FI68857C - SHEET FORM- IMPREGNERINGS- OCH OEVERDRAGSMASSOR SAMT DAERAV FRAMSTAELLDA FORMKROPPAR OCH YTBELAEGGNINGAR - Google Patents

Description

I ,, ANNOUNCEMENT. ,, r _ ^ B] ^ 11 UTLÄGGNI N G S SK Rl FT 6 O 8 57 C .... Patent granted 11 11 1935 ® ® / ρΛ? (45) r ^ + „.rt ^, oln, 'S ^ (51) Kv.lk.4 / lnt.Ci.4 C 08 L 67/06, C 08 K 5/53 SUOMI FINLAND (21) Patent application - Patentansöknlng 792195 (22) Application date - Ansökningsdag 12.07.79 <H> (23) Starting date - Giltighetsdag 12.07.79 (41) Has become public - Blivit offentllg 1 5.01 .8 0

National Board of Patents and Registration / 44) Date of presentation and hearing— 31.07.85

Patent- och registerstyrelsen '' Ansökan utlagd och utl.akriften publieerad (32) (33) (31) Privilege claimed - Begärd priority 1 * 1.07.78 1 * 1.03.79 Federal Republic of Germany-Förbunds-republiken Tyskland (DE) P 2830928.6, p 2909993.2 (71) BASF Aktiengesel1schaft, 6700 Ludwigshafen, Federal Republic of Germany - Förbundsrepubliken Tyskland (DE) (72) Anton Hesse, Luetzelsachsen, Peter Lechtken, Frankenthal,

Walter Nicolaus, Ludwigshafen, Dankmar Scholz, Frankenthal,

Federal Republic of Germany-Forbundsrepubliken Tyskland (DE) (7 **) Oy Kolster Ab (5 * 0 Photocurable molding, dipping and coating compounds and moldings and coatings made therefrom - Ljushärdbara form-, impregne-rings- och överdragsmassor samt därav lice Ida formkroppar och yt-beläggn Ingar

Numerous compounds have been described as sensitizers for the photopolymerization of unsaturated polyester resins (UP resins). When acylines, acyl esters or acyl ethers are used as UV sensitizers, relatively fast UV curing of UP resins is possible, however, mold materials with high-energy radiation after curing (elobopea vapor-high-pressure radiator) are yellow-toned. This detrimental yellowing, which decreases when the molds are stored in the dark but increases again when stored in daylight or artificial light, is noticeably disturbing when coating lighter trees or making light boards or corrugated boards.

According to publication 2 68857 DE-OS 2 104 972 (US-PS 3 G99 022), the yellowing of molded materials prepared from benzoin ether-containing UP resins can be reduced by trivalent phosphorus compounds, but it cannot be disposed of strongly enough to introduce the above-mentioned applications. UV-curing. Also, the addition of benzyl ketals, although leading to storage-resistant, highly reactive, highly hardy UP resins, does not bring an improvement over the more favorable color of the mold materials.

The object of the present invention was to develop photocurable molding, dipping and coating compositions which, compared to the state of the art in UV curing, show a substantially higher reaction rate, the colors of the obtained moldings being comparable or better.

This task is solved by photocurable molding, dipping and coating compositions comprising a mixture of a) at least one ethylenically unsaturated copoly-inert polyester, b) at least one ethylenically unsaturated copolymerizable monomeric compound, c) an inhibitor, (d) UV sensitiser and possibly paraffins, thermally decomposable initiators, fillers, reinforcing agents, glidants, inert solvents, anti-shrink additives and / or other auxiliaries for use with unsaturated polyesters and characterized in that the UV sensitiser is at least on the acylphosphine oxide compound of the formula (I) R1 0 \ "3 PC-FT (I) 2

R

0 wherein R · * "denotes a straight-chain or branched alkyl group containing 1 to 6 carbon atoms, a cyclohexyl, cyclopentyl, aryl, halogen, alkyl or alkoxyl-substituted aryl, S- or N-containing five- or six-membered a heterocyclic group, 2 1.1.2.

R 11a has the same meaning as R, where R and R may be the same or different from each other, or represent an alkoxy group having 1 to 6 carbon atoms, an aryloxy or arylalkoxy group, or 3 68857 1 · 2 R and R are together bonded to a ring ; 3 R denotes a straight-chain or branched alkyl group having 2 to 18 carbon atoms, a cycloaliphatic group having 3 to 10 carbon atoms, a phenyl or naphthyl group, an S-, O- or N-containing five- or six-membered heterocyclic group in which the group -3 min R may optionally include other substituents, or the group 0 R1 0 1. 2 wherein R 3a R 11a has the meaning given above and X represents a phenylene group or an aliphatic or cycloaliphatic divalent group having 2 to 6 carbon atoms and 1 3 optionally one or more of the groups R to R are olefinically unsaturated.

The mold, dipping and coating masses according to the invention are characterized by high reactivity when irradiated with fairly long-wave Uy light (wavelengths between about 300 and 500 nm). Advantageous compared to mold compositions containing acyline derivatives or benzyl ketals as a sensitizer are the substantially lower tendency of the cured mold materials to turn yellow and, in particular, the faster curing of thick-walled glass fiber-containing mold compositions. This has a particularly favorable effect on UV-curing laminates which are produced by hand, roller, centrifugal or fiber spraying methods.

Correspondingly, favorable results are obtained when UV-curing glass-fiber-free, moldable mold masses.

Preferred UV sensitisers are acylphosphine oxide compounds of the formula I in which R represents a cycloalkyl group, a phenyl group, a naphthyl group, an S-, N- or O-containing five- or six-membered heterocyclic group containing at least both ortho positions to the carbonyl group and a substituent A B, wherein A and B are the same or different and represent alkyl, cycloalkyl, aryl, alkoxy, thioalkyl, carbalkoxy, cyano or halogen atoms.

The characteristic "contains substituents A and B at both ortho positions relative to the carbonyl group" is to be understood as meaning that "68857 substituents A and B may be attached to both carbon atoms adjacent to the carbonyl group attachment position, which may be substituted. This means, for example, that the oC-naphthyl group contains substituents A and B at at least 2,8-positions and the β-naphthyl group at least 1,3-positions.

UV sensitizers of this type, in particular the highly preferred 2,4,8-trimethylbenzoyl diphenylphosphine oxide, exceed all the photoinitiators of unsaturated polyester resins known to date. This high reactivity results in strong heat generation when curing laminates. As a result, it is possible to perform curing with radiators that release even less energy. For example, the use of expensive mercury vapor high-pressure radiators can be dispensed with and simpler low-pressure lamps, such as ordinary fluorescent tubes, can be used instead.

The use of preferred highly reactive UV sensitizers further significantly improves the storage durability of sensitized mold, dipping and coating compositions, so that one-component systems with constant curing activity can be prepared throughout the storage period.

With regard to the starting components a) to e) used for the production of photocurable molds, dips and coatings, it is necessary to clarify the following: a) Unsaturated polyesters are not to be understood

Suitable unsaturated polyesters are the customary polyhydric, in particular divalent, carboxylic acids and their esterifiable derivatives, in particular their anhydrides, which are ester-linked to polyhydric, in particular dihydric alcohols and optionally also contain monohydric carboxylic acid and / or monohydric alcohols and / or monohydric alcohols. at least some of the groups must be controlled by ethylenically unsaturated copolymerizable groups, polycondensation products.

5 68857

Suitable polyhydric, especially dihydric, possibly unsaturated alcohols are the usual alkanediols, especially those containing acyclic groups, cyclic groups as well as both groups, and oxaalkane diols, such as ethylene glycol, propylene glycol-1,2, propanediol-1,3, butylene glycol , butanediol-1,4, hexanediol-1,6,2,2-dimethylpropanediol-1,3, diethylene glycol, triethylene glycol, polyethylene glycol, cyclohexanediol-1,2,2,2-bis- (p-hydroxycyclohexyl) propane , trimethylolpropane monoallyl ether or butenediol-1,4. Furthermore, monohydric, trihydric or polyhydric alcohols such as ethylhexanol, fatty alcohols, benzyl alcohols, 1,2-di- (allyloxy) propanol- (3), glycerol, pentaerythritol or trimethylolpropane in secondary amounts may be used. Polyhydric alcohols, especially dihydric alcohols, are generally reacted in stoichiometric or stoichiometric amounts with polybasic, especially dibasic, carboxylic acids or their condensable derivatives.

Suitable carboxylic acids or their derivatives are dibasic olefinically unsaturated, preferably .beta.-olefinically unsaturated carboxylic acids, such as maleic acid, fumaric acid, chloromaleic acid, itaconic acid, citric acid or citric acid, their methylene, methylene. In addition to the polyesters, other modifying dibasic, unsaturated and / or saturated, as well as aromatic carboxylic acids, such as succinic acid, glutaric acid,? , dihydro-phthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, 3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid, endomethylene-tetrachloro-phthalic acid, propylic acid or hexachloroendomethylenetetrahydrophthalic acid, benzoic acid, 1,2,4-benzenetricarboxylic acid or 1,2,4,5-Benzenetetracarboxylic acid. Preferably maleic acid or its anhydride and fumaric acid are used. Since the maximum crosslinking capacity present in this type of polyester plays an important role in the result of the recovery shrinkage system, there are 68857 in this range of applications, i.e. 50 to 100% of the dicarboxylic acids attached to the polyester must be unsaturated.

Mixtures of unsaturated polyesters, including those which are only sparingly soluble in vinyl monomers (b) and readily crystallize, can likewise be used advantageously. Such readily crystallized unsaturated polyesters can be composed of, for example, fumaric acid, adipic acid, terephthalic acid, ethylene glycol, butanediol-1,4, hexanediol-1,6 and neopentyl glycol.

Unsaturated polyesters with preferably terminal double bonds are also suitable.

The unsaturated polyesters have acid numbers in the range of 10 to 200, preferably 20 to 85, and average molecular weights of about 800 to 6000, preferably about 1000 to 4000.

Amorphous and possibly crystallizable unsaturated polyesters are generally prepared by melt condensation or condensation under azeotropic conditions from their starting materials by continuous or discontinuous methods.

With regard to the composition of unsaturated polyesters, H.V. Boenig's book, Unsaturated Polyesters: Structure and Properties, Amsterdam, 1964.

Instead of unsaturated polyesters, urethane-containing unsaturated polyesters can also be used, as already mentioned. To this end, the above-mentioned unsaturated polyesters are reacted with organic polyisocyanates, preferably aliphatic, cycloaliphatic and especially aromatic diisocyanates, and thus the unsaturated polyester chain is extended and the molecular weight is increased. Suitable chain extensions are, for example, aliphatic diisocyanates, such as 1,4-butanediisocyanate and 1,6-hexane diisocyanate, cycloaliphatic diisocyanates, such as 1,3- and 1,4-cyclohexane diisocyanate, 1-Methyl 2,4- and 2,6-cyclohexane diisocyanate and mixtures of isomers, isophorone diisocyanate and 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate and the corresponding mixtures of isomers and preferably aromatic diisocyanates, such as 2,4- and 2,6-toluene diisocyanate and the corresponding mixtures of isomers, 4,4'-, 2,4'- and 2,2'-diphenylmethane-di- isocyanate and 7,685,77 corresponding isomer mixtures and 1,5-naphthylene diisocyanate. To prepare urethane-containing unsaturates, the starting materials are suitably reacted at temperatures between 0 and 120 ° C, preferably between 15 and 60 ° C, in such amounts that the ratio of unsaturated polyester Zerexitinoff-active hydrogen atoms, preferably attached to OH and COOH groups, as N : 0.1 to 0.9, preferably 1: 0.2 to 0.7. The resulting urethane group-containing unsaturated polyesters have acid numbers in the range of 2 to 30, preferably in the range of 5 to 20, and average molecular weights of about 1,000 to 10,000, preferably about 1,500 to 6,000.

Suitable unsaturated vinyl ester resins for the purposes of the invention have the characteristic moiety -CO-OC 2 CHOH-CH 2 O and contain terminal polymerizable unsaturated groups. Vinyl ester resins are prepared by reacting approximately equivalent amounts of polyepoxide resin and unsaturated monocarboxylic acid, e.g., 2 equivalents of methacrylic acid with two equivalents of polyepoxide resin.

Vinyl ester resins of this type are described, for example, in U.S. Pat. No. 3,367,992, according to which the dicarboxylic half esters of hydroxyacrylates or methacrylates are reacted with polyepoxide resins. According to US-PS 3,066,112 and 3,179,623, vinyl ester resins are obtained from monocarboxylic acids, e.g. acrylic and methacrylic acids; also mentioned herein is an alternative preparation method in which glycidyl methacrylate or acrylate is reacted with a sodium salt of a divalent phenol, e.g. bisphenol A, Epoxy-Novolac resin-based vinyl ester resins are described in US-PS 3 301 743. U.S. Pat. No. 3,256,226 discloses vinyl ester resins in which the molecular weight of the polyepoxide is increased by the reaction of a dicarboxylic acid with a polyepoxide resin and an acrylic acid. Further suitable vinyl ester resins are suitable, e.g. according to DE-0S 2534 039 (equivalent to US-PS 3947 422) which contain half-ester groups and are obtained by reaction of a second hydroxyl group of the group -CO-OCH 2 · CHOH-C 0 O with a dicarboxylic anhydride, e.g. with maleic acid, citraconic acid, phthalic acid, tetrabromophthalic anhydride, etc.

8 68857

The photocurable molding, dipping and coating compositions according to the invention generally contain from 10 to 80% by weight, preferably from 15 to 70% by weight, based on the total weight of components (a) and (b) of unsaturated polyester, urethane-containing unsaturated polyester or unsaturated vinyl ester resin. or mixtures of said components (a).

b) Suitable copolymerizable, ethylenically unsaturated monomeric compounds are the allyl and preferably vinyl compounds used in the preparation of polyunsaturated polyester molds, dipping and coating compositions, such as styrene, substituted styrenes such as p-chlorostyrene or vinyl toluene, with, i.e. methacrylic acid methyl ester, acrylic acid butyl ester, ethyl hexyl acrylate, hydroxypropyl acrylate, dihydridicyclopentadienyl acrylate, butanediol diacrylate and (meth) acrylic acid amide, allyl esters of allyl esters such as diallyl phthalate and vinyl esters such as Mixtures of said unsaturated monomers are also suitable. Preferably suitable components (b) are styrene, N-methylstyrene, chlorostyrene, vinyltoluene, divinylbenzene and diallyl phthalate. Component (b) is generally included in the polyester mold, dipping and coating compositions in an amount of 20 to 90, preferably 30 to 85% by weight, based on the total weight of components (a) and (b).

c) The photocurable molding, dipping and brushing compositions according to the invention are stabilized by means of customary inhibitors (c). Examples which may be mentioned are phenolic inhibitors such as hydroquinone, substituted hydroquinones, benzcatechol, tert-butylbenzcatechol, nuclear substituted brentscatechol derivatives; quinones such as benzoquinone, naphthoquinone, chloranil, nitrobenzenes such as m-dinitrobenzene, thiodiphenylamine, N-nitroso compounds such as N-nitrosodiphenylamine and N-nitroso-N-cyclohexylhydroxylamine and mixtures thereof. Also suitable as further stabilizers are salts of divalent copper, for example copper naphthenate or octoate and quaternary ammonium salts of the structure ^ R5R6, R7, R87 X ", in which R5, R6, R7 and R8 represent an alkyl group having 1 to 20 carbon atoms, 6 to 147 carbon atoms an aryl group or an aralkyl group having 7 to 30 carbon atoms and X a halogen atom, preferably chloride.

The addition of a selected UV absorber to stabilize the light of the curing products causes in many cases a slight decrease in the UV curing rate, which, however, can still be subjected to. Suitable are those selected from oxybenzophenone, saicylic acid esters and oxyphenylbenztriazole.

Inhibitors are generally present in the mold, dipping and coating compositions in an amount of 0.005 to 0.5, preferably 0.01 to 0.2% by weight, based on components a) and b).

d) As UV sensitisers (d) according to the invention are considered acylphosphine oxide compounds of the formula r \ 0 it a p-c-ir (i) R 2 -I 1 R 2 -O. Examples of acylphosphine oxide compounds are: acylphosphine oxides and acylphosphinic acid esters. With respect to formula (I), the following shall be specified: R · * · may be a straight-chain or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, amyl- , n-hexyl, cyclopentyl, cyclohexyl, aryl, such as phenyl, naphthyl, halogen-substituted aryl, such as mono-, or dichlorophenyl, alkyl-substituted phenyl, such as methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, dimethylphenyl, alkoxy-substituted aryl, such as methoxyphenyl, ethoxyphenyl, dimethoxyphenyl, S- or N-containing five- or six-membered ring, such as thiophenyl, pyridyl, 2 1 R: 11a may be R and further may be an alkoxyl group having 1 to 6 carbon atoms, such as methoxyl, ethoxyl, i-propoxy, butoxyl, ethoxyethoxyl, aryloxy, such as phenoxy, methyltenoxy, benzyloxy, 1.2 R may be bonded to R as a ring, such as acylphosphonic acid-o-phenyl er e is sä.

10 68857

Rj vol. be ethyl, i-propyl, n-propyl, n-butyl, i-butyl, tert-butyl, i-amyl, n-hexyl, heptyl, n-ok -tyl, 2-ethylhexyl, i-nonyl, dimethylheptyl, lauryl, stearyl, cyclopropyl, cyclobutyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, norbornauienyl, , phenyl, methylphenyl, tert-butylphenyl, isopropylphenyl, methoxyphenyl, 1-propoxyphenyl, thiomethoxyphenyl, N and N-naphthyl, thiophenyl, pyridyl, N-acetoxyethyl or - carboxyethyl-lirynmä.

12 3.

R, R, R may additionally contain C-C double bonds which allow the UV sensitizer to polymerize into the binder.

Examples of appropriate UV sensitizers be mentioned invention intends t i sobutyryyli metyylifosfiinihappometyyliesteri-isobutyryl-fenyylifosfiinihappometyyliesteri through valoyyli-phenylphosphine iinihappometyyliesteri 2-Ethyl-hexanoyl pivaloyl ester fenyylifosfiinihappometyy1 fenyylifosfiinihappoisopropyy1 ester-p-tolyl-fenyylifosfiinihappometyyliesteri o-tolyl-fenyylifosfiinihappometyyliesteri 2,? - dimethylbenzoyl-fenyylifosfiinihappometyyliesteri p-tert-butyl ester fenyylifosfiinihappoisopropyy1 acryloyl-diphenyl phosphine oxide fenyylifosfiinihappometyyliesteri isobutyryl-2-ethylhexanoyl-diphenyl phosphine oxide o-toluyl-diphenyl phosphine oxide p-tert-butyylibentsoyylidifenyylifosf iinioks -amide 3-pyridylcarbonyl-diphenyl phosphine oxide, benzoyl diphenylphosphine oxide akryloyylidifenyylifosfiinioksidi pivaloyl-fenyylifosfiinihappovinyyliesteri adipoyl-bis-diphenylphosphine oxide

Preferred are: pivaloyl-diphenylphosphine oxide p-toluyl-diphenylphosphine oxide 4- (tert-butyl) -benzoyl-diphenylphosphine oxide terephthaloyl-bis-diphenylphosphinexyl-2-enoxy-2-methyl-2-methyl-diphenylphosphine oxyphosphinoxyphosphine oxide -diphenylphosphine oxide i-methyl-cyclohexanoyl-diphenylphosphine oxide pivaloyl-phenylphosphinic acid methyl ester and pivaloyl-phenylphosphinic acid isopropyl ester.

Compounds of this type can be prepared by reacting acid halides of the formula R3-C-X X r ci, Br, of the formula rJ1 P-OR4 R2 ^ 4 ....

R = a straight-chain or branched C 1 -C 6 alkyl or cycloalkyl group having 5 to 6 carbon atoms with the corresponding phosphines.

The reaction may take place in a solvent such as a hydrocarbon or hydrocarbon mixture such as petroleum ether, toluene, cyclohexane, ether, other common inert organic solvents, or also without a solvent at temperatures between -30 ° C and + 110 ° C, preferably between 10 and 70 ° C. . The product can be crystallized directly from the solvent, it remains after evaporation or it is distilled in vacuo.

0 3 m 12 4

POR of acid halides R CX and substituted phosphine R R

recovery takes place according to methods familiar to the person skilled in the literature (e.g. K. Sasse in Houben-Weyl, Volume 12/1, pp. 208-209, G. Thieme-Verlag, Stuttgart).

