SE438321B - UV RADIATOR PREPARATION, TONE-RESISTANT COATING AND COMPOSITION FOR ITS PREPARATION - Google Patents

Description

Although UV absorbers can be added to abrasion resistant coatings as set forth in the above applications, only limited concentrations of UV absorbers can be readily retained in the generally described coatings according to the invention. these inventions. The concentrations that can be used provide only limited protection against UV radiation. Higher concentrations lead to a "rash" on the coatings and a white, misty appearance in the film, which is caused by the precipitating agents precipitating within the film coating or on the surface of the coating. This result is shown in the compositions independent of the catalyst used, whether using highly fluorinated aliphatic sulfonylic or sulfonic catalysts according to US-PS 4,049,861, onium catalysts according to US-PA 764 817, metal ester catalysts according to AU-PS 483 792 or The present invention relates to a coating which is abrasion resistant and resistant to rashes for use on substrates which may be damaged by UV radiation, abrasion and / or soiling. Abrasion-resistant coatings from epoxy-terminated silanes are used according to the invention in combination with absorbents for UV radiation. According to the present invention, epoxy-terminated silanes are copolymerized with aliphatic polyepoxy materials to form abrasion resistant coatings which can retain sufficient concentrations of UV radiation absorbers within the cured copolymer to obtain an effective UV absorber. The epoxy-terminated silane comprises 30-90% by weight of the reactive material which forms the finished composition, the aliphatic polyepoxy material comprises 10-70% by weight of the reactive material, and -20% by weight of other copolymerizable materials may be included as reaction-prone materials, it is preferred to have 50-80% epoxy-terminated silane, 10-50% polyepoxy material and 0-10% co-polymer. The monomers, which absorb UV radiation, and are not included in the description of the reactive materials (but some n be prone to reaction during the copolymerization and still provide absorption of UV radiation) must be present in an amount sufficient to absorb at least 90% of all radiation between 290-400 nm and transmit at least 90% of all radiation between 400 and 780 nm and not less than 75% transmissivity within each 50 nm range between 400 and 780 nm. Preferably, there is no less than 90% transmissivity over each 100 nm range between 400 and 780 nm. Any of the described catalyst systems for curing epoxy-terminated silanes to abrasion-resistant coatings can be used according to the invention. The preferred catalyst systems are highly fluorinated aliphatic sulfonyl catalysts according to US-PS 4,049 861 and onium catalysts according to US-PA 764 817. The thickness of the coating according to the invention may vary between 0.5 and 500 μm, with thicknesses between 0.5 and 50 μm. The most suitable film thickness is between 1.0 and 20 μm.

Epoxy-terminated silanes are compounds or materials having polymerizable (preferably terminal) epoxy groups and terminal, polymerizable silane groups, the bridge between these groups being a non-hydrolysable aliphatic, aromatic or mixed aliphatic-aromatic divalent hydrocarbon group, which may have N and / or 0 atoms in the group chain. Chains without N atoms are preferred and it is especially preferred to have O atoms only adjacent to the epoxy group. The O atoms, for example, could exist in the chain only as ether linkages. These group chains can usually be substituted in a known manner, since substituents on the chain do not to any great extent affect the functional ability of the epoxy-terminated silanes to undergo the essential reactions necessary. for polymerization via siloxane groups or epoxy terminal groups. Examples of substituents which may be present on the linking or bridging component are such groups as NO 2, alkyl (eg CH 3 (CH 2) n CH 2), alkoxy (eg methoxy), halogen etc. In the general structural formula given in the description of the present invention, such permissible substitution on the bridging components is included unless specifically excluded by linguistic means such as "unsubstituted divalent hydrocarbon group". Examples of preferred epoxy-terminated silanes which can be used according to the invention are compounds with the general the formulas o / \ _ io 0112 _ c fl énenen s1 (oR ") m and Ü 419m s1 (oR ') m Hm Nm where R. = a non-hydrolysable divalent hydrocarbon group (aliphatic, aromatic or mixed aliphatic-aromatic) with less than 20 carbon atoms or a divalent group having less than 20 carbon atoms composed of C, N, S and O atoms (these atoms are the only atoms which should be present in the skeleton of the divalent groups), the oxygen being in the form of ether linkage are. It is preferred that no N atoms be present. Two heteroatoms should not lie 1 next to each other within the divalent hydrocarbon group. This description defines divalent hydrocarbon groups for epoxy-terminated siloxanes according to the invention. A more suitable formula for the epoxy-terminated sila- I o .och _ Ü-nz-s fl onlh wherein R 2 represents a non-hydrolyzable divalent hydrocarbon group having less than 20 carbon atoms or a divalent group -s are O 2 1 C112 - cHfR (OR) 3 7803389-1 5 with less than 20 carbon atoms in the skeleton, which is composed of only C, N, S and O atoms, two heteroatoms shall not be adjacent to each other, and R1 denotes an aliphatic hydrocarbon group or an acyl group having less than 10 carbon atoms.

In the compositions used according to the invention, the epoxysilane may have the stated formula, wherein n represents O-1, R represents any divalent hydrocarbon group, such as methylene, ethylene, decal, phenylene, cyclohexylene, cyclopentylene, methylcyclohexylene , 2-ethylbutylene and allene, or an ether group such as -CH 2 -CH 2 -O-CH 2 -CH 2, -fcnz-cnzoß-cnz-cnf, -kj-o-cnz-cnz- and -cazo- (cnzß-R is an aliphatic hydrocarbon group having less than 10 carbon atoms, such as methyl, ethyl, isopropyl, butyl, vinyl, alkyl or any acyl group having less than 10 carbon atoms, such as formyl, acetyl, propionyl or any group of the formula (CH 2 CH 2 O) k 2, wherein k denotes an integer of at least 1, and Z denotes hydrogen.

