulting mixture or solution are irrelevant because the changes, transformations, and/or reactions are such that the specified anti-beta and/or components are selected under the conditions of the present disclosure. The natural result together. Thus, the reactants and other materials are verified as components that are used to carry out the desired chemical reaction or to form a mixture for carrying out the desired reaction. Furthermore, even though the scope of the following claims may refer to substances, ingredients and/or components in the present form ("including", "as", etc.), it is meant to refer to one or more of the first contact, blending or mixing in accordance with the present disclosure. A substance or component that is present before other substances or components. The substance or ingredient may lose its original identity by chemical reaction or transformation during this contact, blending or mixing operation and is therefore completely unimportant to the knowledge and understanding of the disclosure and the scope of the patent application. Each of the patents or publications referred to in any part of this specification is hereby incorporated by reference in its entirety in its entirety. The term "a" or "an" as used herein is not intended to be limiting, and should not be construed as limited to a single element. The term "a" or "an" as used herein is intended to encompass one or more of this element unless the The practice of the invention can vary widely. Therefore, the above description is not intended to be limiting, and should not be construed as limiting the invention to the specific examples set forth above. It is intended to cover the scope of the patent application below. [Simple description of the map]

dnSL pass 0 [component symbol description] 4mi no 0

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Claims (1)

200835700 X. Patent application scope: 1 · A liquid polymerization inhibitor composition formed by including a ginseng (N_-N-phenylhydroxylamine) aluminum salt and the following components: &) 2-hydroxy_2_A Phenylpropiophenone, 2-hydroxy-4,-(2-hydroxyethoxymethylpropiophenone, α,α-diethoxyacetophenone, or 1-benzylhexanol, or two or more thereof a combination of: or b) a diphenyl ketone, at least one acrylate having a benzhydryl phenyl group therein, a combination of two or more thereof; or c) a) Both b and b) are such that if a) is 1-benzylidenecyclohexanol, at least one of the components of b) is also present in the composition. 2. The composition of claim 1, wherein the composition (N-nitroso-N-phenylhydroxylamine) aluminum salt and a) are not used. 3. The composition of claim 1, wherein the composition is (N-nitroso-N-phenylhydroxylamine) aluminum salt and a) but not used, and wherein a) is 2-hydroxyl -2-methylpropiophenone. 4. The composition of claim 1, wherein the composition (N-nitroso-N-phenylhydroxylamine) aluminum salt and b) are not used. 5. The composition of claim 1, wherein the composition (N-nitroso-N-phenylhydroxylamine) aluminum salt and b) but not used, and wherein b) is diphenyl ketone. The nitroso)-2-indenyl cyclic ester, or any of its species, is derived from the reference b) and the form is defined by the reference b) from the reference a) and the form is formed by the reference a) - 200835700 6 - The composition of claim 1, wherein the composition is formed from a ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt and c). 7. The composition of claim 1, wherein the composition is formed from ginseng (N-nitroso-p-phenylhydroxylamine) aluminum salt and c), and wherein c) is 2-hydroxy- 2-methylpropiophenone and diphenyl ketone; 1-benzylidenecyclohexanol and diphenyl ketone; or 2-hydroxy-2-methylpropiophenone and methyl ortho-benzoylbenzoate. 〇8. The composition of claim 1, wherein the amount of the ginseng (nitroso-indolyl-phenylhydroxylamine) aluminum salt used to form the composition is based on the total weight of the composition. At least 5% by weight. 9. The composition of claim 1, wherein the amount of the ginseng (nitroso-indolyl-phenyl-phenylamine) salt used to form the composition is based on the total weight of the composition. At least 10% by weight. A method of producing a liquid polymerization inhibitor composition, the method comprising: combining an aluminum salt comprising ruthenium (nitroso-nitro-p-phenylhydroxylamine) and the following component: 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, α,α-diethoxyacetophenone, or 1-benzene Mercaptocyclohexanol, or a combination of any two or more thereof; or b) diphenyl ketone, at least one ester having a benzhydryl phenyl group therein, or at least one having a benzhydryl phenyl group therein Acrylate, or a combination of any two or more thereof; or c) a) and b) both, -28- 200835700 • a ♦ dream % ivM condition if a) is a 1-benzhydryl ring In the case of hexanol, at least one component derived from b) is also present in the composition. 11. The method of claim 10, wherein the composition is formed using ginseng (N-nitrosyl-N-phenylhydroxylamine) aluminum salt and a) but not b). 1 2 . The method of claim 10, wherein the composition is formed using ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt and a) but not b), and wherein a ) is 2-hydroxy-2-methylpropiophenone. Ο 13. The method of claim 10, wherein the composition is formed using ginseng (N-nitrosyl-N-phenylhydroxylamine) aluminum salt and b) but without a). 1 4 . The method of claim 1 wherein the ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt is used and b) but a) is used to form the composition, and wherein ) is diphenyl ketone. 15. The method of claim 1, wherein the composition is formed using a ginseng (N-nitrosyl-N-phenylhydroxylamine) aluminum salt and c).馨16. The method of claim 10, wherein the composition (formed as "N_nitroso-N-phenylhydroxylamine) aluminum salt and c) is used to form the composition 'and c) thereof 2-methylpropiophenone and diphenyl ketone; 1-benzylidenecyclohexanol and diphenyl ketone; or 2-hydroxy-2-methylpropiophenone and methyl o-besylbenzoate. 1 7 . The method of claim 1 wherein the amount of the ginseng (N-nitroso-N-phenylhydroxylamine) salt used to form the composition is according to the composition -29-.200835700 The total weight is at least 5% by weight. 18. The method of claim 10, wherein the amount of the ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt used to form the composition is at least 1 based on the total weight of the composition. 〇% by weight. 19. A method of preparing a photohardenable formulation comprising a polymerization inhibitor, the formulation comprising at least one photohardenable monomer, oligomer and/or polymer modified to include the polymerization in the formulation The inhibitor is a liquid formed from cerium (N-nitrosophenylhydroxylamine) aluminum salt and the following components: a) 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-( 2-hydroxyethoxy)-2-methylpropiophenone, α,α_=ethoxyacetophenone, or 1-benzylidenecyclohexanol, or a combination of two or more thereof; or b a diphenyl ketone, at least one ester having a benzhydryl phenyl group therein, or at least one acrylate having a benzhydryl phenyl group therein, or a combination of two or more thereof; or c) a) And b) both, where the condition is that if a) is 1-benzimidylcyclohexanol, at least one component derived from b) is also present in the composition. 20. The improvement of claim 19, wherein the composition (N-nitroso-N-phenylhydroxylamine) aluminum salt and a) but not b) are used to form the composition 〇2 1 . The improvement of the ninth item of the formula wherein the composition is formed using the ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt and b) but without using a). -30- 200835700 22. The improvement of claim 19, wherein the composition is formed using a ginseng (N-nitrosyl-N-phenylhydroxylamine) aluminum salt and c). 23. The improvement of claim 19, wherein the amount of the ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt used to form the composition is at least the total weight of the composition. 5 wt%. 24. The improvement of claim 19, wherein the amount of the ginseng (N-nitroso-N-phenylhydroxylamine) aluminum salt used to form the composition is at least 1 based on the total weight of the composition. 〇% by weight. -31- 200835700 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ j \ \\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: