JP2002513078A - Heavy metal-free coating compounds - Google Patents

Abstract

  (57) [Summary] UV-curable cationic polymerizable compositions comprising (a) mono-, bis- or polyaliphatic or aromatic glycidyl ethers, (b) titanium dioxide, (c) iodonium as photoinitiator At least one of the hexafluorophosphates and (d) one of the sensitizer compounds) is characterized by a high resistance to yellowing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to heavy metal free UV curable cationic polymerizable compositions and uses thereof.

[0002]

[Prior art]

J. of Photopolym.Sci. And Techn., Vol. 5 (1992), p.247-254,
F. Hamazu et al. Published a study on the reactivity of sulfonium salts containing different anions. A method for curing cationically curable colored formulations is known from International Patent Publication No. WO 98/02493. JP 61-175921 describes a backside coating for magnetic recording materials based on glycidyl ether formulations. U.S. Pat. No. 4,378,277 discloses a non-colored photopolymerizable formulation comprising a glycidyl ether and a mixture of initiator compounds. US Patent 4,2
No. 87,228 describes a glycidyl ether-containing composition which is colored with titanium dioxide. International Patent Publication No. WO 96/13538 uses aryl iodonium salts as initiators and dicarbonyl compounds as sensitizers.
Disclosed are cationically polymerizable formulations.

[0003]

[Problems to be solved by the invention]

There is a need for techniques for use as radiation curable, reactive, cationically curable, inexpensive, white, and non-yellowing formulations, especially as coatings.

[0004]

[Means for Solving the Problems]

(A) mono-, bis- or polyvalent (tri- or higher) aliphatic or aromatic glycidyl ethers, (b) titanium dioxide, (c) at least one of iodonium hexafluorophosphate as photoinitiator, and ( d) It has been found that compounds including sensitizer compounds fulfill all of the above requirements.

The photoinitiator (c) is, for example, of the formula (I):

[0006]

Embedded image

Wherein R ₁ , R ₂ , R ₃ and R ₄ are, independently of one another, hydrogen, C ₁ -C ₂₀ alkyl or unsubstituted or hydroxy-substituted C ₁ -C ₂₀ alkoxy, , R ₁ , R ₂
, R ₃ and R ₄ are not hydrogen).

[0008] C ₁ -C ₂₀ alkyl is linear or branched, for example _{C 1 -C 12 -, C 1} -C 8 -, C 1 -C 6 - is or C ₁ -C ₄ alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,
Pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl,
Pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl. Branched chain alkyl, in particular _{C 3 -C 8 -, C 3} -C 6 - and C ₃ -C ₄ alkyl is preferred. R ₂ and R ₄ are, for example, C ₁ -C ₁₂ alkyl, C ₁ -C ₈ alkyl or C ₁ -C ₆ alkyl, preferably C ₁ -C ₄ alkyl, such as isobutyl, or C ₁ -C ₁₂ alkyl, for example Dodecyl.

C₁-C₂₀Alkoxy is a straight-chain or branched group, for example C₁-C₁₂-, C ₁ -C₈-, C₁-C₆-Or C₁-C_FourAlkyl. Examples are methoxy, eth
Xy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy,
Isobutyloxy, tert-butyloxy, pentyloxy, hexyloxy,
Butyloxy, 2,4,4-trimethylpentyloxy, 2-ethylhexylio
Xy, octyloxy, nonyloxy, decyloxy, dodecyloxy, hexa
Decyloxy or octadecyloxy, preferably methoxy, ethoxy, propo
Xy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy
Xy, tert-butyloxy, more preferably methoxy. Preferred compounds are
, For example, nC_Four-C₆, N-C₁-C₆, N-C_Two-C₆, N-C₁-C_FourOr nC _Two -C_FourAlkoxy. n-C₁₂-C₂₀Alkoxy is also interesting.

The compounds of formula (I) to be emphasized are those in which R ₁ , R ₂ , R ₃ and R ₄ are C ₁ -C ₂₀ alkyl, preferably C ₁ -C ₁₂ alkyl. Other interesting compounds have the formula (I
Wherein R ₁ , R ₂ , R ₃ and R ₄ are branched C ₁ -C ₂₀ alkyl, preferably branched C ₁ -C ₁₂ alkyl or branched C ₁ -C ₄ alkyl. Things.

Preferred compounds of formula (I) are those wherein R ₂ and R ₄ are C ₁ -C ₂₀ alkyl and R ₁ and R ₃ are hydrogen.

Other interesting compounds of formula (I) are those in which R ₂ and R ₄ are identical.

[0013] R ₂ is C ₁ -C ₁₂ alkyl, preferably isobutyl or dodecyl, R _1,
Compounds of formula (I) in which R ₃ and R ₄ are hydrogen deserve special mention.

Other particularly preferred compounds of formula (I) are those in which R ₂ and R ₄ are C ₁ -C ₁₂ alkyl, for example isobutyl or dodecyl.

A preferred compound of formula (I) is that when R ₁ , R ₂ and R ₃ are hydrogen, R ₂ is C ₁ -C ₄
Which is alkyl.

Another preferred compound of formula (I) is that when R ₁ , R ₂ and R ₃ are hydrogen, R ₂ is C _1-
It is a C ₄ alkoxy. When R ₁ , R ₂ and R ₃ are hydrogen, R ₂ is C ₁₀ −
Compounds of formula (I) is a C ₂₀ alkoxy, preferred.

Examples of compounds of formula (I) are: bis (4-hexylphenyl) iodonium hexafluorophosphate;
(4-hexylphenyl) phenyliodonium hexafluorophosphate; bis (4-octylphenyl) iodonium hexafluorophosphate; (4-
Octylphenyl) phenyliodonium hexafluorophosphate; bis (
(4-decylphenyl) iodonium hexafluorophosphate; (4-isobutylphenyl) phenyliodonium hexafluorophosphate; bis (4-
(Isobutylphenyl) iodonium hexafluorophosphate; (4-dodecylphenyl) phenyliodonium hexafluorophosphate; (2-hydroxydodecyloxyphenyl) phenyliodonium hexafluorophosphate; (2-hydroxytetradecyloxyphenyl) phenyliodonium hexafluoro Phosphate.

The present invention also relates to (4-isobutylphenyl) phenyliodonium hexafluorophosphate, especially dissolved in propylene carbonate.

In certain cases, it may be advantageous to use a mixture of two or more such iodonium salt photoinitiators in the composition of the invention.

The preparation of the photoinitiator compounds of the formula (I) is well known to the person skilled in the art and has been described in the literature. Thus, compounds of formula (I) can be prepared, for example, according to US Pat.
No. 071, 4,329,300 and German Patent 2,754,853. Hexafluorophosphate salts can be prepared, for example, by exchanging the anion of the corresponding simple salt of the iodonium compound (eg, of the bisulfate salt). These methods are described, inter alia, in Beringer et al. In J.
Am. Chem. Soc. 81, 342 (1959). This document also states that
Different preparation methods of the above simple salts, for example the reaction of two aromatic compounds with iodyl sulfate in sulfuric acid; the reaction of two aromatic compounds with iodate in acetic acid, acetic anhydride or sulfuric acid The reaction of two aromatic compounds with iodoacylate in the presence of an acid or the condensation of an iodosyl compound, iodosyl diacetate or iodoyl compound with another aromatic compound in the presence of an acid; I have. In certain cases, the aryl iodide can be oxidized in situ and then condensed with other aromatic compounds. A variant of the condensation step is for example in dilute sulfuric acid (EP 119
068).

In the composition of the present invention, the photoinitiator (c) is used in an amount of 0.05% to
It is conveniently used in an amount of 15%, for example 0.5% to 10%, preferably 0.1% to 5%.

The glycidyl ether component (a) used in the novel formulations is typically a glycidyl ether of a polyhydric phenol obtained by reacting a polyhydric phenol with an excess of chlorohydrin, for example epichlorohydrin. (For example, 2,2-bis (2,
3-epoxypropoxyphenol) glycidyl ether of propane).
Other examples of glycidyl ether epoxides that can be used in connection with the present invention are, inter alia, US Pat. No. 3,018,262 and "Handbook of Epoxy Resins" by Le
e and Neville, McGraw-Hill Book Co., New York (1967). There are also a number of commercially available glycidyl ether epoxides which can be used as component (a), such as glycidyl methacrylate, diglycidyl ether of bisphenol A, such as EPON 828, EPON 825, EPON 1004 and EPON 10 from Shell.
10; obtainable under the trademarks of DER-331, DER-332 and DER-334 manufactured by Dow Chemical Company;
1,4-butanediol diglycidyl ether of phenol formaldehyde novolak, for example, DEN-431, DEN-438 manufactured by Dow Chemical Company; and resorcinol diglycidyl ether; alkyl glycidyl ether such as C ₈ -C ₁₀ glycidyl ether; Examples include HELOXY modifier 7, C ₁₂ -C ₁₄ glycidyl ether, such as HELOXY modifier 8, butyl glycidyl ether, such as HELOXY modifier 61, cresyl glycidyl ether, such as HELOXY modification Agent 62, p-te
rt-butylphenyl glycidyl ether, for example, HELOXY modifier 65, polyfunctional glycidyl ethers, for example, diglycidyl ether of 1,4-butanediol, for example, HELOXY modifier 67, diglycidyl ether of neopentyl glycol As an example, HELOXY modifier 68, diglycidyl ether of cyclohexane dimethanol, as an example, HELOXY modifier 107, trimethylolethane triglycidyl ether, as an example, HELOXY modifier 44, trimethylolpropane triglycidyl ether, Examples are HELOXY modifier 48, polyglycidyl ethers of aliphatic polyols, such as HELOXY modifier 84 (all HELOXY glycidyl ethers are available from Shell). Other suitable glycidyl ethers include those containing a copolymer of acrylates, such as styrene glycidyl methacrylate or methyl methacrylate glycidyl acrylate. An example is
1: 1 styrene / glycidyl methacrylate, 1: 1 methyl methacrylate / glycidyl acrylate, 62.5: 24: 13.5 methyl methacrylate / ethyl acrylate / glycidyl methacrylate. The polymer of the glycidyl ether compound may contain, for example, other functional groups provided that the cationic curing is not impaired. Other glycidyl ether compounds suitable as component (a) and commercially available from Ciba Specialty Chemicals include polyfunctional liquid and solid novolak glycidyl ether resins such as PY 307, EPN 1179, EPN 1180, EPN 1182 and ECN 9699. It is.

Of course, it is also possible to use a mixture of different glycidyl ether compounds as component (a). Glycidyl ethers (a) are, for example, of the formula (II):

[0024]

Embedded image

Wherein x is a number from 1 to 6 and R ₅ is a monovalent to hexavalent alkyl or aryl group.

The glycidyl ethers (a) are preferably, for example, of the formula (II):

[0027]

Embedded image

Where x is a number of 1, 2, or 3, and when x is 1, R_FiveIs unsubstituted or C₁-C₁₂Alkyl-substituted phenyl, naphthyl
, Anthracyl, biphenylyl, C₁-C₂₀Alkyl or C_Two-C₂₀Alkyl
(This is interrupted by one or more of the oxygen atoms) or, if x is 2, R_FiveIs 1,3-phenylene, 1,4-phenylene, C₆-C_Ten Cycloalkylene, unsubstituted or halogen-substituted C₁-C₄₀Alkylene; C_Two-C ₄₀ Alkylene, which is interrupted by one or more oxygen atoms, or
formula:

[0029]

Embedded image

When x is 3, R ₅ is a group of the formula:

[0031]

Embedded image

And y is a number from 1 to 10 and R ₆ is a C ₁ -C ₂₀ alkylene, oxygen or a formula of the following formula:

[0033]

Embedded image

Is a compound of the formula:

The glycidyl ethers (a) are, for example, of the formula (IIa):

[0036]

Embedded image

[0037] (wherein, R ₇ is unsubstituted or C ₁ -C ₁₂ alkyl-substituted phenyl; naphthyl; anthracyl; biphenylyl; C ₁ -C ₂₀ alkyl; C ₂ -C ₂₀ alkyl (which is an oxygen atom 1
Interrupted by more than one); or the following formula:

[0038]

Embedded image

R ₅ is phenylene, C ₁ -C ₂₀ alkylene, C ₂ -C ₂₀ alkylene, which is
Interrupted by one or more oxygen atoms) or the following formula:

[0040]

Embedded image

And R ₆ is C ₁ -C ₂₀ alkylene or oxygen.

Preferred glycidyl ethers are of the formula (IIb):

[0043]

Embedded image

Wherein R ₅ is phenylene, C ₁ -C ₂₀ alkylene; C ₂ -C ₂₀ alkylene (which is
Interrupted by one or more oxygen atoms) or the following formula:

[0045]

Embedded image

And R ₆ is C ₁ -C ₂₀ alkylene or oxygen.