The most preferred epoxy-terminated silanes are those illustrated by the formula: 'CH 2 \ g / CH- (CH 2) m -O- (CH 2) n -Si (OR) 3 and 0 U- (cnz) m -O- (GHz) n-§1 (OR) 3 wherein R represents an alkyl group having up to 6 carbon atoms and m and n independently represent 1-6.

The compositions may additionally contain additives such as surfactants, viscosity modifiers, additives which contribute to dispersion, dyes, etc.

These can be mixed with other epoxy-terminated silanes and comonomers to adjust the physical properties of the finished coating. Comonomers are such materials, __ ~, ._............___..._._....__.._...._. _. _. 7803389-1 10 15 20 25 30 35. ....._._ _ .. _... 6 known in the art can be copolymerized with epoxy groups or silane groups, and they include epoxy compounds and silanes. : The catalysts of the invention are commonly used in amounts from 0.01 to 10% by weight of the reactive constituents of the curable composition. Preferably from 0.5-5% by weight is used, the amount varying with the particular catalyst used. The most suitable catalysts according to the invention are highly fluorinated aliphatic sulfonyl catalysts and onium catalysts. The related high fluorinated aliphatic sulfone catalysts are very useful as are some Lewis and Brönsted acids, but they are not as suitable. The sulfonic materials are defined as highly fluorinated aliphatic sulfonic acids or salts thereof. Fluoroaliphatic sulfonic acids, methanes and imides and their preparation are described in U.S. Pat. No. 4,049,861. The sulfonyl materials are defined as compounds containing two highly fluorinated aliphatic sulfonyl groups attached directly to an imide or methylene (e.g. -NR or -ëR'R "-). The sulfone materials can be illustrated by the formula '(Rfso3) nR wherein R represents hydrogen, an ammonium cation or a metal cation and n has the valence of R.

The preferred sulfonyl catalysts can be illustrated by the formula (RfSO2) -Q- (SO2R'f) wherein Q represents a divalent group consisting of -NR, -I -CR'R "or -C = CHR3 ya; Rfsof, alkenyl with 3-4 carbon atoms, alkyl having 1-20 carbon atoms (preferably 1-4), aryl having 1-20 carbon atoms (preferably up to 10, eg phenyl, naphthyl, pyridyl, benzthienyl, etc.) or alkaryl having 7-20 carbon atoms I - ( preferably to 10), R 'represents hydrogen, chlorine, bromine, wherein R "is composed of hydrogen, chlorine, bromine, iodine, ammonium cations or metal cations and R represents H, alkenyl (3-Å) carbon atoms or aryl having up to 20 carbon atoms. The catalysts in which the N or C atom attached to the highly fluorinated aliphatic (preferably alkyl) group has a hydrogen atom attached thereto are active catalysts. Those that do not have a hydrogen atom are latent and can be activated with heat, acid, chelating agents or combinations thereof in a known manner.

Rf and R'f independently represent highly fluorinated aliphatic groups, which are defined as fluorinated, saturated, monovalent, aliphatic groups having 1 to 20 carbon atoms.

The chain backbone of the group may be straight, branched or large enough (eg at least 3 or 5 atoms) cycloaliphatic and it may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms, which are attached only to carbon atoms. Preferably it contains fluorinated aliphatic the chain of the group does not contain more than one heteroatom, ie nitrogen or oxygen, per two carbon atoms in the chain backbone.A fully fluorinated group is preferred but hydrogen or chlorine atoms may be present as substituents in the fluorinated aliphatic group provided that no more than one atom of each kind is present in the group for each carbon atom, Preferably the fluoroaliphatic group is a saturated perfluoroalkyl group having a straight or branched chain skeleton having the formula CcF2x + 1 wherein x represents 1-18 .

The active sulfonyl catalysts, which are particularly preferred according to the invention, are compounds of the formula wherein Rf and R'f independently represent a highly fluorinated alkyl group and Q represents a divalent group consisting of -NH- or -CHR-, wherein R represents Br, C1, I, H, alkyl groups of 1-20 carbon atoms (preferably 1-4), alkenyl of 3-4 carbon atoms, aryl or aralkyl of up to 20 carbon atoms (preferably up to 10) or R'X, wherein R 'represents an alkylene group having up to 20 carbon atoms (preferably 1-4) and X represents H, Br, Cl, I, -O 2 SR , -cH (o2sRf) 2, -cH- (cn-cool fl, or -cY (cooR2) 2 Br wherein R4 represents H or alkyl of 1-8 carbon atoms and n represents 0-8, and wherein R? represents alkyl of 1 -4 carbon atoms or phenylalkyl, wherein the alkyl group has 1-4 carbon atoms, and Y represents H, Br, Cl, I or NO 2.

The ammonium cation according to the invention can be defined as cations of ammonia, of primary, secondary, tertiary and quaternary amines. Alkyl, aryl, alkaryl, etc. according to the present invention (excl. Rf-type groups defined elsewhere) include such simple substituted groups which are known in the art to be -CH2CH2CH2Cl, .- SO3- <: :>).