The process for the preparation of the compounds according to the invention can be described, for example, as follows: 12 68857

O

/ 0ch3 rgpci -► (OVpx ♦ CH, ^^ N- 'OCH3 *

CH, 0 O

3n jgr (of + CH3C1 or: (° X. ΒΛη 'af® -'

^ Jof

(of s. chjU

Suitable phosphines include e.g. methyl dimetoksifosfiini, butyl dimetoksifosfiini5 phenyldimethoxyphosphine, toluylene-methoxyphosphine, fenyylidietoksifosfiini, toluyylidietoksifosfiini, phenyldiisopropylsilyl isopropoksifosfiini, toluylene isopropoksifosfiini, fenyylidibutoksifosfiini, toluyylidibutoksifosfiini, or dimethyl-limetoksifosfiini, dibutyylimetoksifosfiinidimetyylibutoksifos-olefin, difenyylimetoksifosfiini, difenyylietoksifosfiini, DIFE-nyylipropoksifosfiini , diphenylisopropoxyphosphine, diphenylbutoxyphosphine or similar starting materials which give the compounds of the invention.

Chlorides and bromides are suitable as acid halides, however, acid chlorides are particularly preferred.

Examples of compounds of the invention include, but are not limited to, the following: 13 68857

rO ri CN

On · = O O m O VO m * «k λ * t« * t ·> · «

OsJ (M T-H rH 1-1 r ~ i CN ON

rH r- * rH τ-i »H tH

•B

C/O

>> CO ON U * N f— rt

I O’-1,00 rt .3- VO (Λ CO

^ [S’- r- vo f- co mm mm • H p rH <> 1> 1

P O CO VO ON O O

n, - «o co vo r- om ^ O OOn -« «« μη vom nr m mm mm VO VO VC VO f- I 'll b 3 £ £ 3 ~ δ ^ ta? ϋ 5 ti 3

»D j? ή X -p co trt X-P

+ j w <d ω <d flid co

ω n3 [d cd <o i-Hca 'SiS

r-l H 01 tn i — I (Λ ® ° ** w m «w C · m m O m H Π3 vo vo r · - t— T3 tti, C co

> n

nj

-P

co kn rvi • P * * CO · O · “*

• H A ^ M »I I

S ^ o S

3 rt rl

S

c • 2 rt m p o o • HP. 1 ‘kn CO CO χ rX Γ. o <U 0, o * \ /: nJ '/ * s °

V

, M 'ro i

X I I £ O SZ JZ

c, o-o a, o cu en g, χΛ Λ \ ^ \ / \ / S \ / ° \ ™ ϋ »· Γ ° * f: ° · Γ / 5 <°> ® ^ aj m m X \ \

Λί Ή X X O N N

p co o-o -o V m o r-t -H · \ x m

h rt m m O X

5 £ X X

H £ O o 68857 τ-4 .ry

CTv LO LO O CO O

lo in lp. r- *% · * as * ** ·> * »* · τΗ · * -Η Q * - <2- ON CO K r-l τ-l r-u r *

* r ~ i CO

^ ^ C '- *' / _ ^ iTi - CO \ £> ι_Λ 1 lm ·, ·, »Λ as A as« s

fti LP. and Ό vo cr ^ r \ OVO

c <8- = r <-h ro r ** - m O en co mo CO λλ λλ as «s as as and lo lo rH th th P- Γ" - P- f · '- P- c * ^. p_ p- 0 0 0 0

V -H -μ -H

μ -μ -μ -μ <D3 α> 3 <ΰ 0 ο) 0 X -μ χ -μ χ μ> χ -μ ω β m (ΐ) co 3 ω 3 π3 rd 3 3 3 3 3 3

O iHCO iH-tn (—i tO H M

• μ ^ vs. w <Λ ve.

3 “^ LT \ TH

oo so co m co

Pk

X 1 1 1 I

r— Ό m. = r O ^ O * -i r- <r- <CU r-1

£ -C

^ O, CU

| V / = o S o = (m m \ a- ^ Cu Oh) -s Cu = o H \ / {O / 0 = 0 -C ™ X = O \ W I C-.

1 s «<v © r: 3 '2 °' \ 2 / X x" V = ° o7 £ £ W ° ° ° = ^ r. Xx X o o 15 68857 r ~ - Ό

LO O VO r- LO

. »- O VO O O" '»Hr- OV CO« * "o» »H rH ^ OO LT. Λ · »H r- <

•B

i? »H <M

►> »ζ ^ \ Τ-» f- · cm ^ ϊ >> CO O CD Tl «· * * ^

c {“a M a * M v <0 Ό C '> ON

rtf cO e— co

C

<00 = 3 ® _ ΓΟ

VO O VO VO tM CV

O «« - «« - -Γ T * C \ J ΡΛ ΙΛ ΓΛ VO LTl Λ «

»O \ 0 f *, f— VO VO CNI (M

LO u> 3 3 3 • μ -μ -μ 3

-P -P Ή -P

<t> 3 <1) 3 <1) 3 ti 3 rX + J Λ + J r ^ -HS + j m3 to 3 w 3 m2 3 3 3 3 <33 id 3 O ι-H (0 I — IM i —I to rH 3 -μ 3 Vi> «VH ** 3 _ 3 oo O o

(f)> sO CTN C \ CC

LH ^ A · * • o, ° * ° '£

rH

Ρ »I I I I

C/O

£ X

0- Oh

WSO

/ - \ KN Κ> I £ -C

3 XX Oscjr ^ 0- & - <M

3? "\ / 5 \ / ί \ /, <\ Η ΐ = ° g 3 \ x / oj NX 0 = 0

π o x o I

ν_ »I jC O ro o ^ ° N“ · V gig i 5 H, '= °, °% \ Λ / Cvj XX = o S 3 O = (X ^ O 7 ° = (^ -¾ £ \ / ° VJ '? \ Λ

5 .H O / O 0 = 0 O

3 Ό r ^ Xx-v (Γ P ^ / \ κν

3 »C XXX XXX

H> h ooO ooo 16 68857 ^ τ-ί \ 0 Γ— '· = Γ (—LA 1Λ ^ Ο - = Γ COCO tA ΚΛ cr \ C ~ \ CT \ £ Τ \

rH tH

B

cn ~ _ ^ co - vo σν IT1 t ~ - CO vor- O * -1 cr. T-C

P * 1 * ** A A «V #. M

I I - j = r jr- Ό v £> p— f— q ^> fÖ

C

<CM f \ j cc

O LAr— - = r (Τ '»^ OrA

* * AA «A» #v Γ- * f— · CC CC k * \ fA ηλ {'- • f' · * · LAlA r— r * «- fw 5 5 5 5 ± j + -1 -M 4 - * a> da> ddda; d, χ-μ γ ^ -ρ λ; -h ^ 5 in n) uitti tn rt tn d rt d rt d rtj ro rt rt

O i — ll / D r ~ \ iT} rHUSi— \ W

-μ C ** (Λ ΐ * W, d rt m c vo o

CO VO VO CM ON

in o

Ph, O 1 «* £

O

τ · Η o

CO I

Ph O I

CO ti r -c

CU CU

\ / C-ί s o% vtr / rt cvm O = O <\ i m

Tl o a:, x x t! O O X SZ \ / 0-0 V · \ / \ / 5 \ m

0 = 0 Na. = O CM \ X

- JZ /, X No

\ / "· ° * <_ ° '(V

• S ·> 0r ° / Tr = "\ a! .H rA ° 7C \ s1

3 1 \ r 'V

H> h o o 68857

Particularly suitable UV sensitizers for unsaturated polyester resins are acyl-phenyl-phosphinic acid esters or acyldiphenylphosphine oxides having acyl groups from a secondary or tertiary substituted aliphatic carboxylic acid such as pivalic acid, 1-methylcycloic acid, 1-methylcycloic acid, containing 9 to 13 carbon atoms), 2-ethylhexanecarboxylic acid or a substituted aromatic carboxylic acid such as p-methylbenzoic acid, o-methylbenzoic acid, 2,4-trimethylbenzoic acid, p-methoxybenzoic acid or p-thiomethylbenzoic acid.

Particularly preferred highly reactive UV sensitizers are those compounds of the formula I in which 3 R can be: a cycloalkyl, aryl, naphthyl group, an S-, N- or O-containing five- or six-membered heterocyclic group, e.g. furyl, pyrrolyl -, thionyl, pyranyl or pyridyl group containing at least both ortho positions of the carbonyl group attached to the substituents A and B, wherein A and B are the same or different and represent an optionally branched alkyl group containing 1-6, preferably 1- 4 carbon atoms, e.g., methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl and tert-butyl group; further optionally substituted cycloalkyl group, e.g. cyclohexyl group, optionally substituted aryl group, e.g. phenyl or toluyl group, alkoxy or thioalkyl group containing 1-6, preferably 1-4 carbon atoms in the alkyl group, e.g. methoxy, propoxy, iso- a propoxy, n-butoxy group, methylthio, ethylthio, propylthio, iso-propylthio, n-butylthio, sec-butylthio, and tert-butylthio; a carbalkoxy group containing 1 to 6, preferably 1 to 4 carbon atoms in an alcohol group, e.g. a carbomethoxy, carboethoxy, carbopropoxy, carboisopropoxy, carbobutoxy and carbo-sec-butoxy group, a cyano group or a halogen atom, for example a chlorine , a bromine or iodine atom.

Acylphosphine oxide compounds containing 3 R as bond may be represented, for example, by the following structural formulas, 18 _____ 6 8 8 5 7

An ^ a r1r2-po-co- / h \ r1r2-po-co- / \ y_y w

B B

AK Ay- \ rV-po-co- / ^ r1r2-po-co-f \ W X b - / "" Λ \

A A

R ^ 2-PO-COt ^ N | ^ H] \ _ R1R2-PO-CO -Γ N, s, 0

B

X

wherein X optionally represents other substituents on cycloalkyl, aryl, naphthyl or heterocyclic groups and has the meaning A or B.

