| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 31.12.02 |
| PATENT TITLE |
Polymeric material composition |
| PATENT ABSTRACT |
A polymeric material composition with improved weatherability and resistance to discoloration, comprising 100 parts by weight of a polymer material and 0.001-10 parts by weight of a triazine compound represented by the following formula (I): ##STR1## (wherein A represents ring A; X and Y each independently represents ring A or ring B; R.sub.1 represents a C1-C25 alkyl group substituted by a (meth)acryloyloxy group, wherein the alkyl group may further be substituted by a hydroxyl group, a C1-C8 alkoxy group, or a C1-C8 acyloxy group, or the alkyl group my contain, as an insertion, an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amido group, or an imino group; R.sub.2 represents a hydrogen atom; R.sub.3, R.sub.4, R.sub.5 and R.sub.6 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C12 alkyl group, a C1-C12 alkenyl group, a C1-C12 alkoxy group, a C1-C12 alkoxycarbonyl group, or an arylalkyl group, wherein the alkyl group, the alkoxy group, the alkoxycarbonyl group, and the arylalkyl group may be substituted by a hydroxyl group, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a sulfonic acid group, a glycidyloxy group, a cyano group, an isocyanate group, or a (meth)acryloyl group, or, the alkyl group, the alkoxy group, the alkoxycarbonyl group, and the arylalkyl group may contain, as an insertion, an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amido group, or an imino group; and the substitution and the insertion may occur in combination, and R.sub.3 represents a hydrogen atom in the case of R.sub.3 being in the 5-position.) |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | February 22, 2001 |
| PATENT CT FILE DATE | April 12, 1999 |
| PATENT CT NUMBER | This data is not available for free |
| PATENT CT PUB NUMBER | This data is not available for free |
| PATENT CT PUB DATE | October 19, 2000 |
| PATENT CLAIMS |
What is claimed is: 1. A polymeric material composition comprising 100 parts by weight of a polymer material and 0.001-10 parts by weight of a triazine compound represented by the following formula (I): ##STR6## wherein A represents ring A; X and Y each independently represents ring A or ring B; R.sub.1 represents a C1-C25 alkyl group substituted by a (meth)acryloyloxy group, wherein the alkyl group may further be substituted by a hydroxyl group, a C1-C8 alkoxy group, or a C1-C8 acyloxy group, or the alkyl group my contain, as an insertion, an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amido group, or an imino group; R.sub.2 represents a hydrogen atom; R.sub.3, R.sub.4, R.sub.5 and R.sub.6 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C12 alkyl group, a C1-C12 alkenyl group, a C1-C12 alkoxy group, a C1-C12 alkoxycarbonyl group, or an arylalkyl group, wherein the alkyl group, the alkoxy group, the alkoxycarbonyl group, and the arylalkyl group may be substituted by a hydroxyl group, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a sulfonic acid group, a glycidyloxy group, a cyano group, an isocyanate group, or a (meth)acryloyl group, or, the alkyl group, the alkoxy group, the alkoxycarbonyl group, and the arylalkyl group may contain, as an insertion, an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amido group, or an imino group; and the substitution and the insertion may occur in combination, and R.sub.3 represents a hydrogen atom in the case of R.sub.3 being in the 5-position. 2. The polymeric material composition according to claim 1, wherein the polymeric material contains a hetero atom. 3. The polymeric material composition according to claim 2, wherein the polymeric material contains a hetero atom in its backbone chain. 4. The polymeric material composition according to claim 3, wherein the polymeric material is a polycarbonate resin. 5. The polymeric material composition according to claim 2, wherein the polymeric material is a poly(meth)acrylate resin. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
TECHNICAL FIELD The present invention relates to a polymeric material composition having improved properties in terms of weatherability and resistance to discoloration by virtue of a specific triaryltriazine compound incorporated in the composition. The triaryltriazine compound has at least one aryl group which is a 2-hydroxyphenyl group having, at the 4-position thereof, an alkyl group substituted by a (meth)acryloyloxy group. BACKGROUND OF THE INVENTION Polymer materials such as polyethylene, polypropylene, styrene resin, polyvinyl chloride, polycarbonate, and polyester; organic pigments; and organic dyes may not endure prolonged use, due to deterioration caused by light and resultant discoloration or lowering of mechanical strength. Conventionally, in order to prevent deterioration of such organic materials and to control the wavelength of light penetrating the materials, a variety of UV-absorbers have been used. Examples of such UV-absorbers include benzophenone, benzotriazole, 2,4,6-triaryltriazine, and cyanoacrylate compounds. These UV-absorbers exhibit various UV absorption