The choice of the most suitable perfluoroalkylsulfonylmethanational group equivalents (eg the catalyst depends on the particular monomer compositions in which the catalyst is to be used and the application for which the composition is intended).

It is often preferred to add, in addition to the fluoroalkylsulfonyl protonic acid catalysts, from about 0.01-5%, preferably about 0.1-2%, of a second siloxane hydrolysis and condensation catalyst, although the use of these compounds is not necessary in the compositions of the invention for to effect curing of coatings of the composition. As illustrated by the examples, certain such catalyst combinations provide synergistic effects, thereby obtaining an increased cure rate over the rate obtainable with the fluoroalkylsulfonyl protonacid catalyst alone. Such siloxane hydrolysis and condensation catalysts are well known and are described in part in U.S. Pat. No. 4,049,861.

The metal ester catalysts used in the invention are metal esters of aluminum, titanium or zirconium having at least two ester groups of the formula -OR directly bonded to the metal, wherein R represents a hydrocarbyl group with 1-18 carbon atoms, preferably alkyl or acyl having 1-8 carbon atoms. The remaining metal valences can be met with organic components, inorganic components, complexing agents or even recurring -O-Ti-O groups, etc. (if the remaining valences are not met by OR groups, halides or alkyl groups are preferably used). As long as two of the ester groups are present, the metal ester can react to the finished polymeric structure and catalyze the reaction to form an abrasion resistant coating.

It is usually preferred that all metal valencies be satisfied through ester groups, but other groups may be present as long as at least two ester groups are present. Compounds of the formula R'nM (oR) mm are therefore useful, when R has the indicated meaning, m represents the valence of M: and n represents 0, 1 or 2 so that mn is always at least 2, and R 'represents an organic or inorganic component bound to M or a complexing agent which satisfies M's valence requirements.

Compounds of formula M (OR) m are generally preferred because of their availability and generally good properties. M represents metal, preferably titanium, aluminum or zirconium.

It is critical that the metal ester not be completely hydrolyzed or hydrolyzed to a stage where less than two ester groups per titanium atom are present on the metal ester. If the metal ester is hydrolyzed in this way, the ambifunctional silane and the metal ester will co-precipitate to an insoluble material because the reaction-prone sites of the silane on the ester have been removed.

V. onl catalysts preferred according to the invention are aromatic organic adducts of an aromatic. Group Va, VIa or VIIa organoatomic cations, in particular phosphorus, antimony, sulfur, nitrogen or iodine atoms, and an anion. When these onium catalysts are described, for convenience, the atom from group Va, VIa or VIIa, which gives the main name of the adduct (ie phosphorus in phosphonium, sulfur in sulfonium, iodine in iodonium, etc.), will be called the nominative atom. Aromatics used in describing the groups of onium catalysts used in the present invention refer to an aromatic or heterocyclic ring (phenyl, naphthyl, 6- or 7-1edaa netocycle composed of only C-, N-, S -, O- and Se-substituted or unsubstituted 5-, atoms having at most one atom in the ring selected from S-, O- or 'Se atoms), the ring being so attached to the nominative atom that it is at least as electron withdrawing as benzene. For example, phenacyl <0 -ë-CH2- is a suitable aromatic group (since it is at least as electron withdrawing as benzene), but benzyl <šâ> -CH2- is not as suitable due to the instability of this compound, which adversely affects law - _ ring stability. Representative aromatic rings are phenyl, naphthyl, thienyl, pyranyl, furanyl and pyrazolyl, which rings may be optionally substituted.

A descriptive formula for the onium catalysts according to the invention is (mn - 13+ X- (H15 wherein R represents an aromatic group which is at least as electron withdrawing as benzene, R1 represents R or alkyl (straight, branched, cyclic or substituted) or alkenyl with 1 to 18 carbon atoms, n denotes a positive integer of at least 1 (preferably 2) up to A's valence plus one, a denotes 0 or a positive integer up to 10 15 78033894 ll A's valence (preferably A minus l), n plus a is equal to A's valence plus one, A represents an atom from group Va, VIa or Vlla, and X represents an anion, wherein, when A represents halogen, n represents at least 2.

These onium materials are previously known. For example, Belgian Patents 833,472, 828,668, 828,669 and 828,670 disclose the use of certain onium compounds as cationic polymerization catalysts for certain monomers. Other organo groups attached to the nominative group of group Va or VIa may be the same aromatic. group or a substituted or unsubstituted alkyl or cycloalkyl group. The organic groups have up to 4 carbon atoms, R 'represents an alkyl group having up to 6 carbon atoms and u represents 0 or 1.

The presence of catalytic amounts of moisture has been found to be necessary to initiate the condensation of silanes with these catalysts. Atmospheric moisture is usually sufficient, but water can be added to the system if desired or if polymerization is required in the absence of air for any particular purpose.

Examples of suitable onium salts are, but not limited to: A. Onium salts with a cation of Group Va of the Periodic Table 4 acetofenyltrifenylammoniumklorid difenylmetylammoniumtetrafluoroborat \ tetra (4-chlorophenyl) phosphonium tetrafenylfosfoniumjodid tetrafenylfosfoniumhexafluorofosfat (4-bromophenyl) trifenylfosfoniumhexafluorofosfat tetrafenylarsoniumtetrafluoroborat tetrafenylbismoniumklorid di- (l-naphthyl dimethylammonium tetrafluoroborate tri- (3-thienyl) methylammonium tetrafluoroborate diphenyacyldimethylammonium hexafluorophosphate 7805389-1 Examples of these and other onium salts and their preparation are described in Belgian Pat. No. 828,668.