[0047] Alkyl groups, for example C ₁ -C _{20 alkyl, C 1 -C 18 -, C} 1 -C 12 -, C 1 -
_{C 10 -, C 1 -C 8} -, C 1 -C 6 - it is or C ₁ -C ₄ alkyl. The meaning of these groups has been given above. C ₁ -C ₂₀ alkylene is linear or branched;
For example _{C 1 -C 18 -, C 1} -C 16 -, C 1 -C 14 -, C 1 -C 12 -, C 1 -C 10 -,
_{C 1 -C 8 -, C 1} -C 6 -, C 2 -C 12 -, C 2 -C 8 -, C 4 -C 8 - or C ₁ -C ₄
Alkylene. Examples are methylene, ethylene, propylene, isopropylene,
n-butylene, sec-butylene, isobutylene, tert-butylene, pentylene,
Hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tetradecylene, heptadecylene or octadecylene. C ₁ -C ₂₀ alkylene is preferably, for example, ethylene, decylene, of the formula:

[0048]

Embedded image

It is understood to mean the group

Halogen is fluoro, chloro and bromo, preferably bromo and chloro, most preferably bromo.

Halogen-substituted C ₁ -C ₄₀ alkylene has, for example, the following formula:

[0052]

Embedded image

Is a group of

C ₂ -C ₂₀ alkylene, which is interrupted by one or more oxygen atoms
Is also a straight or branched chain, and may be, for example, 1 to 9 times
It has been interrupted 1-5 times or once or twice. Thereby, -CH ₂ -OC
H ₂ —, —CH ₂ CH ₂ —O—CH ₂ CH ₂ —, — [CH ₂ CH ₂ O] _y — (where y
It is _{1~9), - (CH 2 CH} 2 O) 7 CH 2 CH 2 - or -CH ₂ -CH (C
_{H 3) -O-CH 2 -CH} (CH 3) - structure is given as.

C ₆ -C ₁₀ cycloalkylene is, for example, 1,4-, 1,3- or 1,6-
Is cyclohexylene, or has the formula:

[0056]

Embedded image

(Wherein the alkylene group is preferably in the 1,4-position).

R ₅ is preferably of the formula:

[0059]

Embedded image

Is a group of

R ₆ is preferably C ₁ -C ₁₂ alkylene, more preferably the following formula:

[0062]

Embedded image

Or oxygen.

Other examples of component (a) include reacting a compound containing at least two free alcoholic and / or phenolic hydroxyl groups per molecule with the corresponding epichlorohydrin under alkaline conditions, Or polyglycidyl ether and poly (β-methylglycidyl) ether obtained by reacting in the presence of an acid catalyst and subsequently treating with an alkali. It is also possible to use mixtures of different polyols. These ethers may be acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycol, propane-1,2-diol and poly (oxypropylene) glycol, depending on the poly (epichlorohydrin). , Propane-1,3-diol, butane-1,4-diol,
Poly (oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol and From sorbitol, alicyclic alcohols such as resorcitol, quinitol, bis (4-
From hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane and 1,1-bis (hydroxymethyl) cyclohex-3-ene, and alcohols containing aromatic nuclei, such as N, N-bis It can be prepared from (2-hydroxyethyl) aniline and p, p'-bis (2-hydroxyethylamino) diphenylmethane. These ethers are derived from mononuclear phenols such as resorcinol and hydroquinone, and polynuclear phenols such as bis (4-hydroxyphenyl) methane, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, 1,2,2-tetrakis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (
It can also be prepared from bisphenol A) and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. Other suitable hydroxy compounds for the preparation of polyglycidyl ethers and poly (β-methylglycidyl) ethers are aldehydes such as formaldehyde, acetaldehyde, chloral and furfural, and phenols such as phenol, o-cresol,
Novolaks obtained by condensing m-cresol, p-cresol, 3,5-dimethylphenol, 4-chlorophenol and 4-tert-butylphenol.

Poly (N-glycidyl) compounds include, for example, epichlorohydrin and amines containing active hydrogen bonded to an amino nitrogen atom, such as aniline, n-butylamine, bis (4-aminophenyl) methane and bis (4-aminophenyl) methane. (4-methylaminophenyl)
It can be obtained by dehydrochlorinating a reaction product of at least two methanes. Other suitable poly (N-glycidyl) compounds are triglycidyl isocyanurate and N, N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethylene urea and 1,3-propylene urea and hydantoins, such as 5,5 5-
It is dimethylhydantoin.

[0066] Poly (S-glycidyl) compounds are also suitable. Examples are the di-thiols di-S-
Glycidyl derivatives such as ethane-1,2-dithiol and bis (4-mercaptomethylphenyl) ether.

Other suitable compounds (a) are also epoxy resins (where the glycidyl group or β-methylglycidyl group is bonded to a different heteroatom, for example the N, N, O-triglycidyl derivatives, glycidyl ether / glycidyl ester of salicylic acid or p-hydroxybenzoic acid, N-glycidyl-N
'-(2-glycidyloxypropyl) -5,5-dimethylhydantoin and 2
Glycidyloxy-1,3-bis (5,5-dimethyl-1-glycidylhydantoinyl-3) propane).

Diglycidyl ethers of bisphenols are preferred. Examples thereof include diglycidyl ethers of bisphenol A such as ARALDI manufactured by Ciba Specialty Chemicals.
T GY 250, a diglycidyl ether of bisphenol F and a diglycidyl ether of bisphenol S. Diglycidyl ether of bisphenol A is particularly preferred.

If desired, the composition can also contain radically polymerizable materials, including ethylenically unsaturated monomers, oligomers or polymers. Suitable materials contain at least one ethylenically unsaturated double bond and are capable of addition polymerization. Such radically polymerizable materials are mono-, di- or polyacrylates and mono-, di- or polymethacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n −
Hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, trimethylolpropane triacrylate, 1,
2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, sorbitol hexaacrylate, bis [1- (2- Acryloxy)]-p-ethoxyphenyldimethylmethane, bis [1- (3-acryloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane and trishydroxyethyl isocyanurate trimethacrylate; molecular weight of 200 to 500 Bisacrylates and bismethacrylates of polyethylene glycols having a copolymerizable mixture of acrylated monomers; and vinyl compounds such as styrene, diallyl phthalate, divinyl Succinate, including divinyl adipate and divinyl phthalate. If desired, mixtures of two or more of these radically polymerizable materials can be used.