Examples of highly reactive UV sensitizers of this type are: 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethoxybenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethylbenzylbenzyl-2-phenyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl, 2,6-dimethoxybenzoyl, trimethylbenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-tolylphosphinic acid methyl ester, 2,4,6-trimethoxybenzoyl-diphenylphenylphosphine oxide, 2,6-dichlorobenzoylphenylphenyl, 2,6-dichlorobenzoylphenylphenyl diphenylphosphine oxide, 2,6-dimethylthio-benzoyl-diphenylphosphine oxide, 2.3.4.6-tetramethylbenzoyl-diphenylphosphine oxide, 19 68857 2-phenyl-6-methylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenyl-diphenyl-diphenyl-diphenyl benzoyl-naphthylphosphinic acid ethyl ester, 2,6-dichlorobenzoyl-naphthylphosphinic acid ethyl ester 1,3-dimethylnaphthalene-2-carbonyl-diphenylphosphine oxide, 2,8-dimethylnaphthalene-1-carbonyl-diphenylphosphine oxide, 1.3-dimethyl-diphenylphosphine oxide, 1,3-dimethylnaphthalene-2-carboxylate 2,4,6-Trimethylpyridine-3-carbonyl-diphenylphosphine oxide, 2,4-Dimethylquinoline-3-carbonyl-diphenylphosphine oxide, 2,4-Dimethyl-furan-3-carbonyl-diphenyl-phosphine oxide 2,4-Dimethoxy-furan-3-carbonyl-diphenyl-phosphine oxide-2,4-dimethyl-phosphine oxide Phenylphosphinic acid methyl ester 2,4,5-Trimethyl-thiophene-3-carbonyl-diphenylphosphine oxide.

Preferred are: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethyl-benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzylbenzylbenzylbenzyl

Particularly preferred highly reactive UV sensitizers are acyl-phenylphosphinic acid esters and acyldiphenylphosphine oxides having acyl groups of a di-ortho-substituted aromatic carboxylic acid such as 2,4,6-trimethyl-benzoic acid, 2,6-dimethoxy-benzoic acid -benzoic acid or 2,3,5,6-tetramethylbenzoic acid, derivatives.

The acylphosphine oxide compounds used according to the invention are added in amounts of 0.005 to 5% by weight, preferably 0.01 to 3% by weight, based on the weight of the unsaturated polyester (a) and the ethylenically unsaturated monomeric compounds (b).

(e) Examples of polyester or vinyl ester resin additives in (e) are: thickeners, glidants, inert solvents, anti-shrink additives and / or other excipients used in polyester blends.

68857 20

The paraffins having use in the photocurable mold, dip and coating compositions according to the invention have a melting point in the range from 25 to 90 ° C, preferably from 45 to 60 ° C. Paraffin with a melting point of 46-48 ° C has been found to be particularly advantageous and therefore particularly used.

Instead of paraffins, other waxy substances can also be added, e.g. paraffin oxidation products known as montanava or their esters, carnauba wax, long-chain fatty acids such as stearic acid, stearyl stearate, kerinine and the like.

In order to reduce the evaporation of the monomers and to form a non-stick surface, the unsaturated mold masses contain 0.01 to 5% by weight, preferably 0.05 to 1% by weight, in particular 0.1 to 0.5% by weight of paraffin, based on components a) and b) of the total weight.

Suitable thickeners are, for example, alkaline earth metal oxides, such as calcium oxide, calcium hydroxide, magnesium hydroxide and preferably magnesium oxide, and mixtures of these oxides or hydroxides. These can also be partially replaced by zinc oxide.

The thickener content of the polyester or vinyl ester molding compositions according to the invention is generally between 0.5 and 5%, preferably between 1 and 3% by weight, based on the mixture of components a) and b).

In addition to the acylphosphine oxide compounds according to the invention, suitable peroxides are: peroxides, e.g. peresters such as tert-butyl peroxoate, tert-butyl perpivate, percarbonates, such as bis- (4-tert-butylcyclohexyl) peroxydiacarbonate, peroxydicarboxylate benzoyl peroxide, dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide, hydroperoxides such as cyclohexanone peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide and tert-butyl hydroperoxide as well as azo compounds such as azodiisomeric dinitrile, tetraphenylethanediol and / or β-tetrasubstituted dibenzyl compounds as described, e.g., in Kunststoffe 66, 693 (1976). The thick laminate structures are then cured using glass fibers and quartz radiation when, in addition to the acylphosphine oxide compounds according to the invention 6885 7, small amounts of, for example, 0.05 to 1% by weight, preferably 0.1 to 0.3% by weight, based on the total weight of components a) and b) are used. thermally decomposable initiators. These initiators decompose into radicals in the heat generated by photopolymerization, so that curing can also take place in deeper layers, which are only insufficiently exposed to UV light.

Also particularly preferred are the acylphosphine oxide compounds according to the invention and known photoinitiators, e.g. aromatic ketones, e.g. -tert.-butyltrichloroacetophenone, use of aromatic disulfides and naphthalenesulfonyl chlorides. With the use of said photoinitiator combinations, in many cases it is possible to achieve lower residual styrene contents from UP resin molding materials at comparable exposure times than with the use of acylphosphine oxide compounds alone, although the curing activity (measured as the temperature of the resin sample increases during exposure) decreases. The photoinitiator combinations suitably contain 15-85% by weight, preferably 25-75% by weight of acylphosphine oxide compounds and 15-85% by weight, preferably 25-75% by weight of aromatic ketone, aromatic% by weight based on the total weight of the mixture. The combinations are used in amounts of 0.005 to 7% by weight, preferably 0.01 to 4% by weight, based on the weight of components (a) and (o).

In addition, common fillers, reinforcing agents, glidants, inert solvents and other auxiliaries are most often added to the curable unsaturated molding, dipping and coating compositions according to the invention.

Suitable fillers are, for example, the usual powdered or granular inorganic or organic fillers which are permeable to long-wave UV light, such as alumina hydrate, quartz sand, finely divided silicic acid, asbestos, talc, barium sulphate, light slag (calcium sulphate) and

Suitable reinforcing agents are inorganic or organic fibers or planar fabrics, possibly woven therefrom, such as carpets, e.g. glass, asbestos, cellulose and 22 6885 7 synthetic organic large polymers, such as polyamide, polyacrylonitrile, and polyesters, e.g. terephthalates.

Fillers and reinforcing agents can be used in amounts of 5 to 200% by weight, preferably 10 to 70% by weight, based on the total weight of components a) and b). In many cases, the combination of powdered and fibrous fillers is favorable (e.g. in the manufacture of containers). After the lamination process, the laminate can be covered with a UV-permeable foil and cured with low-energy UV radiation from fluorescent tubes (eg TAK 4 0 W / 05, Philips) for a long time or with Hg steam high-pressure lamps (Η0Κ 6, 80 W / cm, Philips) in a very short time.

Examples of lubricants that can be considered are zinc, magnesium and calcium stearate and polyalkylene ether waxes.

Further suitable inert solvents which may be used are ketones, esters, hydrocarbons in amounts of up to 100% by weight, based on components a). Possible additional shrinkage reducing additives are, for example, thermoplastic polymers, such as polystyrene, styrene copolymers, polyvinyl acetate or poly (meth) acrylate in amounts of from 1 to about 30% by weight, based on components a) + b).

As radiation sources for curing mold, dipping and coating compositions, mention may be made, for example, of fluorescent tubes, mercury-plated pressure radiators and direct sunlight.

The mold, dipping and coating compositions of the invention can be used in many technical fields. They are suitable, for example, for the following purposes: 1. Thin-layer resins

Only thin layers about 0.5 mm thick act as protection for the back laminate and its hydrolysis-sensitive glass fiber. The resins must meet high requirements for curing activity and the moldings must have only a slight yellowing tendency. The transparent thin layers are applied to the mold by spraying or brushing, then they are gelled or cured by UV radiation, and then a glass-fibrous mold mass is applied.

23 6885 7 2. Fiber-reinforced moldings a) for clear sheets

The construction sector is characterized by high transparency and low yellowing. Continuously working machines are used to produce smooth, longitudinally or transversely corrugated clear sheets. Glass-silk mats are wetted with light-stabilized UP resins between cover foils, deaerated, and finally cured. By adding the acylphosphine oxide initiators according to the invention, curing can also be carried out more rationally with UV radiation from Hg-steam high-pressure radiators or also with so-called blue light lamps (literature on the production of bright plates: PH Selden, "Glasfaservoffe," Glasfaserverstärkte " Heidelber-New York, 1967).

(b) Discontinuous processes for the production of fiber-reinforced moldings, in particular glass-fiber-reinforced molds, which are suitable for UV-curing are: Hand-working process, fiber spraying, centrifugation and rolling process (for a description, see P. H. Selden, "Glasfaserverstärkte Kunststoffe").

The utensils produced in this method are, for example, boats, container boards (chipboard and fiber boards coated on both sides with fiberglass-reinforced plastic), pipes, tanks.

c) UP resin-thin layers for fiberglass molded materials (GFK) and paper laminates.

The surface quality of GFK and paper laminates can be improved by applying a thin layer to it. The following advantages are achievable: 1. GRP laminates, such as corrugated sheets: a) Gloss lasts longer when exposed to the weather and thus less soiling.

b) Transparency deteriorates less when exposed to the weather due to the glass resin protection of the interface.

2. Paper laminates based on unsaturated polyester, urea or melamine resins: 24 68857 (a) Surface gloss increases.

b) Surfaces are less sensitive to contact compared to melamine resins.

C) The effect of the high transparency of the UP thin layer gives the impression of a surface coated with a clear lacquer.

The thin layer itself must be applied to a support (e.g. foil) before the laminate is made. In this case, a 20 to 200 μm thick UP resin layer is applied to the separation foil, which is then UV-cured. Complete curing occurs next when the laminate is cured.

Thin layer fabrication according to conventional methods has the following disadvantages: a) When curing with organic peroxides in heat, high styrene losses have to be accounted for, so that there is a risk of undercuring.

b) Curing with peroxide and accelerator, although reducing the loss of styrene, reduces the working time (30-60 min) and the specific color of the mold caused by the accelerator (Co-salts).

c) UV curing with known photoinitiators results in yellowish thin layers; yellowing intensifies even more when exposed to the weather. The mold masses according to the invention do not suffer from the described disadvantages of other methods. On the contrary, rapid UV light curing results in almost colorless thin layers which do not turn yellow in daylight or artificial light.

3. Immersion coatings For use in casting resins that can be used, for example, for coating electronic components, the new sensitizers are excellently suitable. When coating opaque objects, even, all-round lighting must be provided.

The parts and percentages mentioned in the examples are calculated by weight, unless otherwise stated. Volume parts relate to parts like liters to kilograms.