spectra attributed to the structures thereof. Also, the compatibility and volatility of the UV-absorbers differ depending on the material. Therefore, an appropriate UV-absorber is chosen in accordance with the intended use of the polymer material. Particularly, a thin film-like material employed as a protective layer must contain a large amount of UV-absorber in order to enhance the UV-shielding effect of the layer. Therefore, there is demand for an UV-absorber having excellent compatibility with a substrate layer, low volatility, and high absorption coefficient. A 2,4,6-triaryltriazine UV-absorber exhibits a high absorption coefficient and excellent heat resistance. However, when the UV-absorber is incorporated into a polymer material, the UV-absorber may impart color to a resin of the material during processing, which is detrimental to practical use. Japanese Patent Publication (kokoku) No. 42-25303 and Japanese Patent Application Laid-Open (kokai) No. 4-117410 disclose that, when a (meth)acryloyl-group-containing UV-absorber is incorporated into a skeleton of a polymer material through polymerization, or when the UV-absorber is oligomerized to thereby form a high-molecular-weight UV-absorber, the UV-absorber thus obtained exhibits persistent UV-absorbing effect in the polymer material. During the polymerization or oligomerization, the UV-absorber is copolymerized with a compound having an ethylenic unsaturated bond, and thus (meth)acryloyl groups present in the polymer material are lost. For this reason, it has never been expected that discoloration of polymer materials could be prevented if an UV-absorber is added into a polymer material without loss of (meth)acryloyl groups. DISCLOSURE OF THE INVENTION In view of the foregoing, the present inventors have performed extensive studies, and have found that a triazine compound represented by the following formula (I) having a substituent at a specific position thereof and having a (meth)acryloyl group exhibits UV-absorbing effects; and that a polymeric material composition containing the triazine compound exhibits excellent weatherability and excellent heat resistance without inducing discoloration of the organic material. The present invention has been accomplished on the basis of these findings. Accordingly, the present invention provides a polymeric material composition comprising 100 parts by weight of a polymer material and 0.001-10 parts by weight of a triazine compound represented by the following formula (I): ##STR2## (wherein A represents ring A; X and Y each independently represents ring A or ring B; R.sub.1 represents a C1-C25 alkyl group substituted by a (meth)acryloyloxy group, wherein the alkyl group may further be substituted by a hydroxyl group, a C1-C8 alkoxy group, or a C1-C8 acyloxy group, or the alkyl group may contain, as an insertion, an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amido group, or an imino group; R.sub.2 represents a hydrogen atom; R.sub.3, R.sub.4, R.sub.5 and R.sub.6 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C12 alkyl group, a C1-C12 alkenyl group, a C1-C12 alkoxy group, a C1-C12 alkoxycarbonyl group, or an arylalkyl group, wherein the alkyl group, the alkoxy group, the alkoxycarbonyl group, and the arylalkyl group may be substituted by a hydroxyl group, a halogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a sulfonic acid group, a glycidyloxy group, a cyano group, an isocyanate group, or a (meth)acryloyl group, or, the alkyl group, the alkoxy group, the alkoxycarbonyl group, and the arylalkyl group may contain, as an insertion, an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amido group, or an imino group; and the substitution and the insertion may occur in combination, and R.sub.3 represents a hydrogen atom in the case of R.sub.3 being in the 5-position.) The present invention will next be described in more detail. BEST MODES FOR CARRYING OUT THE INVENTION Triazine Compounds Examples of the alkyl group which is to be substituted by a (meth)acryloyloxy group to form a (meth)acryloyloxy group-substituted alkyl group R.sub.1 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, isooctyl, sec-octyl, tert-octyl, and 2-ethylhexyl. Examples of the alkyl group having a substituent include 2-acetoxypropyl, 2-hydroxypropyl, and 2-butoxymethylethyl. Examples of constituent chains of the alkyl group, in which an oxygen atom or another atom is inserted, include polyoxyethylene and polyoxypropylene. More specifically, examples of the group represented by R.sub.1 include (meth)acryloyloxyalkyl groups such as acryloyloxyethyl, methacryloyloxyethyl, 2-hydroxy-3-methacryloyloxypropyl, 2-(2-methacryloyloxyethyloxy)ethyl, and 2-hydroxy-3-(2-methacryloyloxyethyloxy)propyl. Examples of the alkyl groups represented by R.sub.3, R.sub.4, R.sub.5, or R.sub.6 in formula (I) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tert-amyl, octyl, tert-octyl, decyl, undecyl, and dodecyl. Examples of the arylalkyl group include 1-methyl-1-phenylethyl, benzyl, and 2-phenylethyl. Examples of the C1-C12 alkenyl groups represented by R.sub.3, R.sub.4, R.sub.5, or R.sub.6 include linear