B.

Onium salts with a cation of Group VIa of the Periodic Table I _ triphenylsulfonium 4-klorofenyldifenylsulfoniumtetrafluoroborat trifenylsulfoniumjodid 4-cyanofenyldifenylsulfoniumjodid trifenylsulfoniumsulfat 2-nitrifenylfenylmetylsulfoniumsulfat trifenylsulfoniumacetat trifenylsulfoniumtrikloracetat trifenylteluroniumpentaklorovismutat trifenylselenoniumhexafluoroantimonat Examples of these and other onium salts with a cation of Group VIa of the periodic system and appearance are of which are given in the Belgian patents 828 670 and 833 472 as well as the American patent application Serial No 609 897.

C.

Onium salts with a cation of Group VIIa of the Periodic Table difenyljodoniumjodid 4-klorofenylfenyljodoniumjodid diphenyliodonium 4-trifluorometylfenylfenyljodoniumtetrafluoroborat difenyljodoniumsulfat d (A-methoxyphenyl) jodoniumklorid difenyljodoniumtrikloroacetat 4-ium chloride metylfenylfenyljodoniumtetrafluoroborat aifenylbromo f 1- (2-karboetoxinaftyl) fenyljodoniumklorid 2,2'-diphenyliodonium hexafluorophosphate I Examples of these and other halonium salts and their preparation are described in Belgian Patents 828 669 and 845 746. The compositions of the invention can be prepared by mixing the onium salt with the epoxy-terminated silane composition until a solution is formed. Since many of the onium salts have limited solubility in the silicon-containing compound, it is often preferred to first dissolve the onium salt in a liquid diluent which is inert to the components of the composition and then mix in this solution in the reactive composition. Suitable inert diluents are alcohols such as ethanol, esters such as ethyl acetate, ethers such as diethyl ether, halogenated hydrocarbons such as dichloroethane, and nitriles such as acetonitrile. For reasons of durability, these solvents and solutions must be anhydrous.

The aromatic iodonium salts have the formulas êrl \\ Ari (mb / I Ga Q 6 Arz Ar2 ._- wherein Arl and Arz represent aromatic groups having 4-20 carbon atoms and these consist of phenyl, naphthyl, thienyl, furanyl and pyraxolyl groups, W represents Ö, š, š = O, å = O, = š = O and / or R11-å, wherein R11 represents aryl having α-carbon atoms or acyl with 2-20 carbon atoms (such as phenyl, acyl , benzoyl, etc.), a carbon-to-carbon bond or R 12 -C-R 13, wherein R 12 and R 13 are cooling groups having 1-4 carbon atoms and / or alkenyl groups having 2-4 carbon atoms, b is zero or 1, and Q is a halogen-containing complex anion consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexachloroantimonate or hexafluoroantimonate, a fluoroaliphatic sulfonic acid, bis- (fluoroaliphatic sulfonyl) methane or bis (fluoroaliphatic sulfonyl) imide.

Preferred compounds in this group are those wherein n = 0. Other preferred materials are those in which Ar 1 and ego represent hydrogen, α 1 -Ar 2 represents phenyl. 1soszs9¿1 10 15 20 25 30 14 The aromatic sulfonium salts have the formulas: Arl _ _ 'Ar] - (m / ~ Aíf 1 S C) ¿¿C) and Ar§ ___? C) (2 () In R1, R1 in which Ar1 and Ar2 may be the same or different and consist of aromatics (as previously defined for the aromatic iodonium salts) and R 1, W and Q are as previously defined. are those in which Arz and R1 represent phenyl.

Suitable examples of preferred aromatic onium salt photocatalysts are: * difenyljodoniumtetrafluorborat difenyljodoniumhexafluorarsenat difenyljodoniumhexaklorantimonat diphenyliodonium hexafluorophosphate diphenyliodonium hexafluoroantimonate difenyljodoniumbis (trifluoromethylsulfonyl) methane Other suitable preferred aromatic oniumsaltfoto- catalysts are corresponding trifenylsulfoniumsalter.

Still other preferred types are listed in Belgian Patent Specification 845 746 and include triarylsulfonium hexafluorophosphate, tritolylsulfonium hexafluorophosphate, methyldiphenylsulfonium tetrafluoroborate, etc.

The aromatic onium salt photocatalysts which can be used in the photopolymerizable compositions of the invention are inherently photosensitive only in the UV range. They are latent catalysts, which must be mixed with the reactants and then activated by radiation.

They can further be made photosensitive to the visible part of the spectrum as well as to the part of the UV region which is close to the visible part of the spectrum with sensitizers for known photolysable iodonium compounds as disclosed in US-PS 3,729,313; The polyepoxy compounds of the invention have the formula MC / ÅCH) n a b wherein R represents an aliphatic or cycloaliphatic group of such kind that the epoxy compound has a molecular weight of at least 100 per epoxy group to prevent rash. In particular, it is preferred that the compound have a molecular weight of at least 150 per epoxy group to provide significant flexibility improvement. Aliphatic and cycloaliphatic refers to hydrocarbons, which may also have ether and ester acids and ten-ether groups. n denotes the valence of R and is an integer of 2-6 (preferably 2). a and b represent H or, when fused, the atoms necessarily form a 5- or 6-membered cycloaliphatic ring. R is preferably selected so that the flexible epoxy compound upon homopolymerization gives a polymer having a transition temperature or glass transition temperature (Tg) below -25 ° C.