The examples and comparative examples were performed using the following unsaturated polyester resins:

Resin A is a styrene solution of an unsaturated polyester formed with 0.01% hydroquinone from 65% maleic acid, o-phthalic acid, ethylene glycol and propylene glycol-1.2 in a molar ratio of 1: 2: 2.4: 0.70. The unsaturated polyester has an acid number of 50.

Resin B is a styrene solution of an unsaturated polyester formed from 67% maleic acid, tetrahydrophthalic acid and diethylene glycol in a molar ratio of 1: 0.5: 1.5 stabilized with 0.01% hydroquinone. The unsaturated polyester has an acid number of 43.

Resin C is a styrene solution of an unsaturated polyester formed from 66% maleic acid, o-phthalic acid and propylene glycol-1.2 in a molar ratio of 1: 0.5: 1.5 stabilized with 0.01% hydroquinone. The unsaturated polyester has an acid number of 50.

Resin D is a styrene solution of an unsaturated polyester formed in a molar ratio of 1: 0.67: 0.72: 1 from 65% maleic acid, isophthalic acid, propylene glycol-1,2 and diethylene glycol in a molar ratio of 0.01%. The unsaturated polyester has an acid number of 26.

Resin E is a styrene solution of an unsaturated polyester formed in a molar ratio of 1: 1: 1.7: 0.35 from 65% fumaric acid, adipic acid, neopentyl glycol and propylene glycol-1,2 in a molar ratio of 1: 1 with 0.01% hydroquinone. The unsaturated polyester has an acid number of 17.

Resin F is a mixture of 55% resin A and 45% 0.01% hydroquinone stabilized styrene solution of maleic acid, adipic acid, propylene glycol-1,2 and diethylene glycosate in a molar ratio of 1: 0.5: 0.55: 1. with an acid number of 30.

Resin G is a styrene solution of an unsaturated polyester formed in a molar ratio of 1: 0.25: 1: 0.25 from maleic acid, o-phthalic acid, propylene glycol-1,2 and diethylene glycol in a molar ratio of 1: 0.25% with hydroquinone. The unsaturated polyester has an acid number of 43.

Resin H is a styrene solution of an unsaturated polyester formed in a 1: 1: 2 molar ratio of 65% maleic acid, o-phthalic acid and propylene glycol-1.2 stabilized with 0.01% hydroquinone. The unsaturated polyester has an acid number of 52.

Resin J is a styrene solution of an unsaturated polyester 26 6 8 8 5 7 formed in a 1: 2: 3 molar ratio of 65% maleic acid, o-phthalic acid and propylene glycol-1.2 stabilized with 0.01% hydroquinone. The unsaturated polyester has an acid number of 30.

Resin K is a commercial vinyl ester resin Derakane 411-45, manufactured by Dow Chemical Co., Midland, Mich. U.S).

The following compounds of the prior art were used as UV sensitizers in the comparative examples: I benzyldimethyl ketal II benzoin methyl ether III benzoin isopropyl ether IV methylolbenzoin methyl ether.

The examples of the invention were carried out using the following acylphosphine oxides and acylphosphinic acid esters: XVI 2-Methyl-2-ethylhexanoyl-diphenylphosphine oxide XVII 1-Methyl-cyclohexanoyl-diphenylphosphine oxide XVIII Pivaloyl-phenylphosphinic acid methyl ester XIX Pivaloyl-phenylphosphinic acid isopropyl ester. The following acylphosphine oxides were used as highly effective UV sensitizers: XX 2,4,6-trimethylbenzoyl-diphenylphosphine oxide XXI 2,6-dimethoxybenzoyl-diphenylphosphine oxide XXII 2,6-dichlorobenzoyl-diphenylphosphine oxide XXIII 2,3,5,6-tetramethyl-tetramethyl 4,6-trimethylbenzoyl-fenyylifosfiinihappometyy-ester.

The acylphosphine oxide compounds used according to the invention were prepared as follows:

Pivaloyl diphenylphosphine oxide X.

To a mixture of 1350 volumes of petroleum ether (boiling range 40-70 ° C), 180 volumes of N, N-diethylaniline and 67 volumes of methanol are added with stirring at 0 ° 225 parts of diphenylchlorophosphine dissolved in 220 volumes of 68857 petroleum ether. The mixture is then stirred for a further 2 hours at room temperature. After cooling to about + 5 °, the separated amine hydrochloride is filtered off with suction and the filtrate is then distilled at 1.3-2.6 kPa to remove any boiling matter. Methoxy-diphenylphosphine is then fractionally distilled at 13.3 to 133 Pa. Kp60120 - 124 ° C. Yield: 175 parts (80% based on diphenylchlorophosphine).

64.8 parts of methoxy-diphenylphosphine are added dropwise to 36.2 parts of pivaloyl chloride with stirring at 30-60 ° C. When the addition is complete, the reaction is allowed to proceed for a further 30 minutes, cooled to 0-10 ° C and the precipitated product is crystallized from cyclohexane.

Yield: 69.5 parts of pivaloyl diphenylphosphine oxide (81% of theory).

Sp. 110-112 ° C, NMR (CDCl 3, δ f), 1.33 (s), 7.4 - 8.0 (m).

Analysis for C 17 H 18 O 3 (286): C 71.33 H 6.64 P 10.84.

found: C 70.0 H 6.5 P 11.0.

p-toluyl-diphenylphosphine oxide XI

To 77 parts of toluic acid chloride is added 108 parts of methoxy-diphenylphosphine (as described above) dissolved in 200 parts by volume of toluene. It is then heated for 60 minutes at 50 [deg.] C., then cooled, the toluyldiphenylphosphine oxide is filtered off with suction and recrystallized from cyclohexane. Yield: 117 parts (73% of theory), m.p. 105 ° NMR (CDCl 3, δ f) 2.35 (s); 7.2 - 8 (m).

Analysis (-2ο ^ 1702 ^ (320) calculated for C 75.00 H 5.31 P 9.69 found C 75.3 H 5.8 P 9.3.

4- (tert-butyl) -benzoyl-diphenylphosphine oxide XII

In analogy to X, 41.3 parts of p-tert-butylbenzoic acid chloride are reacted with 45.4 parts of methoxydiphenylphosphine dissolved in 20 parts of toluene at 50 ° C for 90 minutes. After evaporation of the solvent on a rotary evaporator, it is recrystallized from cyclohexane.

Yield 63 parts (83% of theory) m.p. 136 ° C

NMR (CDCl 3, δ): 1.3 (s); 7.3 - 8.1 (m); 8.5 (d)

Analysis for C23 H23 P 2 362 Calculated C 76.24 H 6.35 P 8.56 Found C 76.0 H 6.5 P 8.7.

28 68857

Terephthaloyl-bis-diphenylphosphine oxide XIII In analogy to XI, 52 parts of terephthaloyl acid dichloride dissolved in 200 parts of toluene and 108 parts of methoxydiphenylphosphine are prepared from 46 parts of terephthaloyl-bis-diphenylphosphine oxide. (Yield 35% theoretical), m.p. 205 ° C.

NMR (CDCl 3, tf): 6.8-8.2 (m).

Analysis for C 32 H 24 O 4 ^ 2 ^ 53 ^ calculated C 71.91 H 4.49 P 11.61 found C 71.8 H 4.8 P 11.0.

2-Methylbenzoyl-diphenylphosphine oxide XIV In analogy to XI, 77 parts of 2-methylbenzoic acid chloride and 108 parts of methoxydiphenylphosphine are prepared in 134 parts of 2-methylbenzoyl-diphenylphosphine oxide.

(Yield 84% of theory), m.p. 107 ° C.

NMR (CDCl 3, tf): 2.5 (s); 7.2 - 8 (m); 8.8 (m)

Analysis for C 2 C) H 17 O 2 P (320) calculated C 75.00 H 5.31 P 9.69 found C 74.7 H 5.4 P 9.5.

V eratoyl-diphenylphosphine oxide XV In analogy to X, 43.2 parts of methoxydiphenylphosphine are added dropwise at 50 ° C to 35.3 parts of 2,2-dimethyl-heptanecarboxylic acid chloride (Versatic acid chloride). Stir for 3 hours at 50 ° C, cool to 15 ° C and stir the mixture into a slurry containing 60 g of silicic acid in 350 ml of toluene, stir for a further hour under ice-cooling. It is then filtered off with suction and the solvent is distilled off under reduced pressure. Versatoyl diphenylphosphine oxide remains as a viscous oil.

Yield: 62 parts (90% of theory).

NMR (CDCl 3, δ): 0.4 - 2.3 (m); 3.6 - 8.1 (m)

Analysis for C 21 H 22 O 2 P (342) calculated for C 73.68 H 7.89 P 9.06 found C 73.6 H 8.1 P 8.6.

2-Methyl-2-ethylhexanoyl-diphenylphosphine oxide XVI In analogy to X, 88 parts of 2-methyl-2-ethyl-hexanoic acid chloride and 108 parts of methoxydiphenylphosphine are obtained as 165 parts of 2-methyl-3-ethyl-hexanoyl-diphenylphenylphosphine phosphine. Column chromatography on silica gel 60 (eluent: toluene / ether 3: 1) gives the product as a slightly yellowish oil. Yield: 154 parts (90% of theory).

29 68857 NMR (CDCl 3, δ): 1.2 (s); 0.5 - 2.2 (m); 7.3 - 8.1 (m)

Analysis for C 23 H 18 N 2 O 3 (342) calculated C 73.68 H 7.89 P 0.06 found C 73.9 H 8.1 P 9.4.

1-methyl-cyclohexanoyl-diphenylphosphine oxide XVII

According to the procedure of XI, 80 parts of 1-methyl-1-cyclohexanecarboxylic acid chloride and 108 parts of methoxydhenylphosphine without solvent are obtained, 100 parts of 1-methyl-cyclohexanoyl-diphenylphosphine oxide as an oily crude product (eluted with silica gel), which is purified by chromatography on silica gel. Yield 42 parts (26% of theory) m.p. 80 ° C.

NMR (CDCl 3, δ δ): 14 (s); 1.1 - 1.6 (m); 2.1 - 2.4 (m); 7.3 - 8.0 (m)

Analysis calculated for C 73.62 H 7.06 P 9.51.

found C 73.3 H 7.1 P 9.6.