or branched propenyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl. In such an alkenyl group, an unsaturated bond may be present at any position. Examples of the C1-C12 alkoxy groups and the C1-C12 alkoxycarbonyl groups represented by R.sub.3, R.sub.4, R.sub.5, or R.sub.6 include derivatives of alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tert-amyl, octyl, tert-octyl, decyl, undecyl, and dodecyl. Examples of the arylalkyl group include a cumyl group and a phenylmethylene group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the triazine compounds represented by formula (I), which are used in the present invention, include the following No. 1 to No. 6 compounds. ##STR3## ##STR4## The method for synthesizing the triazine compounds of formula (I), which are used in the present invention, is not particularly limited, and the compounds may be synthesized by means of any customary method. For example, any of the compounds may be synthesized by means of the following synthesis method: a method in which 2-(2,4-dihydroxyphenyl)-4,6-diaryl-s-triazine is reacted with glycidyl methacrylate, to thereby yield 2-(2-hydroxy-4-(2-hydroxy-3-methacryloyloxypropyloxy)phenyl)-4, 6-diaryl-s-triazine; a method in which 2-(2,4-dihydroxyphenyl)-4,6-diaryl-s-triazine is reacted with alkylene oxide to yield 2-(2-hydroxy-4-(2-hydroxyalkoxy)phenyl)-4,6-diaryl-s-triazine, followed by reaction with (meth)acrylic acid, to thereby yield 2-(2-hydroxy-4-(2-(meth)acryloyloxyalkoxy)phenyl)-4,6-aryl-s-triazine; or a method in which benzamidine hydrochloride is reacted with phenyl resorcylate to yield 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-s-triazine, followed by reaction with alkylene oxide and then with (meth)acrylic acid, to thereby yield 2-(2-hydroxy-4-(2-(meth)acryloyloxyalkoxy)phenyl)-4,6-diphenyl-s-triazine. Polymer Material Examples of the polymer material used in the present invention include thermoplastic resins, thermosetting resins, and elastomers. Examples of thermoplastic resins include .alpha.-olefin polymers such as high-density, low-density, or linear low-density polyethylene, polypropylene, polybutene-1, and poly-3-methylpentene; polyolefins and copolymers thereof such as ethylene/vinyl acetate copolymers and ethylene/propylene copolymers; halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride/vinyl acetate copolymers, vinyl chloride/ethylene copolymers, vinyl chloride/vinylidene chloride copolymers, vinyl chloride/vinylidene chloride/vinyl acetate terpolymers, vinyl chloride/acrylate copolymers, vinyl chloride/maleate copolymers, and vinyl chloride/cyclohexylmaleimide copolymers; petroleum resins; coumarone resins; polystyrene; polyvinyl acetate; acrylic resins; copolymers of styrene and/or .alpha.-methylstyrene and other monomers (such as maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, and acrylonitrile), such as AS resins, ABS resins, MBS resins, and heat-resistant ABS resins; polymethyl methacrylate; polyvinyl alcohol; polyvinyl formal; polyvinyl butyral; linear polyesters such as polyethylene terephthalate and polytetramethylene terephthalate; polyphenylene oxide; polyamides such as polycaprolactam and polyhexamethylene adipamide; polycarbonate; branched polycarbonate; polyacetal; polyphenylene sulfide; polyurethane; cellulose resins; and blends thereof. Examples of thermosetting resins include phenolic resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins. Examples of elastomers include isoprene rubber, butadiene rubber, acrylonitrile/butadiene copolymer rubber, and styrene/butadiene copolymer rubber. Of the above-described polymer materials, hetero-atom-containing polymer materials are particularly preferred because such polymer materials are highly compatible with triazine compounds of formula (I). Examples of the hetero-atom-containing polymer materials include polycarbonate; branched polycarbonate; linear polyesters such as polyethylene terephthalate and polytetramethylene terephthalate; polyamides such as polycaprolactam and polyhexamethylene adipamide; polyphenylene oxide; polyphenylene sulfide; poly(meth)acrylates such as polymethyl (meth)acrylate and polybutyl (meth)acrylate. Of these polymer materials, polymer materials containing a hetero-atom or an aromatic group in the main chain thereof are particularly preferred. Examples of such polymer materials include polycarbonate, polyethylene terephthalate, and polyphenylene oxide. These polymer materials may be used singly or in combination of two or more species. For example, these polymer materials may be used as composite materials such as polycarbonate/ABS and polycarbonate/polyester; or may be used as laminate films. Such a laminate film comprises a first polycarbonate film and a second polycarbonate film or poly(meth)acrylate film containing the specific triazine compound of formula (I) used in the present invention. Polymeric Material Composition The polymeric material composition of the present invention comprises a polymer material and a triazine compound represented by formula (I). In the composition, the amount of the triazine compound is 0.001-10 parts by weight on the