When a radically polymerizable composition is added to the new formulation, the corresponding radical photoinitiator (s), such as benzophenone and benzophenone derivatives, acetophenone and acetophenone derivatives, such as α-hydroxycyclohexyl phenyl ketone or 2 -Hydroxy-2-methyl-1-phenylpropanone, α-hydroxy- or α-aminoacetophenone, for example, (4-methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)- 1-benzyl-1-dimethylaminopropane, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzyl ketals, for example, benzyl dimethyl ketal, phenylglyoxalate and phenylglyoxalate derivatives , Mono- or bisacylphosphine oxides, for example (2,
4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-
Dimethoxybenzoyl)-(2,4,4-trimethylpent-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or bis (2,4,6-trimethylbenzoyl)-(2 It is also useful to add one or a mixture of (4-dipentoxyphenyl) phosphine oxides.

The novel compositions can also contain vinyl ether monomers, for example cyclohexane dimethanol divinyl ether or hydroxybutyl vinyl ether. Other further components can be, for example, hydroxy-functional components such as alcohols, polyester polyols, polyether polyols, castor oil and the like.
Examples are aliphatic and cycloaliphatic polyols, such as alkylene diols, preferably containing 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2 -, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, preferably 200
Polyethylene glycols having a molecular weight of ~ 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol,
, 4-dihydroxymethylcyclohexane, glycerol, tris (β-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. The polyols can be partially or completely esterified with one or different unsaturated carboxylic acids, the free hydroxyl groups in the partial esters being modified by other carboxylic acids, for example etherification or esterification. It is possible to be. Examples of the esters are trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene Glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate , Dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pen Erythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentitaco Nate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4
-Butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol modified triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylate and oligoester methacrylate, It may be glycerol di- and triacrylate, 1,4-cyclohexanediacrylate, bisglycols and bismethacrylates of polyethylene glycol having a molecular weight of 200 to 1500, or a mixture thereof.

Component (a) of particular interest is a pure glycidyl ether formulation, ie a mixture consisting of only one or several different glycidyl ether compounds. The titanium dioxide pigment (b) can be added to the novel composition in a very wide range of forms. Therefore,
For example, they can be incorporated in the form of fine particles or powder. Particle size is generally 10
Although it is 0 to 400 nm, it is not limited to this size. The titanium dioxide pigments used are preferably surface-treated, for example with stabilizers, in order to increase the dispersibility. Such stabilizer components are usually oxides or hydrated oxides of silicon, magnesium or aluminum, or amines or other organic compounds. An example is shown in U.S. Pat. No. 4,054,498. Although titanium dioxide can exist in different crystalline forms, it is preferred to use the commercially available rutile form. The amount of titanium dioxide component (b) in the polymerizable composition can vary widely depending on the desired opacity, for example from 5% to 60%, typically 2%, based on the composition.
It is 0% to 55%, preferably 40% to 50%.

To improve the dispersion of the pigment in the formulation to be polymerized, it is possible, for example, to first predisperse the pigment in a part of the formulation and then incorporate this dispersion in the rest of the formulation It is.

Suitable sensitizer compounds (d) are, for example, compounds from the class of the aromatic hydrocarbons, for example anthracene and its derivatives, compounds from the group of xanthones and their derivatives, benzophenones and their derivatives For example, Michler's ketone, Mannich base or bis (p-N, N-dimethylaminobenzylidene) acetone.
Other suitable compounds are thioxanthones and derivatives thereof such as isopropyl thioxanthone or dyes such as acridines, triarylmethanes, such as malachite green, indolines, thiazines, such as methylene blue,
Oxazines, phenazines, for example, safranins or rhodamines. Particularly suitable compounds are aromatic carbonyl compounds such as benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin derivatives, as well as 3- (aroylmethylene) thiazolines, and eosin, rhodamine and erythrosine dyes.

The sensitizer compound should be soluble in the photopolymerizable composition and should not contain any functional groups that significantly affect the cationic crosslinking step. Further, the light absorption of the compound should be in the range of about 300-1000 nm.

Suitable sensitizers are (as described in part above) the following classes of compounds: ketones, coumarins (eg ketocoumarin), xanthones, acridines, thiazole dyes, thiazine dyes Oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrogens, p-substituted aminostyryl ketone compounds, aminotriarylmethanes, merocyanines, squalilium dyes and pyridinium dyes. Preferred compounds are ketones (eg, monoketones or α
-Diketones), ketocoumarins, aminoaryl ketones and p-substituted aminostyryl ketone compounds. For applications requiring deep curing (eg, curing of highly filled composites), at the emission wavelength desired for photopolymerization, less than about 1000 lmol ^-1 cm ^-1 , preferably about 100 lmol ^-1 cm ^-1. It is preferred to use a sensitizer having an extinction coefficient of less than. Alpha-ketones are one example of a class of sensitizers having this property. Suitable ketone sensitizers are, for example, those of formula (IV):

[0077]

Embedded image

Wherein X is CO or CR _a R _b , R _a and R _b are independently of each other hydrogen, alkyl, alkaryl or aralkyl, b is 1 or 2, and A and Z are, independently of one another, aryl, alkaryl or aralkyl (these radicals are unsubstituted or substituted), or A and Z together form a ring, which can be substituted or Unsubstituted, alicyclic, aromatic or heteroaromatic).

Suitable ketones of this formula are, for example, monoketones, where b is 0
For example, 2,2-, 4,4- or 2,4-dihydroxybenzophenone, dipyridyl ketone, difuranyl ketone, dithiophenyl ketone, benzoin, fluorenone, chalcone, Michler's ketone, thioxanthone, isopropylthioxanthone, 2-fluoro-9-fluorenone, 2- Chlorothioxanthone, acetophenone, benzophenone, 1- or 2-acetonaphthone, 9-acetylanthracene, 2-, 3- or 9-acetylphenanthrene, 4-acetylbiphenyl, propiophenone, n-butyrophenone, valerophenone, 2-, 3- Or 4-acetylpyridine, 3-acetylcoumarin and the like. Suitable diketones are aralkyldiketones such as anthraquinone, phenanthrenequinone, o-, m- and p-diacetylbenzene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7. −
And 1,8-diacetylnaphthalene, 1,5-, 1,8- and 9,10-diacetylanthracene. Suitable diketones wherein b is 1 and X is C
O) is 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedion, 3,4-heptanedion, 2,3 -Octanedione, 4,5-octanedione, benzyl, 2
, 2 '-, 3,3'- and 4,4'-dihydroxybenzyl, furyl, di-3,
3'-indolylethanedione, 2,3-bornanedione (canforquinone),
Biacetyl, 1,2-cyclohexanedione, 1,2-naphthaquinone, acenaphthaquinone and the like.