Pivaloyl-phenylphosphinic acid methyl ester XVIII

To a mixture of 1000 parts by volume of toluene, 421 parts by volume of Ν, Ν-diethylaniline and 100 parts by volume of methanol is added at 0 ° C 214 parts of phenyldichlorophosphine. It is then stirred for a further 1 hour at room temperature, the amine chloride precipitate is filtered off with suction and distilled fractionally. Dimethoxyphenylphosphine distills at 46-50 ° C / 27-40 Pa.

Yield 190 parts (93% of theory).

110.5 parts of dimethoxyphenylphosphine are added dropwise to 78.7 parts of pivaloyl chloride at 15 ° C. It is then heated for a further 30 minutes at 50 ° C and then the reaction mixture is distilled. Pivaloylphenylphosphinic acid methyl ester distills between 104-107 ° C / 40 Pa.

Yield: 101.3 parts (65% of theory) NMR (CDCl 3, δ): 1.3 (s); 3.75 (d); 7.4 - 8 (m).

Pivaloyl-phenylphosphinic acid isopropyl ester XIX

A mixture of 600 volumes of petroleum ether, 263 parts of Ν, Ν-diethylaniline and 120 parts of isopropanol is added dropwise over 143 hours at 0 ° C to 143 parts of phenyldichlorophosphine. It is then stirred for a further 1 hour at room temperature and distilled after further work-up as described in Example 1. Diisopropoxyphenylphosphine distills between 68 and 72 ° C / 40 Pa. Yield 126 parts (69% of theory).

158 parts of diisopropoxyphenylphosphine are slowly added to 84 parts of pivalic acid chloride at 50-60 ° C. Stir for a further 2 hours 68857 30 n and distill off its fractions in vacuo. Pivaloylphosphine acid isopropyl ester distills between 119-121 ° C / 67 Pa.

Yield: 112 parts (60% of theory).

NMR (CDCl 3, δ) 125 (s); 1.33 (t); 4.5 (m); 7.3 - 8 (m) Analysis: C 11 H 18 O 3 P (268): calculated C 62.68 H 7.84 P 11.57 found C 63.0 H 8.0 P 11.4.

2,4,6-Trimethylbenzoyl-diphenylphosphine oxide XX In a stirrer equipped with a reflux condenser and a dropping funnel, 648 parts of methoxydiphenylphosphine are slowly added to 547.5 parts of 2,4,6-trimethylbenzoyl chloride at 50-55 ° C. Stir for a further 4-5 hours at 50 ° C, dissolve the contents of the flask at 30 ° C in ether and add petroleum ether until turbidity begins. On cooling, 910 parts (87% of theory) of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide crystallize out. Sp. 80-81 ° C, pale yellow crystals.

2,6-Dimethoxybenzoyl-diphenylphosphine oxide XXI In the apparatus described for the preparation of initiator XX, 20 parts of 2,6-dimethoxybenzoyl chloride are suspended in 20 parts by volume of toluene and 21.6 parts of methoxydiphenylphosphine are added dropwise to this mixture at 50-55 ° C with stirring. Stir for a further 3 hours at 50 ° C and then crystallize directly from toluene. 32 parts of yellowish crystals are obtained, m.p. 124-126 ° C.

Other highly potent initiators synthesized by analogous preparation can be found in Table 2.

31 6885 7

CD

r-ι c- ~ r- cd cm D-. cdcdj-cncshcoj- -

rt a r * rs λ λ rv rv CD

oooo αοαο oooo οοοο H

en 00 CD C- 'cd cd (H

pi, OHrHJ-J- ^ CDLD CS -

^ pC rv n rv rv r rv rv rv rv O

, - | CDCDCDlDOOOOCDCD CD ι I

(ti g Ή H en <

•B

C/O

• H CD LO zT LO

trt CO O CO Γ- COCD C \ J CM lOlO

f * rvrvrvrvrvrvrvr r. rv c LOLO COCO O O CO CD Γ- * Γ ***

fjj r ^ -O-aDcDCDcDC ^ r ^ COCO

S 3 p p 3 p o h -P -P -μ h ro + j + -> -M + J + ->

μ O og op (Uppo OP

x) 2 H 2 -P 2 -P 2 -μ 2 -P

H cnrejcngcngcng en O

en 00 00 00 00 Hi S

X HcnHcnHcnHcn H en

• S

e * cd en lo

• H pH CM LO CM CM

• H · Λν. CO i — li — I r-H LO

<-H PiC-? I I I I I,

en co O o zt zt co H

o 00 OM LO CM LO

4- ^ ι — I ι — I ι — I

I-I

£ CO · ^ rt Ά rt X, Dh

rÖ - 1111 I

+ -> en

"B

> 0 o

| J 4-) dP o \ ° öP o \ ° dP

μ H t- ~ oo es co H

, 2 m oo co oo cd oo

S

5.

: n3, rj

4-> I H

-μ -H> v HHII · Η δ & · Η Ά '· υ Η · Η -'η ·' η 8 1 * 8¾ & 'Sj V q 2 8 ο 8-3 -Pc, qg 2 So -μ · η -μ q ο ο Hi 1 ag s .s S3 ssr-a $ · 1 I $ 3 a «.¾¾ erg ¢ 3¾

• h Sim cnen P o OH 2 OHO

en -pen 20 OH -mho E »P

W g ο o H Q Η ι>, H h p ω

B H H H H eo q p H O

I · Η H (UH 2> ι - O H -Ρ · Η · Η

PH S> v H>, vocn-H I H H

es -P> v -a £ ό e? «Ym cD ^, ^ iS tl G ι S oo q en"> 1 po

fcöp | O cd H -OO J CP

- O CD H -h es, Q H «O O (4-1 -H es X) Cd p g

- • H and Ό H

3 ° - m m H H B

s s s a s s 32 68857 UV curing activity

To measure curing activity, temperature changes in unsaturated polyester resin (UP resin) or vinyl ester resin during UV exposure were recorded; For this purpose, a wax-coated thermal detector connected to a temperature printer (Tastotherm Script 3 N, standard detector T 300 from Deutsche Gulton GmbH) was immersed in a 10 g UP resin-filled tin-plated cap with a diameter of 5 cm (UP resin layer). 4.8 mm). To avoid heat loss during UV exposure, the hat was embedded in polyurethane rigid foam. The radiation source was a UV field from 5 parallel fluorescent tubes (TLAK 40 W / 05, Philips). The distance between the radiator / UP resin surface was 8.5 cm.

From the recorded temperature-time curves, the curing time HZ25 ° C-T was taken as the characteristic parameters for the curing activity.

»ΤΠΑ V c and maximum curing temperature T · The curing time is the period during which the temperature of the sample rises from 25 ° C to T. .

max

Example 1 Preparations containing 0.2% of various sensitizers from resin C were cured with UV light as described above.

A comparison of the curing activity (Table 3) shows that the initiator X according to the invention has the fastest possible curing; followed by benzyldimethyl ketal (I) as the most preferred of the literature and partly commercial products. The following comparative experiments were therefore worked primarily using this initiator X.

33 68857

Table 3 UV curing of resin C containing 0.2% of different sensitizers in a 4.8 mm thick layer UV sensitizer HZ 0 (> T Tmax

imin / s / x J

I 8/10 123 II 10/25 119 III 11/50 110 IV 10/00 123 X 7/15 125 3 “68857

Example 2

Table 4. UV curing activity of sensitizers according to the UV invention compared to benzyldimethyl ketal (I)

Resin Sensitizers% H2oco „m T

25 C-T night r- max r- |

[min / sj [_CJ

AX 0.2 5/36 122 XI 0.2 15/00 124 XI 0.35 15/15 122 XII 0.35 14/45 120 XIII 0.35 21/15 109 XIV 0.35 8/15 117 XV 0 , 2 13/45 90 XV 0.35 16/15 86.

XVI 0.2 15/15 90 XVI 0.35 16/00 88 XVII 0.2 10/40 96 XVII 0.35 11/05 98 XVIII 0.35 18/15 106 XIX 0.35 39/25 85 I 0 , 2 6/54 120 BX 0.2 5/50 127 X 0.35 4/40 126 XI 0.35 10/05 133 XVIII 0.35 13/00 112 I 0.2 5 / 3Ο 128 CX 0.2 7/15 125 XVIII 0.35 18/45 112 I 0.2 8/15 136 DX 0.2 5/45 123 I 0.2 8/00 128 EX 0.2 9/00 107 X 0.5 9 / 00 102 I 0.2 13/00 102 I 0.5 11/15 89 PX 0.2 7/15 111 I 0.2 10/30 127 35 68857

Example 3 UP resins containing a UV absorbent are used to prepare UV-stabilized sheet materials, e.g., thin layers or clear sheets. These additions can affect the UV curing rate. The following experiments show how strong this effect is.

Preparations of resin A, commercial UV absorbers (0.1%) and 0.2% sensitizer I or X in each case, were cured by the described reactivity measurement using fluorescent tubes. The results in Table 5 show that UV-absorbent formulations are expected to be slower to react than UV-unstabilized formulations. At the same time, however, it is found that the preparations according to the invention harden much faster than those containing sensitizer I.

Table 5. UV curing of light-stabilized resin A preparations

Sensitizer UV stabilizer HZ „co ,,„ T,

(0.2%) <0> 1%) A * / s / W

5/36 122 X ®Cyasorb UV 5311 2 ^ 14/00 97 ®Sanduvor EPU2) 10/30 117 I ____ ____—-—— ^ 6/5 ^ 120 I Cyasorb UV 531 33/15 39

Sanduvor EPU 20/00 110

Manufacturer: American Cyanamid 2

Manufacturer: Sandoz 36 68857

Example 4

To indicate the effect on the UV curing rate of mineral filler additives, Resin A, sensitized with 0.2% initiator X, was UV cured in the presence of various fillers (radiation source: fluorescent tubes TUV 40 W / 05, Philips). According to the described measurement method, the recorded temperature-time curve produced the values of the curing time and the maximum curing temperature.

The results of these studies are shown in Table 6.

Table 6. UV curing of filler-containing resin A fillers Filler (%) ^ 2 5 ° C-T, ^ max Mat / si ma * s

Alumina hydrate (30) 7/50 117

Alartinal BM2) 1 2

Silicic acid (2) 8/30 129

Gypsum (CaSO 2 .2H 2 O) (30) 8/40 111

Barium sulphate (30) 8/40 87

Quartz powder (30) 6/00 112

The film thickness of the molds (wheels) was 4.8 mm.