Useful polyepoxides, which are also flexible epoxy compounds within this definition, further include those containing one or more cyclohexene oxide groups, such as epoxycyclohexanecarboxylates, which may be exemplified by 3,4-epoxycyclohexylmethyl 2,4-epoxycyclohexanecarboxylate, 3 4-Epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate. A more detailed list of flexible epoxy compounds according to the invention can be found in US-PS 3 ll? 099, in particular column 2, line 59-column 4 line 22, which section is incorporated into this text by this reference.

Other suitable flexoxy epoxy compounds are polyglycidyl ethers of aliphatic polyols, such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polypropylene glycol diglycene and carbon dioxide. , diglycidyl ether of 2,5-dioxanediol and the triglycidyl ether of trimethylol-propane, epoxidized.polwolefins, such as dipentenediokide (e.g. "ERL-4269" from Union Carbide Corp) and epoxidized polybutadiene (e.g. Oxiron 2001 from FMC Corp). Other suitable aliphatic polyepoxy compounds are described in the Handbook of Epoxy Resins, McGraw-Hill Brook Co. (1967).

The UV absorbers preferably used in the invention can be divided into the following class of BENZOPHENONES: This class includes substituted 2-hydroxybenzophenones. These are available with different substituents on the basic molecule to give the right compatibility, non-volatility and certain absorption properties. Typical substituted 2-hydroxybenzophenones are 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone and 2,2'-dihydroxy-4-4'-dimethoxybenzophenone. Substituted 1'-2-hydroxybenzophenones are considered a class. BENSOTRIAZOLES: This class includes derivatives of 2- (2'-hydroxyphenyl) benzotriazole. Typical examples are 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-t-octylphenyl) g benzotriazole. Substituted 2- (2'-hydroxyphenyl) benzo-triazoles are also a class recognized in this field as UV> radiation absorbers. SUBSTITUTED ACRYLATES: These are another recognized class of UV absorbers.

Typical examples are ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate and p-methoxy-benzylidenemalonic acid dimethyl ester.

ARYL ESTERS: This recognized class includes aryl salicylates, benzoates and esters of resorcinol. Typical examples are phenyl salicylate, p-t-octylphenyl salicylate, resorcinol monobenzoate and 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate. Combinations of these UV absorbers are often used to combine the properties of the individual absorbers. Preferred absorbents are (I) 2,4-dihydroxybenzophenone, (II) 2,2'4,4'-tetrahydroxybenzophenone, (III) 2- (2'-hydroxy-5-methylphenyl) benzotriazole and (IV) 2- ( 3 ', 5'-di-t-amyl--2'-hydroxyphenyl) benzothiazole. 10 15 20 25 30 7803389-1 17, _ The following examples further illustrate the invention.

EXAMPLE 1 A coating formulation (A) was prepared as follows. 6.0 g of Y-glycidoxypropyltrimethoxysilane were partially hydrolyzed (40% methoxy groups were removed) and volatiles were removed. 4.0 g of diglycidyl ether of 1,4-butanediol was added to the partial hydrolyzate alone with 0.1 g of bis (trifluoromethylsulfonyl) phenylmethane in ethyl acetate, 0.01 g of inert, fluorinated oligomeric smoothing agent, 8.89 g of ethyl acetate and 1.0 g g 2,4-dihydroxybenzophenone.

A second opaque formulation (B) above for A but without the addition of UV absorber. Two color photographs were coated with formulations A and B, respectively, with a steel coating rod wound with wire No. 22.

The coatings were allowed to cure at room temperature for 4 hours and then placed under a 200 W UV lamp (medium mercury pressure) together with an uncovered paint was prepared as a photograph. After 7 hours, the uncoated photograph and the photograph having the coating B began to fade, but no bleaching was observed on the color photograph coated with the preparation A. After 17 hours of irradiation, severe bleaching and color destruction had taken place on the non-coated photograph. the coated photograph and the photograph covered with formulation B, but no bleaching or discoloration could be observed on the photograph covered with formulation A containing the UV filter I. The photographs covered with formulations A and B were extremely resistant to abrasion with steel wool (No. 000) and drying with a wet paper towel.

EXAMPLE 2 Coating preparations were prepared as in Example 1 but the following UV absorbers and amounts were used: Preparation BCDE 18 UV absorber No 0.2 g (2%) I 0.2 g (2%) II 0.2 g (2%) IV The procedure of Example 1 was repeated and coatings were applied to color prints, which had a white background and areas of pure blue? purple and yellow. These covered photographs were placed under a 275 W GE solar lamp (25 cm distance). After 2 days of irradiation, it could be noted that the blue area on the B-covered area had faded and the white background began to turn yellow. The pressures covered with C, D and E showed little or no change. The visual assessments after _ 4 days of irradiation are given in the following table I. 7803389-1 19 mn fl nß fl wnßm cwm fifl uxw fl n uwmbw mø fl uw fl mnßw: mona wnmm fl n umm> w ÜDHHDNHÜW fl xw fl n umm> m umH m> w VXW f n #MM> m mc fl u | W f mHmw Gwmc fi UUHWHQ H Hmxwm .MI N fl dm umm> m uwxuh fi> HQ Note umm> w uwxohä HH Q H fl w ummbw uwxowë HU Hmm umxumš cwmGH m wdsumxmn Hw al MAMCO al vmuøm fl m MO flfl mmm al etc. u f> |> DH H f w f tra U 7803389 -1 20 The following examples describe UV-cured protective coatings with 100% solid material. The preparations (FK) described in Table II were covered with a wire-printed rod No. 3 on ink printing as described in Example 2. The coatings were immediately cured under a 200 W UV lamp (with medium mercury pressure). for 40 s after which it was heated at 60 ° C for 10 min.