Preferred sensitizers are from the group of the anthracenes, xanthones, benzophenones and thioxanthones, and also include derivatives of these compounds. Thioxanthones are particularly preferred, especially isopropyl thioxanthone.

The sensitizer compound (d) is usually present in the novel composition in an amount of 0.1% to 3%, for example 0.2% to 1.5%, preferably 0.4% to 1.0%. Is added to

The novel composition comprises 40-70% of the glycidyl ether component (a), 20-60% of titanium dioxide (b), 0.5-10% of the photoinitiator (c) and the sensitizer compound (d) 0
. Conveniently contains 1-3%.

Other additives may be added to the novel composition in addition to components (a), (b), (c) and (d). Examples are light stabilizers such as UV absorbers, for example of the hydroxyphenylbenztriazole, hydroxyphenylbenzophenone, oxalic amide or hydroxyphenyl-s-triazine type. These compounds can be used separately or as a mixture, with or without the addition of steric hindered amines (HALS).

The novel compositions can contain as further additives, inter alia, electron donor compounds. Examples of such compounds are described in U.S. Patent No. 5,545,676. Examples are alkyl aromatic polyethers or alkyl-aryl-amino compounds, wherein the aryl group is substituted by one or several electron withdrawing groups. Examples thereof are 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, 3-dimethylaminobenzoic acid, 4-dimethylaminobenzoin,
4-dimethylaminobenzaldehyde, 4-dimethylaminobenzonitrile and 1,2,4-trimethoxybenzene.

Other conventional additives include optical brighteners, fillers, dyes, depending on the end use requirements.
It is a wetting agent or a flow control agent. The novel compositions comprise, as further additives, dispersants,
Emulsifiers, antioxidants, light stabilizers, dyes, pigments, fillers such as talc, gypsum, silicic acid, rutile, carbon black, zinc oxide, iron oxide, reaction accelerators, flow regulators, wetting agents, thickeners , May also include matting agents, defoamers, antioxidants and other auxiliaries conventionally used in paint-based technology. Suitable dispersants are, for example, high molecular weight organic compounds containing polar groups, for example polyvinyl alcohols, polyvinylpyrrolidone or cellulose ethers. Suitable emulsifiers are nonionic or ionic emulsifiers.

The choice of the additives depends on the respective field of application and the properties desired in the field. Additives are standard in the art and are therefore used in amounts known to those skilled in the art.

The novel compositions are used in different fields, for example in coating materials, laminating adhesives
It can be used, for example, in printing inks for wood or metal materials, in white enamel formulations, or in paints used, inter alia, for paper, wood, metal or plastic materials.

The compositions according to the invention can be applied to all types of substrates (substrates), for example wood, textiles, paper, ceramics, glass, plastics materials, such as polyesters, polyethylene terephthalates, polyolefins or cellulose acetate (especially membranes). And the metals to which the protective coating is to be applied, for example Al, Cu, Ni, Fe, Zn, M
It can be used to coat or bond g or Co and GaAs, Si or SiO ₂ .

The substrate can be coated by applying a liquid composition, solution or suspension to the substrate. The choice of the solvent used and its concentration depends mainly on the type of composition and the coating process used. The solution should be inert, ie it should not chemically react with the components and can be removed on drying after coating. Suitable solvents are, for example, ketones, ethers and esters, for example methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1 -Methoxy-2-propanol, 1,2-dimethoxyethane,
Ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate. The formulation is applied uniformly to the substrate by known application methods, such as centrifugation, dipping, knife application, curtain coating, brush application, screen printing, spraying, in particular electrostatic spraying and reverse roll coating.

The coating thickness and the type of substrate depend on the desired field of application. The coating thickness is generally about 0.1 μm to more than 100 μm, for example 1 μm to 30 μm, preferably 4 μm to 2 μm.
It is within the range of 0 μm.

Another area in which the novel compositions can be used is metal coatings, such as coated metal sheets and tubes, tin cans or bottle lids. The metal to be coated can be uncoated or pre-coated. Suitable substrates are in particular metals, such as aluminum or tinplate.

The new white compositions are distinguished by having very good resistance to yellowing
Attached. Another advantage is that heavy metal anions commonly used in the art, such as SbF ₆ The anion is absent from these compounds.

The new formulations are cured by irradiation with light of a wavelength between 200 and 600 nm. If necessary, the formulation can be subjected to a heat treatment after the irradiation. Heat treatment is 50-250 ° C
For example, it is conveniently carried out at a temperature in the range from 100 to 220 ° C, preferably from 150 to 210 ° C. Accordingly, the present invention also relates to a method for polymerizing the above composition, comprising irradiating the composition with light at a wavelength of 200 to 600 nm, and a corresponding method followed by heat treatment following irradiation.

The UV irradiation for curing the novel formulations is usually carried out using light having a wavelength of from 200 to 600 nm. Suitable radiation includes, for example, sunlight or light from artificial light sources.
A large number of widely different types of light sources can be used, for example a point light source and an array of reflectors. Examples are carbon arc lamps, xenon arc lamps, high and low pressure mercury lamps (metal halogen lamps), microwave-excited metal vapor lamps, excimer lamps, super actinic fluorescent lamps, doped with metal halides if necessary. Fluorescent lamps, argon glow lamps, flash lamps, floodlights for photography, electron beams and X-rays. Examples of suitable lamps are fusion lamps such as Fusion H (primary emission: medium pressure mercury spectrum), Fusion D (primary emission: 350-450 nm), Fusion V (primary emission: 400-450 nm) or Fusion M (primary emission). : 360 to 370 nm and 40
0 to 410 nm). The distance between the lamp and the substrate to be irradiated can vary depending on the purpose and type of application or the strength of the lamp, but is for example between 2 cm and 150 cm. Other suitable lamps are laser light sources, for example excimer lasers. It is also possible to use lasers in the visible range. Irradiation using a fusion lamp such as Fusion H, Fusion D, Fusion V or Fusion M is of particular interest.

The present invention also relates to the use of the above-mentioned composition and to a method for preparing coatings, paints, print inks, powder coatings, laminating adhesives, dental compositions, especially white enamel formulations.

In another aspect, the present invention provides a novel composition comprising a coated substrate coated on at least one of its surfaces with one of the above compositions and the novel composition.
It relates to a coated substrate applied at a coating thickness of μm, for example 1-30 μm, preferably 4-15 μm.

The following examples illustrate the invention in detail. In the remainder of the description and in the claims, parts and percentages are by weight unless otherwise indicated. Where alkyl or alkoxy groups containing three or more carbon atoms are given without their isomeric forms, the respective n-isomer is referred to.