2

Manufacturer: Martinswerke, Bergheim / Erft

Example 5

The curing activity of the resin A preparations according to the invention was also determined by means of long-wave radiation of a lamp equipped with sodium iodide (HRI, 2000 W "Power-Star"). In contrast to the described method, the distance of the lamp from the substrate surface was 60 cm.

Table 7. UV curing of mold masses according to the invention at an initiator content of 0.2% 37 6 8 8 5 7

Sensitizer ^ Z25 ° C-T ^ max Color of mold mass max I 9/00 140 strongly yellowed X 6/45 142 water clear XI 9/25 145 water clear XII 10/55 170 water clear XV 13/10 120 water clear XVIII 14/10 135 water clear

The molding materials made from the pulps according to the invention are not yellowed compared to the benzyldimethyl ketal contents (I).

Example 6

Preparation of glass fiber reinforced UP mold masses a) Resin A (preparations containing 0.15% benzyldimethyl ketal (batch 1) or 0.15% pivaloyl diphenylphosphine oxide (batch 2)) was prepared from 5 and 100 mm thick glass fiber tolaminates and irradiated with UV-cast T 40 W / 05, Philips) at a distance of 11 cm. After the specified exposure times, the Barcol hardness of the opposite laminate surface of the light source was measured (Barcol-Impressor, Model 934-1). The results are summarized in Table 8.

38 6 8 8 5 7

Table 8. UV curing of GF-UP laminates

Exposure time 5 No. laminate Exposure time 10 No. laminate <-y Barcol hardness <,> Barcol hardness Ο * 11 * 1? Not 1 Lot 2 VitLn / jj? Ax / Mi Lot 2 14 0 0 45 0 0 16 0 4-6 50 0 2-4 18 0-4 12-20 55 0 4-20 20 0-10 25-30 60 0 10-20 25 6-15 3 ^ -38 70 0 20-35 30 20-30 42-46 80 0 25-35 35 28-35 - 100 0 28-37 40 35-45 b) For curing with a mercury vapor high-pressure radiator, batches were prepared 1 and 2 9 mm thick carpet laminates (glass fiber content 39%) for polyester foil and were drawn on a drawing table at a distance of 35 cm under UV radiators. The effective exposure time was 3 minutes, the thickness of the laminate was 9 mm.

If, after the molding materials had cooled, the Barcol hardness was determined on the side opposite the radiator, the initiator according to the invention (pivaloyl-diphenylphosphine oxide X also proved to be superior to benzylide-methyl ketal CI). The barcol hardness in lot 2 was 50, in lot 1 zero.

Example 7 UV curing of clumps made of UP resin A a) In glass plate molds (16 x 11 x 11 cm) with inner foil surfaces covered with yellow foil, 1800 g of resin A-catalyzed on the other hand with benzyldimethyl ketal (I; 0 .05%), on the other hand, with pivaloyldiphenylphosphine oxide (X, 0.05%). Fluorescent tubes (TUV 40 W / 0.5, Philips). In this case, the experimental arrangement was such that UV light (from a field of 10 parallel lamps, 87 x 49 cm) could penetrate through the glass base plates into the resin preparation. The distance between the lamp / mold was 17 cm, the layer thickness to be cured was 9 cm · 39 68857 These experiments clearly showed that the sensitizer system according to the invention allows substantially faster through-curing than benzyldimethyl ketal. When a chelating mold material is obtained with benzyl dimethyl ketal after exposure for 9 hours, the upper layer of which is still flowable, according to the invention, the preparation results in a clear cured mold material after exposure for 1 1/2 hours.

b) In the following experiments, the dependence of the cured layer thickness of different resin preparations on the exposure time was measured. For this purpose, sensitized mixtures of resin A and photoinitiators were exposed in each case in a crystallization dish (diameter: 9 cm), the side walls of which were covered with UV-impermeable paper (Tesakrepp), fluorescent tubes (TUV 40 W / 05, Philips) from above. The distance of the resin surface from the radiation source was 11 cm.

The narrow vertical viewing opening in the wall covering allowed the curing process to be followed into the deeper layers. The boundary between the cured and uncured resin layer was easily known due to different refractive indices. The results are summarized in Table 9.

When benzyl dimethyl ketal cured at only 18 62 mm in 80 minutes, the result was 62 mm for pivaloyl diphenylphosphine oxide (X), i.e. the whole lump. The addition of tert-butyl peroctoate shortened the curing time to 30 minutes.

68857 ι + Ο

Table 9. UV curing of thick film resin preparations

Composition Coke film- Cured thickness Exposure time film thickness (mm] [min]

_M

Resin A 62 10 8 20 14 + benzyldimethyl-ketal (0.15%) gjj Jg

Resin A 62 10 13 20 21 + Pivaloyl diphenyl-28 phosphine oxide) 55 55 80 62

Resin A 60 10 18 + Pivaloyl diphenyl phosphine oxide 30 60 (0.15%) + tert-butyl perchoate (0.15%)

Resin A ^ 5 10 7 + Versatoyl diphenyl-phosphine oxide (XV) 30 14 (0.2%) 60 18 120 45 1) 0.187% of 80% initiator triturated with dibutyl phthalate was added.

i + l 6885 7

Example 8 To evaluate the yellowing of UP resin moldings due to light, 4.8 mm thick spheres (5 cm in diameter) were cured from different resins sensitized with 0.2% UV initiator by exposure to fluorescent tubes (TUV 40 W / 05, Philips) and subsequently exposed to 40 minutes of radiation from a field of 10 fluorescent tubes of the same type at room temperature. The distance of the radiation source from the surface of the wheel was 11 cm.

Yellowing was assessed by the Yellownes index according to ASTM D 1925-67. The measurement was performed using a Zeiss DMC 25 instrument.

It is clear from the results of Table 10 that the moldings made from the preparations according to the invention are in all cases less yellowed than from the known preparations (containing sensitizers I to IV).

4 2 68857

Table 10. Yellowing of .UV-cured mold masses made from different UP resins UP resins UV sensitizer Yellowness index (0.2%) Al 5.74 II 5.43 III 5.33 IV 4.21 X 2.84 XI 2.59 XII 1.82 XVIII 2.61 XV 2.75 XVI 2.87 BI 10.84 II 9.18 III 6.10 IV 5.93 X 3.81 XI 4.93 XII 3.73 XVIII 5, 38 FI 7.28 II 5.62 III 4.83 IV 5.55 X 3.37 XI 3.39 XII 3.37 XVIII 3.58 EI 13.37 X 6.00 43 68857

Example 9

To ensure that the sensitizers according to the invention likewise produce less colored products when UV-curing peroxide-containing mold compositions, preparations of resin A, tert-butyl peroctoate and sensitizers I, II and X were exposed in a UV-permeable mold (5.3 x 3.4 x 1 , 45 cm) with fluorescent tubes (TUV 40 W / 05, Philips) at a distance of 15 cm for 25 minutes. Next, the cooled clumps were exposed to the same UV light for 1 hour at room temperature.

The mold wave containing sensitizer X has the Lowest Yellowness Index, it is also the least yellowed (Table 11).

Table 11. Yellowing of peroxide-containing UV-cured resin A moldings

Sensitizer Tert-butyl peroctoate Yellowness index (0.35%) /% / I 0.05 6.04 II 0.1 5.10 X 0.1 3.37

Example 10

Manufacture of a thin layer that can be pressed onto paper laminates or GRP surfaces.

By way of example, a preparation of resin A, 0.5% of sensitizer X and 1% of benzoyl peroxide, a film having a thickness of about 100 μm was coated on a separation foil and transported under a mercury vapor high-pressure lamp at a rate of 1 m / min. The distance between the lamp / foil © was 25 cm. The thin layer thus cured could be heat pressed on a paper laminate or GRP surface. The thin layer was not yellowed.

In the following Examples 11-17, particularly preferred highly reactive UV sensitizers were used.

Example 11

Preparations of UP resins A, C, G, B and vinyl ester resin K containing 0.2% of different sensitizers were cured with UV light as described above.

A comparison of the curing activity shows (Table 12) that the initiators XX to XXIV have the fastest cures possible. Although pivaloyl-phenylphosphine oxide achieves the activity of 2-dichlorobenzoyl-diphenylphosphine oxide (χχχχ), its activity decreases over time when stored in UP resins.

Table 12. UV curing of sensitized UP resins and vinyl ester resin by exposure to fluorescent tubes UP resin or UV initiation HZ25 ° CT max 'vinyl ester max resin (0.2%) Γ "1 lmin / s | AX 8/00 li2 »CI 9/45 119 GI 10/15 123 BI 8/30 122 KI 15/53 63 ~~ A XXX" 13/22 hit C III 13/07 109 G III 13/15 114 B III__11 / 13__. 1 ° 8_ “Ϊ7 13/22 nights G XV II / 30 117 G IV 11/15 123 g XV 9/08 122” 7 x '7/30 107 C x 6/45 116 GX 6/38 123 BX 5 / 3Ο 123 A XX 4/30 125 C XX 4/00 129 G XX 3/38 127 B XX 3/15 127 K XX ._ 3/35 92 145 68857

Table 12 (continued) UP resin UV initiator ^ 25 ° CT ^ mak [° vinyl ester max s resin, r-, (0.2%) £ min / sj A XXI 5/23 120 C XXI 5/00 123 G XXI 4/25 132 B XXI 4/15 125 K XXI 6/30 91 A XXII 7/08 105 C XXII 6/35 m B XXII 5/51 ii5 K XXII 10/45 72 A XXIII 5/15 102 C XXIII 4/45 119 B XXIII 4/36 122 K XXIII 6/30 87 A XXIV 6/15 94 C XXIV 4/38 110 K XXIV 7/38 91

Example 12

Preparations of UP resins A or B and various UV initiators were stored in sealed containers at 60 ° C and then cured activity was measured at room temperature - as described in Example 11.