A solid photographic color print was used as a comparison. l 7803389-1 .umvmuäo NANM »mv Eoc al mc al AXM fl n mm> w ummwnw fl uo uumuuøuusm WMS uwwmuño EOO al Mo al CXM fl n m flfi uumë nw _umUmuE0 mw fl n vwv Eoc al mc flfl xman mwcmwwuwn Gm .cwv fi øumxmn al» fl>: MW M mc al cmumw al MM> m sm wwmm | f> mm5 OMS fifl w muxomuo: ma .mc al CXW fl n nmnnwuw fi po: Ma .mmbw umxoæä uwmwnw> Oum muxomu mm fifi uñmm Mumm fl> MMO SWS fifl w: www øsmum> m A «.mN OWS mmšm flfl about 3 mßw cm wmvs: mc f c f muummn wummmw m uwnwm 21 m fifl mw wow ßuçußß GIAQ uaßuï _ qxeque xošxqßxgg mo ~ o_o N_0 Ml nom m_o ~ oo N ~ O bl wow uwxoäë mO NO_O ~ .o ml vom mo N0.0 N_O OI WOW uwxuæš mO N0.0 NO HH fifl mßmß. a fl ø fi wuw »GE uwnm fl øcmßmmnmmc fi nvnz mmmmmmmmmm> H Hw @ mEwc0 fl umH0wQm |> D Hoxuoø fl m bm Hm fl mâ v> fl uxmu> uuw fl H wmnm mm ^ mm @ uw Öu wm 02. on fi w@H/=.~ \ m @ mwo oo nu ~ mu | mu ~ muo «^ ~ muvo ~ mumu 1 N J \ / d \\ EU m ^ wzov fl wm ^ ~ mu.o ~ mumo | Nmo / d \\ ^ EmHwV hG fl G © wHwm \ HwUm @ ümumwm dvaossse-1 10 15 20 25 30 35 u. N ..... ..w ~ ..,. ___. Example 4 Rigid polyvinyl chloride sheets can also be protected according to. the invention. In this example, it was found that a primer was desirable to increase the bond between the abrasion resistant coating containing the UV absorber and the sheet. A terpolymer of ethyl methacrylate, butyl acrylate and methacryloxypropyltriethoxysilane (80: 17: 3) was applied from a solution (with 10% solids) in toluene / ethyl acetate (50/50) with an applicator rod wound with wire No. 14, after which the lh was dried at room temperature before the upper coating was applied.

After priming, the abrasion resistant coatings (with or without the necessary modifiers as described later) were applied from a solution of 50% solid material in ethyl acetate with wire No. 14 wound applicator rod.

The coatings were allowed to cure for 5 days at room temperature.

All abrasion resistant coatings showed good "shack patterned" adhesion (to at least 85%) and excellent abrasion resistance to steel compared to polyvinyl chloride. Three samples were compared: A) a control sample (without abrasion resistant coating); B) an abrasion-resistant coating with UV absorber but without flexible epoxy material; and C) an abrasion resistant coating with UV absorber and flexibilizing epoxy material. The composition of the coatings used in B and C Var = Component (deiar) (deiar) Y-glycidoxypropyltrimethoxysilane 1,0,0 6,0 diglycidyl ether of 1,4-butanediol - 4,0 2,4-dihydroxybenzophenone 2.0 2,0 ethyl acetate 7 12.0 12.0 trifluoromethylsulfonylphenylmethane 0.1 0.1 inert fluorinated oligomeric surfactant 0.01 0.01 10 15 20 25 30 35 vsozzse-1 23 The samples were treated in cycles by placing them 25.4 cm from a 275 W solar lamp for 4 h and then immersed in water for 4 h. The results were as follows: 20 h Light brown discoloration Hair-thin cracks on the surface No change 95 h Brown discoloration throughout The surface very cracked but no discoloration No change 650 h Sample dark brown and opaque Severe cracking Narrow fine cracks begin to appear 800 h Test completely failed CUPOUJI fl OUJWOWI fl Large cracks and slight discoloration begin to appear in the coating 'C Further cracking but no discoloration Examples 5-15 The following materials were used in these example.

A. Y-glycidoxypropyltrimethoxysilane B. a 40% hydrolyzed precondensate of Y-glycidoxypropyltrimethoxysilane C. 1,4-butanediol diglycidyl ether D. 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate E. bis (2-2- epoxycyclohexylmethyl) succinate F. 2- (2'-hydroxy-5'-methylphenyl) benzotriaxol (5% in isopropyl acetate) G. 2- (3 ', 5'-di-t-amyl-2'hydroxyphenyl) benzotriazole ( 10% in isopropyl acetate) H. Isopropyl acetate I. Inert fluorinated oligomeric surfactant J. bis (trifluoromethylsulfonyl) phenylmethane K. Inert organosilicone-containing surfactant.