[0098]

【Example】

Example 1 Preparation of p-isobutylphenylphenyliodonium hexafluorophosphate 400 g of (diacetoxyiodo) benzene in 800 ml of acetic acid in a 1.5 liter flask equipped with a reflux condenser, thermometer, stirrer and nitrogen inlet. (1.24mol
) And heated to 40 ° C., after which 365.6 g of p-toluenesulfonic acid (1.
(92 mol) were added in portions over 3 hours. The reaction mixture was stirred at 40 ° C. overnight,
Cooled to room temperature and filtered. The filter cake was washed with water and dried under vacuum at 60 ° C. to give 372.4 g of hydroxy (tosyloxy) iodobenzene. In a 750 ml flask equipped with a reflux condenser, thermometer, stirrer and nitrogen inlet,
157 g (0.4 mol) of hydroxy (tosyloxy) iodobenzene and 67.15 g (0.5 mol) of isobutylbenzene were added to 12 ml of acetic acid and 40 ml of acetonitrile.
Was heated at 85 ° C. for 48 hours. After cooling the reaction mixture to room temperature, water 5
00 ml were added and the mixture was extracted with dichloromethane. After drying the organic phase over magnesium sulfate and filtering, the solvent was removed under vacuum. Solid was precipitated by treatment with hexane. Filtration provided 131.2 g of 4-isobutylphenylphenyliodonium tosylate as a beige solid. In a 750 ml flask equipped with a reflux condenser, thermometer, stirrer and nitrogen inlet,
40.7 g (80 mmol) of 4-isobutylphenylphenyliodonium tosylate and 29.5 g (1 mmol) of potassium hexafluorophosphate in 500 ml of acetone
(60 mmol) was refluxed overnight. The cooled suspension was filtered and the filtrate was concentrated under vacuum. 200 ml of dichloromethane were added and the solution was washed with water. After drying over magnesium sulfate and filtration, the solvent was removed in vacuo to give 36.5 g of p-isobutylphenylphenyliodonium hexafluorophosphate in the form of a colorless oil. ¹ H-NMR spectrum (measured with dimethyl sulfoxide-d ₆ ) showed displacement signals of the following values [ppm]: 8.22 (4H, m, ArH), 7.64 (1H, m, ArH), 7.53 (2H) , m, ArH), 7.34 (2H, m, Ar
H), 2.47 (2H, m, 2 CH ₂ ), 1.82 (1H, m, CH (CH ₃ ) ₂ ), 0.82 (6H, d, J = 6.2Hz, 2
_{CH3) C 16 H 18 F 6} IP elemental analysis: calculated C 39.86% H 3.76% F 23.64 % 26.32% P 6.42% Found C 40.14% H 3.89% F 23.63 % I 26.20% P 6.28%

The compounds of Examples 2 to 6 below were prepared from the corresponding substituted aromatic compounds by
It was prepared in the same manner as in Example 1.

Example 2 (4-hexylphenyl) phenyliodonium hexafluorophosphate Prepared from hexylbenzene. The title product was obtained as a brown oil. ¹ H
-NMR were measured in CD ₃ CN. [Ppm]: 8.02 (4H, m, ArH ), 7.71 (1H, m, ArH), 7.53 (2H, m, ArH), 7.36 (m, 2H, Ar
H), 2.65 (2H, t, J = 7.7Hz, ArCH ₂ ), 1.55 (2H, m, CH ₂ ), 1.28 (6H, m, (CH ₂ ) ₃ ), 0.85 (3H, t, J = 6.5 According to Hz, CH ₃ ) ¹ H-NMR, the product contained about 8% of the 2-hexyl isomer product.

Example 3 (4-octylphenyl) phenyliodonium hexafluorophosphate Prepared from octylbenzene. The title product was obtained as a reddish oil. ¹ H-NMR was measured by CD ₃ CN (ppm): 8.0 (4H, m, ArH), 7.70 (1H, m, ArH), 7.52 (2H, m, ArH), 7.36 (m, 2H, ArH)
), 2.65 (2H, t, J = 7.7Hz, ArCH ₂ ), 1.57 (2H, m, CH ₂ ), 1.25 (10H, m, (CH ₂ ) ₅ ), 0.85 (3H, t, J = 6.5Hz The product contained about 8% of the 2-octyl isomer product, according to (CH ₃ ) ¹ H-NMR.

Example 4: (2,4-dimethoxyphenyl) phenyliodonium hexafluorophosphate Prepared from 1,3-dimethoxybenzene. The title product is 129-130 ° C.
Was a solid. ¹ H-NMR was measured in DMSO-d ₆ [ppm
]: 8.19 (1H, d, J = 8.8Hz H 6), 8.07 (2H, m, H 2 '6'), 7.63 (1H, m, H 4 '), 7.4
_{9 (2H, m, H 3} '5'), 6.80 (1H, m, H 3), 6.69 (1H, dd, J = 8.8 and 2.1Hz, H 5)
, 3.94 (3H, s, OCH ₃ ), 3.83 (3H, s, OCH ₃ )

Example 5: (2,4-Diethoxyphenyl) phenyliodonium hexafluorophosphate Prepared from 1,3-diethoxybenzene. The title product was a solid with a melting point of 158 ° C. ¹ H-NMR was measured in DMSO-d ₆ [ppm]: 8.17 (1H, d, J = 8.8Hz H 6), 8.05 (2H, m, H 2 '6'), 7.64 (1H, m, H ₄ ′), 7.5
_{0 (2H, m, H 3} '5'), 6.75 (1H, m, H 3), 6.66 (1H, dd, J = 8.8 and 2.5Hz, H 5)
, 4.14 (4H, m, 20CH ₂ ), 1.33 (6H, m, 2CH ₃ )

Example 6: (2,4-Diisopropoxyphenyl) phenyliodonium hexafluorophosphate Prepared from 1,3-diisopropoxybenzene. The title product was a solid with a melting point of 125 ° C. ¹ H-NMR was measured with DMSO-d ₆ (ppm):
8.15 (1H, d, J = 8.8Hz H 6), 8.03 (2H, m, H 2 '6'), 7.63 (1H, m, H 4 '), 7.5
0 (2H, m, H ₃ ′ ₅ ′), 6.73 (1H, m, H ₃ ), 6.66 (1H, dd, J = 8.8 and 2.2Hz, H ₅ )
, 4.78 (2H, m, 20CH), 1.23 (12H, m, 4CH ₃ )