basis of 100 parts by weight of the polymer material, preferably 0.005-10 parts by weight. When the amount of the triazine compound falls within the above range, weatherability and resistance to discoloration of the polymeric material composition are improved. The method for application of the triazine compound of the present invention to the polymer material is not particularly limited. When the triazine compound is added to the polymer material, the compound may assume the form of powder, aqueous dispersion such as emulsion and suspension, or solution of organic solvent. However, when the triazine compound is added to the polymer material during polymerization, or when the compound is added to the material under the conditions such that reaction of a (meth)acryloyl group occurs at a processing temperature, the resultant polymeric material composition considerably colors during processing, which is detrimental to practical use. The polymeric material composition of the present invention may be used in combination with additives that are used for general purposes, such as antioxidants and stabilizers, if necessary. Examples of particularly preferred additives include antioxidants such as phenolic antioxidants, sulfur-containing antioxidants, and phosphite antioxidants; and hindered amine light stabilizers. Of these, hindered amine light stabilizers such as 2,2,6,6-tetramethylpiperidine compounds are more preferable because such a light stabilizer and the triazine compound of the present invention exhibit synergistic effects. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethyleneglycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis [3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate amide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanura te, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionylox y}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and triethyleneglycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]. Examples of sulfur-containing antioxidants include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; and .beta.-alkylmercaptopropionate esters of polyols such as pentaerythritol tetra(.beta.-dodecylmercaptopropionate). Examples of the phosphite antioxidant include trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylph enyl]phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, di(stearyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, tetra(tridecyl)bisphenol A diphosphite, tetra(tridecyl) isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl) fluorophosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphorphenanthrene-10-oxide, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6- yl)oxy]ethyl)amine, and a phosphite of 2-ethyl-2-butylpropyleneglycol and 2,4,6-tri-tert-butylphenol. Examples of hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl benzoate, N-(2,2,6,6-tetramethyl-4-piperidyl)dodecylsuccinimide, 1-[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]-2,2,6,6-tetrameth yl-4-piperidyl-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis(2,2,6,6-tetramethyl-4-piperidyl) cebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) cebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydr oxybenzyl) malonate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, tetra(2,2,6,6-tetramethyl-4-piperidyl)butane tetracarboxylate, tetra(1,2,2,6,6-pentamethyl-4-piperidyl)butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) di(tridecyl)butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) di(tridecyl)butane tetracarboxylate, 3,9-bis[1,1-dimethyl-2-{tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy )-butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[1,1-dimethyl-2-{tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonylo xy)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,5,8,12-tetrakis[4,6-bis{N-(2,2,6,6-tetramethyl-4-piperidyl)butylamino}-1 ,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane, a condensation product of 1-(2-hydroxyethyl)-2,2,6, 6-tetramethyl-4-piperidinol/dimethyl succinate, a condensation product of 2-tert-octylamino-4,6-dichloro-s-triazine/ N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, a condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine/ dibromoethane, 2,2,6,6-tetramethyl-4-piperidyl-1-oxime, bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxime) cebacate, and 2,2,6,6-tetramethyl-4-piperidyl-N-oxime benzoate. Other additives may be incorporated in the polymeric material composition of the present invention, if necessary. Examples of the additives include heavy metal deactivating compounds, nucleating agents, metallic soap, organotin compounds, plasticizers, epoxy compounds, foaming agents, antistatic agents, fire retardants, lubricants, and processing aids. Applications of the polymeric material compositions are not particularly limited. However, the compositions are particularly suitable for forming a thin-film-like material. Examples of the thin-film-like material include synthetic resin films, sheets, paints, and fibers that are used for nonwoven or woven fabrics |
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