All coatings were applied with a rod wound with wire No. 22 except Examples 10, 12, 14 and 51, which were applied with a rod wound with wire No. 14, and dried overnight. Polyethylene terephthalate was used as the adhesive layer. 7eosss9 + 1 10 15 20 25 30, 24 0 The samples were exposed to a 275 W solar lamp for 3 days at a distance of 25.4 cm. The results are shown in Table III.

Table'III Ex _ - EEIAEÉBEEÉQÉEEK 5 - 3 2 - - 1,5 2,9 0,1 0,5 ~ 6 - 3 - 2 - - 1,5 2,9 0,1 0,5 - 7 - 3 - 2 - - 1.5 2.9 - 0.5 0.1 s 3 - - 2- - - 1.5 2.9 - 0.5 0.1 9 - 3 - 2 - - 2.5 1.9 0.1 0.5 - 10 - 3 1 1 - 3.0 ¿1.4 0.1 0.5 - 11 - 3 1 1 - - 01.5 2.9 0.1 0.5 - 12 - 3 1 - 1 3.0 - 1.4 0.1 0.5 - 13 - 3 1 - 1 - 1.5 2.9 0.1 0.5 - 14 - 3 2 - - 3.0 - 1.4 0.1 0.5 - 15 - 3 ~ 2 - 3.0 '- 1.4 0.1 0.5 - Examples 6, 7, 9, 10, 12, 14 and 15 showed -no rash or discoloration.- Examples 8 and 13 showed weak results on thorough examination but no discoloration.

Examples 5 and 11 clearly showed reduced rash but no misalignment.

The impact in Examples 5, 8, 11 and 13 occurred due to the use of less effective flexing epoxides in combination with UV absorbers, which showed the highest impact properties. The rash was still reduced. All coatings showed excellent abrasion resistance. In Examples 16-21 These examples show that other catalyst systems can be used. A standard preparation of 60 parts of Y-glycidoxypropyltrimethoxysilane, 30 parts of 1,4-butanediol diglycidyl ether and 10 parts of bis (3,4-epoxycyclohexylmethyl) succinate was prepared. Aliquot portions of this formulation were charged with varying amounts of catalyst known to be used in curing epoxy-terminated silanes. Among these were bis (trifluoromethylsulfonyl) phenylmethane (BPM) (1.5% in ethyl acetate), tin tetrachloride (20% II, 2-dichloroethane), antimony pentafluoride (5% in ClCF2CFCl2), anti monpentachloride (10% in 1,2-dichloroethane) and perchloric acid (10% in 1,2-acetic acid). Different amounts of UV absorber and 0.1% by weight of an organosilicone liquid of the formula ÉHB to-si + 5- + oc-cH¿ + E CH3 CH3 where m and n denote integers of at least 2 so that the average average molecular weight (Én) of the liquid becomes about 1500, its density 0.99 and the viscosity 125 cSt at 25 ° C, was added before the compound was cured. After coating over the color films and curing to an abrasion resistant film, the samples were examined for impact resistance, abrasion resistance and UV protection. All the samples turned out to be of high quality. The specific compositions were as follows in addition to 10 parts of the standard curable composition. In Table IV, 2,4-dihydroxybenzophenone is denoted by DHB, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate by ECD.

Table IV '_. - 'v A _ _ UV absorption ~ Example Catalyst Weight% average Weight% 16 BPM 0.15 DHB' 5 17 BPM 0.15 Ecn 5 18 * snc14 z, o man 5 19 * sbF5 o, 25 nns 5 20 ” sbc15 0.5 DHB 5 21 ”Hclo4 2.0 nns 5 X8-10% by weight of ethyl acetate was necessary to keep these catalysts in reaction-soluble solution.

In the practice of the present invention, it has been found that the precipitation tendency of UV absorbers is reduced regardless of the catalyst system used. As previously noted, any substrate that needs to be protected from UV radiation can be protected with the coating composition of the invention. The coating composition, which has both reaction-prone silane and epoxy groups, will of course adhere to many surfaces. Primer can be used to increase adhesion when necessary. When it is desired to protect conventional, wet-processed photographic color film or paper, it is necessary to place the protective coating over the surface to be viewed. The composition is usually impermeable to the water-half of the emulsion after development. Coating materials and solvents and if placed over the emulsion prior to development, developing solutions may not permeate the coating to act on the exposed emulsion. Some photographic color elements contain developing solutions in the photographic element and do not need to be permeated by developing solutions based on the element. In such designs of photographic elements, the abrasion-resistant, UV-absorbing coating can be applied to the element before development and before exposure. In fact, when active solutions are released in photographic films by the failure of capsules or layers physically protecting the coating according to the invention against scratching of the surface of the photographic element, which scratching occurs after the rupture as well as protection against bleaching of dyes in the element, which bleaching is accomplished by UV radiation.

In the description of the present invention, the emphasis has been on the protection of dyes from UV radiation, but it is obvious that any substrate, which can be adversely affected by UV radiation, can be protected with the present compositions. Polyolefins are known to be damaged by UV radiation, vinyl resins can cause serious discoloration problems originating from the cation due to UV radiation and both can be protected with existing coating compositions. An arbitrary, solid, 10 '15 7803389 ~ 1i 27 rigid or flexible surface can be protected with these compositions, but primer may be suitable in special cases.