Example 7: Preparation of bis (p-isobutylphenyl) iodonium hexafluorophosphate In a 6 liter flask equipped with a reflux condenser, thermometer, stirrer and nitrogen inlet, 211.2 g (1. 57 mol) and potassium iodate 140
. 3 g (0.65 mol) are dissolved in a mixture of 1850 ml of acetic acid and 525 ml of acetic anhydride.
Cooled to ° C. A mixture consisting of 385 ml of acetic acid and 310 ml of sulfuric acid was added dropwise. The mixture was stirred overnight at room temperature and sodium bisulfate 39.15 in 2000 ml of water.
g was added. The solvent was extracted with hexane and dichloromethane. The organic phase was dried over magnesium sulfate, filtered and the solvent was removed in vacuo to give 304.9 g of bis (4-isobutylphenyl) iodonium bisulfate in the form of a brown oil. In a 1.5 liter flask equipped with a reflux condenser, thermometer, stirrer and nitrogen inlet, bis (4-isobutylphenyl) iodonium bisulfate 152.4
g (0.31 mol), potassium hexafluorophosphate 68.7 g (0.37 m
ol) and 750 ml of water were stirred for 5 hours. The solution was extracted with dichloromethane, then the organic phase was washed with water. Drying over magnesium sulfate, filtration and evaporation to remove the solvent gave 107.4 g of bis (4-isobutylphenyl) iodonium hexafluorophosphate in the form of a brown resin. ^{The 1} H-NMR spectrum (measured with CDCl ₃ ) showed displacement signals of the following values [ppm]: 7.85 (4H, m, ArH), 7.20 (4H, m, ArH), 2.42 (4H, d, J = 7.2Hz, 2CH ₂ ), 1.79
(2H, m, 2CH (CH 3) 2), 0.82 (12H, d, J = 6.6Hz, 4CH 3)

The following compounds of Examples 8 to 13 were prepared from the corresponding substituted aromatic compounds in a manner similar to that of Example 7.

Example 8 Bis (4-butylphenyl) iodonium hexafluorophosphate Prepared from n-butylbenzene. The title product was an orange resin. ¹ H-
NMR was measured by CD ₃ CN [ppm]: 7.95 (4H, m, ArH), 7.35 (4H, m, ArH), 2.65 (4H, t, J = 7.7 Hz 2CH ₂ ), 1.54 (
4H, m, 2CH ₂ ), 1.3O (4H, m, 2CH ₂ ), 0.89 (6H, t, J = 7.2Hz, 2CH ₃ )

Example 9: Bis (4-hexyl-phenyl) iodonium hexafluorophosphate This is a resin prepared from hexylbenzene. ¹ H-NMR was measured by CD ₃ CN [ppm]: 7.94 (4H, m, ArH), 7.34 (4H, m, ArH), 2.64 (4H, t, J = 7.7 Hz, 2CH ₂ ), 1.56
(4H, m, 2CH ₂ ), 1.27 (12H, m, 6CH ₂ ), 0.85 (6H, t, J = 6.5Hz, 2CH ₃ )

Example 10: Bis (4-octylphenyl) iodonium hexafluorophosphate This is a resin prepared from octylbenzene. ¹ H-NMR was measured by CD ₃ CN [ppm]: 7.95 (4H, m, ArH), 7.34 (4H, m, ArH), 2.64 (4H, t, J = 7.7 Hz, 2CH ₂ ), 1.56
(4H, m, 2CH ₂ ), 1.26 (20H, m, 10CH ₂ ), 0.85 (6H, t, J = 6.6Hz, 2CH ₃ )

Example 11 Bis (4-isopropylphenyl) iodonium hexafluorophosphate Prepared from 4-isopropylphenol. ¹ H-NMR signal was measured with DMSO-d ₆ [ppm]: 8.14 (4H, m, ArH), 7.40 (4H, m, ArH), 2.92 (2H, sept, J = 6.9 Hz, 2CH), 1.1
6 (12H, d, J = 6.9Hz, 4CH ₃ )

Example 12: Bis [4 (1,1-dimethylprop-1-yl) phenyl] iodonium hexafluorophosphate Prepared from 4 (1,1-dimethylprop-1-yl) phenol. ¹ H-N
MR signal was measured in DMSO-d ₆ [ppm]: 8.14 (4H, m, ArH ), 7.48 (4H, m, ArH), 1.61 (4H, m, 2CH 2), 1.21 (12H, s,
4CH ₃ ), 0.56 (6H, m, 2CH ₃ )

[0112] Example 13: was prepared from a mixture of bis (4-C ₃ -C ₁₄ alkyl phenyl) iodonium hexafluorophosphate C ₈ -C ₁₄ phenols which are substituted in the 4-position by alkyl. ¹ H-NMR signal was measured with CDCl ₃ [ppm]: 7.88 (4H, m, ArH), 7.30 (4H, m, ArH), 2.80-2.35 (≒ 2H, m), 1.75-1.35 (≒
12H, m), 1.35-0.65 (≒ 30H, m)

Example 14: Preparation of p-butoxyphenylphenyliodonium hexafluorophosphate In a 350 ml flask equipped with a reflux condenser, thermometer, stirrer and argon inlet, 100 g of diacetoxyiodobenzene (200 g of acetic acid) was added. .31 mol) and heated at 40 ° C., followed by 45.8 g (0.48 mol) of p-toluenesulfonic acid.
Was added in portions over 3 hours. The reaction solution was stirred at 40 ° C. overnight, cooled to room temperature and filtered. The filter cake was washed with water and dried under vacuum at 60 ° C. to give 71.2 g of hydroxy (tosyloxy) iodobenzene. In a 200 ml flask equipped with a reflux condenser, a thermometer, a stirrer and an argon inlet, 14.1 g (0.036 mol) of hydroxy (tosyloxy) iodobenzene and 5.1 g (0.034 mol) of 4-butoxybenzene were charged with acetonitrile. Heat at 40 ° C. for 2 hours in a mixture consisting of 5 ml and 2 ml of acetic acid. After cooling the reaction mixture to room temperature, 100 ml of water were added and the mixture was extracted with methylene chloride. The organic phase was dried over magnesium sulfate, filtered, and concentrated on a rotary evaporator. Solid was precipitated by treatment with hexane. Filtration gave 17.0 g of p-butoxyphenylphenyliodonium tosylate in the form of a beige solid having a melting point of 169-171 ° C. In a 200 ml flask equipped with a reflux condenser, thermometer, stirrer and argon inlet, 17.0 g (0.032 m) of butoxyphenylphenyliodonium tosylate was added.
ol) and 6.6 g (0.036 mol) of potassium hexafluorophosphate were stirred in 50 ml of acetone at room temperature overnight. The resulting suspension was filtered and the filtrate was concentrated on a rotary evaporator. 50 ml of methylene chloride were added and the solution was washed with water. After drying over magnesium sulfate and filtration, the solvent was removed under vacuum. Solid was precipitated by treatment with hexane. Filtration gave 15.0 g of p-butoxyphenylphenyliodonium hexafluorophosphate in the form of a beige solid having a melting point of 101-103 ° C. Calculated value C 38.56% H 3.64% F 22.88% P 6.22% J 25.47% Actual value C 39.84% H 3.72% F 21.61% P 6.18% J 25.32%

Examples 15-16: The compounds of Examples 15-16 were prepared analogously to the method of Example 14 using the corresponding extracts. The compounds and their physical data are shown in Table 1 below.

[0115]

[Table 1]

Example 17 A white enamel formulation was prepared by mixing the following components: Diglycidyl ether of bisphenol A (ARALDIT GY 250, Ciba Special Chemicals, Switzerland) 35.3%, trimethylolpropane Triglycidyl ether 14.1%, C12 / ₁₄ alkyl glycidyl ether 9.4%, rutile titanium dioxide (R-TC2, manufactured by Tioxide, UK) 39.2%, p-isobutylphenylphenyliodonium hexafluorophosphate (
See Example 1) 1.5%, isopropylthioxanthone 0.5%. The mixture was heated to 60 ° C. and shaken for 6 minutes. The mixture was again heated to 60 ° C., shaken for 6 minutes, and then stirred at 60 ° C. for 30 minutes. The formulation was applied to 300 μm aluminum sheets using a 12 μm spiral applicator. Irradiation, 80
Performed using two UV processors with two W / cm medium pressure mercury lamps. The maximum speed of the belt at which the sample was cured while the surface was tack free was determined. The higher the belt speed, the more reactive the formulation. Further, immediately after irradiation, the sample was placed in a circulating air oven for 180 minutes.
After a final heat treatment at 5 ° C. for 5 minutes, the yellowing of the coating was determined by the Yellowness Index (YI) according to ASTM D-1925-7. The lower the YI value, the less yellowing of the coating. The formulation was tack-free cured at a belt speed of 12.5 m / min. Immediately after irradiation, the measured YI value was -2.5, and after subsequent heat treatment was -3.4.

Example 18 A white enamel formulation was prepared by mixing the following components: Diglycidyl ether of bisphenol A (ARALDIT GY 250, Ciba Special Chemicals, Switzerland) 17.0 parts, trimethylolpropane 17.0 parts of triglycidyl ether, C _12/14 13.0 parts alkyl glycidyl ether, rutile titanium dioxide (R-TC2, manufactured by British company Tioxide) 50.0 parts, p- isobutylphenyl iodonium hexafluorophosphate (
2.0 parts, 1.0 part of isopropylthioxanthone, 2.0 parts of dispersant (Disperbyk 110, manufactured by Byk Chemie, Germany), 2.0 parts of wax (0.5 parts of polyfluor 540). The mixture was heated to 60 ° C. and shaken for 6 minutes. The mixture was again heated to 60 ° C., shaken for 6 minutes, and then stirred at 60 ° C. for 30 minutes. The formulation was applied to 300 μm aluminum sheets using a 12 μm spiral applicator. Irradiation, 12
0 W / cm microwave excited M-fusion lamp (fusion UV system)
The sample to be cured on the belt was passed under the lamp using a UV processor of the same type. The maximum speed of the belt at which the sample was cured while the surface was tack free was determined. The sample was cured to a tack-free surface at a belt speed of 10 m / min.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR , BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS , JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Baudin, Giselle, Switzerland 4123 Alshwill Baselmatweg 141 F-term (reference) 2H025 AA00 AB20 AC01 AD01 BE07 CA01 CA03 CA09 CA43 CC08 CC20 4J036 AA01 DA04 DB28 DD03 FA03 FA09 GA24 HA02 JA01 JA06

Claims (14)

[Claims] 1. A mono-, bis- or polyvalent aliphatic or aromatic glycidyl ether, (b) titanium dioxide, (c) at least one of iodonium hexafluorophosphate salts as a photoinitiator, and (D) A UV-curable cationically polymerizable composition containing a sensitizer compound. 2. The photoinitiator (c) has the formula (I): Wherein R ₁ , R ₂ , R ₃ and R ₄ are, independently of one another, hydrogen, C ₁ -C ₂₀ alkyl or unsubstituted or hydroxy-substituted C ₁ -C ₂₀ alkoxy, provided that R ₁ , R ₂
, R ₃ and R ₄ are not hydrogen). 3. The composition according to claim ₂ , wherein in the compound of the formula, R ₂ is C ₁ -C ₁₂ alkyl, especially isobutyl or dodecyl, and R ₁ , R ₃ and R ₄ are hydrogen. 4. The sensitizer compound (d) is a compound selected from the group consisting of anthracenes, xanthones, benzophenones and thioxanthones.
The composition of claim 1. 5. The method according to claim 4, wherein the sensitizer compound (d) is a thioxanthone derivative. 6. A glycidyl ether (a) having the formula (II): The composition of claim 1, wherein x is a number from 1 to 6 and R ₅ is a monovalent to hexavalent alkyl or aryl group. 7. The composition according to claim 1, wherein the proportion of component (a) is 40 to 70%, and titanium dioxide (b)
) Is 20 to 60%, the ratio of the photoinitiator (c) is 0.5 to 10%, and the ratio of the sensitizer compound (d) is 0.1 to 3%. The composition of claim 1. 8. A (4-isobutylphenyl) phenyliodonium hexafluorophosphate compound optionally combined with propylene carbonate. 9. A coated substrate having at least one of its surfaces coated with the composition according to claim 1. 10. The coated substrate according to claim 9, wherein the composition according to claim 1 is applied at a coating thickness of 0.1 to 100 μm. 11. The method for photopolymerizing a composition according to claim 1, comprising irradiating the composition with light having a wavelength of 200 to 600 nm. 12. The method according to claim 11, wherein a heat treatment is performed after the irradiation. 13. The process according to claim 11, for the preparation of coatings, paints, printing inks, powder coatings, laminating adhesives or dental compositions, in particular white enamel formulations. 14. Use of the composition according to claim 1, for the preparation of a coating, paint, printing ink, powder coating, laminating adhesive or dental composition, in particular a white enamel formulation.