Flexibility is another desirable aspect of the invention in many areas. When you want to protect conventional color photographic materials, direct-developing film or cinema film, flexibility is required. The UV-absorbing abrasion-resistant compositions according to the invention, when applied to a substrate or a free film, can show excellent flexibility. The coating and films can be easily wound around a cylinder with a diameter of 15 cm at room temperature and they often have sufficient flexibility to be able to be wound around a cylinder with a diameter of 5 cm. Particularly suitable are substrates of flexible or rigid synthetic polymer resins, such as poly (vinyl chloride), polycarbonate, polyethylene terephthalate, acrylic resins, poly (vinyl chloride-vinyl acetate) copolymers, isocyanate-based resins and polymethyl methacrylate. Painted surfaces can also be protected in a suitable way.

Claims (8)

1. 780338-9-1 10 l5 20 25 30 l. 28 PATENT CLAIMS UV radiation-absorbing, impact-resistant, abrasion-resistant film between 0.5 and 500 Fm thick is characterized in that it comprises a reaction product of: l) 2) 3) 5) 30-90% by weight of reactive constituents of an epoxy-terminated silane, in 10-70% by weight of reactive constituents of an aliphatic polyepoxide, 0-20% by weight of reactive constituents of a comonomer polymerizable with epoxy. or silane groups, 4) a UV absorbing material, comprising benzophenones, benzotriazoles, substituted acrylates and aryl esters, present in sufficient quantity for the film to absorb at least 90% of all radiation between 290 and 400 nm and for the film to release through at least 90% of all radiation between 400 and 780 nm, the film having no less than 75% transmittance over a 50 nm range between 400 and 780 nm, and a catalyst in an amount of 0.01-10% by weight of the reactive the ingredients. 2. A film according to claim 1, characterized in that the epoxy-terminated silane constitutes 50-90% by weight of the reactive constituents, the flexibilizing epoxide material constitutes 10-50% by weight of the reactive constituents and that the copolymer constitutes O- 10% by weight of the reactive constituents. Film according to Claim 1, characterized in that the epoxy-terminated silane has the formula O / c - CH (-R 2 -} Si (OR 1) 3 and H 2 Ys) 4n 2 -> s 1 (on 1) 3 10 15 20 25 Wherein R 2 represents a non-hydrolyzable divalent hydrocarbon group having less than 20 carbon atoms or a divalent group having less than 20 carbon atoms, the skeleton of which is composed of only C, N, S and O atoms, two heteroatoms must not be adjacent to each other in the skeleton of the divalent groups, and that R1 represents an aliphatic hydrocarbon group having less than 10 carbon atoms or an acyl group having less than 10 carbon atoms. A film according to claim 1, wherein the epoxy-terminated silane has the formula: characterized CH CH- (CH 2) m O- (CH 2) n ~ Si (OR) 3 2 "/ I \ b» wherein m and n are independently each other represents 1-4 and R represents an alkyl group having up to 6 carbon atoms. A polymerizable composition comprising 1) 30-90% by weight of an epoxy-terminated silane, 2) 10-70% by weight of a polyepoxy resin of the formula Rfc / OÉH »wherein r represents an aliphatic or cycloaliphatic group, n has the valence of R an integer of 2-6, a and b denote H or when they are fused, denote the atoms necessary for the formation of a 5- or 6-membered cycloaliphatic ring, the epoxy resin on homopolymerization giving a polymer having a glass transition temperature below -25 ° C and wherein the epoxy resin has a molecular weight of at least 100 per epoxy group, 3) a sufficient amount of UV radiation absorbing agents, including benzophenones, benzotriazoles, substituted acrylates and aryl esters, for absorbing at least 90% of all radiation between 290 and 400 nm through a wet film with a thickness of 200 μm and 4) a catalyst in an amount of 0,01-10% by weight of the reactive constituents. Polymerizable composition according to claim 5, characterized in that the epoxy-terminated silane is illustrated by the formula I o nac - \ cH4R2-> s1 (o1zl) 3 and ° 1 \ @ (- n-) s1 (on) 3 wherein R2 denotes a non-hydrolyzable divalent hydrocarbon group having less than 20 carbon atoms or a divalent group having less than 20 carbon atoms, the skeleton of which is composed of only C, N, S and O atoms, two heteroatoms not adjacent to each other within the skeleton of the divalent groups, and R1 represents an aliphatic hydrocarbon group having less than 10 carbon atoms or an acyl group having less than 10 carbon atoms. Polymerizable composition according to claim 6, characterized in that the epoxy-terminated silane has the formula CH - CH '(CH) / 2, wherein m and n independently represent 1-4 and R represents an alkyl group having up to 6 carbon atoms . Polymerizable composition according to any one of claims 5-7, characterized in that the catalyst consists of an onium catalyst which comprises an aromatic adduct of (1) a diaromatic, triaromatic or tetraaromatic organoatomic cation of an atom of group Va , VIa or VIIa and (2) an anion, wherein the onium catalyst can be illustrated by the formula 0 2 m-Of (CH 2) n “Si (OR) 3 7803389-1 31 2 (RM-A + x '<ål> a wherein R 2 represents an aromatic group which is at least as electron withdrawing as benzene, R represents alkyl or alkenyl, A represents an atom from group Va, VIa or VIIa, X represents an anion, n represents a positive integer up to A's valence plus one, a denotes 0 or an integer up to A's valence minus one and n plus a is equal to the valence of A plus one and wherein at least two of the specified R 2 groups are attached to A.