Table 13 shows the measurement results before and after storage. They show very clearly that the activity of initiators XX to XXIV has remained unchanged under the experimental conditions. Storage experiments over a longer period of time at room temperature also show this direction (Table 14).

te 68857 (Ti m £ tn 0) tn

ju X

υ H §1 o 'en aj r- o cn> λ ai o ov ai

: (tj .O. nnjtM ai aj om O O coO

^ * ('E- · 1 rl H rl H rl rH rH rH

«I

<u a

C -H

• HO CO

e -h m • H S 9 * 2 e_s t! ί I .-. O r * 'rAco O o Aj no

fj ^ O W 1 O LA CM n ΗΛΟ LA - ^ - O

ω O - v x -x v x x -x n x

(- p LA C IA- = T LA ΗΛ A-MO - = T MO MO

s e N ~ -ä tn> ", E, sa - -μ es>: • H 1> d tn .b

3 O I — I MO MO MO VO MO OO o o O

-μ -p X O LO MO Ό MO H— C “- A- A- A-

0) tn 1 M

| §5 rd

-B

13 'S 1 O 1 LA LA t— OMA LA IA AJ O

tl g. O AJ AJ AJ H (M O H O CA tH

fd Eh 1 H rl H rl rl rl rl rH rH

f α § o. a) o ω

O a) 3 M

x «> 5 g C! 1 I ω .μ (U: r0 St E- ·

π · π £) · Η I, -. O O LA OLA CO H LA LACO

>. bring OIcqI ΓΛΙΛΗ OJ rH OLA rH H A

-PC?] R OM MMM Mm mm m m M

+ - * 0> »fä LAC · ΐΓ · = Χ ΗΛ LA- = T A- LA LA MO ~

(U tn | Ai -H

-P -H p> ro is, £,

tn S _>> x I I

• H * H

X o .H

b + -> m tu tn -p o: m h

I P Q

> ^ i <<ö <ccq <ca <<< o 3> δ co -p

rH rcJ

fd

O -H

X P> Ή ^ ^ · Η U x »b C O **. m H-H-PfM MM M>>

2 · * MH M M H MM

5 m XXX XX XX X XX

t- <W XXX XX XX X XX

1 + 7 68857

Example 13

Preparations from UP resins A or B and various UV initiators were stored in closed containers at room temperature and in the dark, and the curing activity was measured from time to time by the method described in Example 11. The results in Table 14 show that initiator XX provides storage-resistant UV-curable UP resins.

Table 14. Investigation of the curing effect of UV-sensitized UP resins at room temperature after storage UV initiator [%] χχ (0.20) XX (0.35) UP resin

A A

Storage time [X] 0 0 HZ25 ° C-T. , [min / sj 4/30 5/38

max rQ η J

T, L CJ 118 118 max

Storage time [dj 83 63 HZ25 ° C-T, [inin / s] 4/00 6/00 t L ° c] 113 106 max

Example 14 To evaluate light-induced yellowing of UP resin moldings, 4.8 mm thick spheres (5 cm in diameter) were cured from UP resins A, H and J sensitized with different UV initiators, illuminated with fluorescent tubes (TL AK W / 05, Philips) and they were then exposed to the same light source (5 fluorescent tubes in parallel) for 60 or 120 minutes at room temperature. The distance from the radiation source 'to the surface of the wheel was 8.5 cm.

Yellowing was evaluated using the Yellowness Index according to ASTM D 1925-67. The measurement was performed by looking at a Zeiss DMC 25.

It is clear from the results in Table 15 that the mold materials from the preparations according to the invention are in all cases less yellowed than the mold materials from the known benzyldimethyl ketal (I) -containing preparations.

48 68857

Table 15. Yellowing of UV-cured UP resin mold materials UP resin UV initiator Exposure time

Yellcwness- [%] [mirij index HI (0.2) 60 13.18 HI (0.2) 120 14.56 JI (0.2) 60 13.88 JI (0.2) 120 16.38 H XX (0.2) 60 3.78 H XX (0.2) 120 4.19 J XX (0.2) 60 3.82 J XX (0.2 120 4.19 A XXI (0.2) 60 3 .08 A XX (0.15) 60 2.87

Example 15 UV curing of UP resin mold masses a) 50 parts of preparations of UP resin G containing 0.1% UV initiator XX or 0.1% benzyldimethyl ketal (I),

D

was mixed with 40 parts of filler Martinal BH 2 (Al 2 Oj.SH 2 O, Martinswerke, Bergheim / Erft) and 1.5% magnesium oxide "light" (manufactured by Merck, Darmstadt) (measured from UP resin). These mixtures were impregnated with several layers of glass fiber mats (^ Vetrotex Textilglasmatte M 123-40-450) measuring 10 x 12 cm, allowed to thicken for three days at room temperature between polyester foils and finally cured by exposure to fluorescent tubes (TL AK W / 05), followed by thermocouple muottimassassa. The distance from the radiator (5 fluorescent tubes in parallel) - the surface of the mold mass was 8 cm; the exposure time followed the time when the mold mass had reached its maximum curing temperature.

After cooling the mold masses, the Barcol hardness (Impressor 935) on the lower and upper surfaces was determined.

From the results in Table 16, the advantages of the preparation containing UV initiator XX according to the invention can be seen quite clearly. With three layers of fiberglass mats - corresponding to a layer thickness of 3.8 - 4.5 mm - 68857 - an exposure time of 5 min 15 s is sufficient, with a layer thickness of 6.6 - 7.2 mm (= 7 layers of fiberglass mat) an exposure time of about 13 min is sufficient to achieve sufficient curing through. In the case, the benzyl dimethyl ketal (I) -based mold mass, despite doubling the exposure time, does not achieve through-curing of the laminate with 7 layers of fiberglass mat.

50 68857 d ω ι μ d · μ 3 H) d en en o

p r — I · Η I I ι — I

? H) ft CM LO I

0 σ> oo o X \ \ ι — I - ^ rd it <X) to O I -M en en cn

0: d ft II I

ft ι — I · Η CN H it CO> i (¾ σ> σι en co Ρ -μ α> en> Ρ ο ρ λ; -μ ω ο-, ι Ρ X ο

> C d LO

; π Ρ ρ, ^ and ro σ f Μ £ «« * ι G μ Ο Ε σ ο ο Ο QJ ft ν- 'ιι = τ μ> ft 03 CO LO ι d o Q) ·> r> *> oo

E M fti 00 CO σ CM

• Η ^ ι — j

Cfl ft ss d ω ffi a) rG Λί μ rri O OO O CM μ μ ft EO o- oo cd o d 25 h - eg co μ c / 3 • Η μ rtf

d ft rH

μ ω B bo co M 2 h

ft co d '- / H

qj μ H o

Cl, O) I> - »CMd)

I> O CO K H

0 O O "m co LO o ro

J-> y, U-> q rftrH CM

μ ι cn tI ^ \ m ooq5 d;> n S LO oo lo ομ e e »M e- 'μ cm cmo 1 * 1

p I <* P CU

yo> • H μ μ co μ «> d G cm d μ e m · (->

3 d O

d μ -h »μ • ro -h co e μ Ρ X ro o- d fcM d S * 5 | 3 K ω ft «μ" ai g-g o ™ |.-S .CM ομ ι en H μ £ U d <C CO S μ ft

"ρ LO 00 CM JP dP

C9 C / 3 r \ * \ r

X. 3 * [> r-i OO

• H rri ^ #> en £ u & Il ι oo cd

-P to S 3 · H

μ p w co x> OD

rri C «n» s rQ C ro co co dj CL; X -n Ö g "'-H 5 | § co ft s g μ o -a 3 μ to μ ^ μ ^ ^ oo

1 -? S ^ H H

H H

68857 b) Rubbable, fiberglass-free UP resin mold masses were prepared by thickening for 3 days preparations of UP resin G, filler AljOg.St ^ O (Martinat BM 2. Martinswerke, Bergheim / Erft), 1.5% magnesium oxide "light" ( based on UP resin) and UV initiator XX or benzyl dimethyl ketal (I) (in each case 0.1% based on UP resin). The weight ratio of UP resin to filler was 60:40.

In the tinned sheet metal cover, a 2 cm thick layer was now exposed to fluorescent radiation (TL AK W / 05, Philips) for 35 minutes, during which time the temperature was monitored by means of a thermocouple immersed to a depth of 1 cm in the mold mass. The distance between the radiator / mold surface was 6 cm. After cooling, the undiluted lower layer of mold mass was removed mechanically and the Barcol hardness (Impressor 935) was measured after cleaning from the new upper surface thus obtained.

The molding compound according to the invention had a cured 12.6 mm thick layer, with the known molding compound containing benzyldimethyl ketal (I) only a 7 mm thick layer (cf. Table 17).

52 6 8 8 5 7 $ a, (Λ ro 2 γΗ ο g-5 7

O dj LO

XI -μ LD (Ώ ο · 5 χ χ o ί-ι: r0 γο οο rn, —I en σι

Cm> η ω Β to & ω en ο

3 S

ω δ

> X

ο ^

X -H S

ι 3 g to ρ> C ^ Λ 3 3 CM Ο st; -Η> 3 5 ω α)

• S

Its f -t-> ο ΐ S $ • Η ι rn is cm ω> S to j-

| j ^ H

s g '5 a

4- »M

H E

O

S o% O O

P H ^ Csl OJ

3 S

(/} <ö | * P-.

r f

H O

g 6 ~ s g * 5

3 -H H

^ · 1ηο X

OJ C '-y X M

H M

68857 53

Example 16

Preparations of UP resin A and UV sensitizer XX and I and their mixtures were irradiated in layer thickness with 10 mm fluorescent tubes (TL-AK 40 W / 05, Philips). The UP resin samples were 5 cm in diameter in tinned sheet metal lids that stood on a cork plate (5 mm thick) to prevent greater heat loss. The distance from the fluorescent tubes to the resin surface was 8 cm. After exposure and cooling, the rod was in each case sawed from the mold masses, extending to the entire layer thickness, and its residual styrene content was reported titrimetrically according to DIN 16 945. The results obtained are summarized in Table 18.

They show that the residual styrene contents in the mold samples containing the sensitizer combinations XX and I are lower than in the sensitizers XX and I alone.

Table 18 - Residual styrene content of UV-cured UP resin mold materials made of resin A

Example rryyppx ^ ”^ er '^ c ^" t ^ n Exposure time Residual styrene content Pamo », W (% by weight) calculated from the ___weight___ a XX 0.1 10 1.35 20 1 of components (a) and (b), 3 b XX XI 0.05 + 0.05 10 1.07 20 0.65 c XX + I 0.075 + 0.025 10 1.06 20 0.8 dl 0.1 10 Partly still running 20 1.15 f 54 68857

Example 17

The photocuring of unsaturated polyester resins can also be carried out using the photoinitiators according to the invention in two stages, in the first stage after a short exposure time a flexible, storage-resistant semi-finished product is formed which can be molded, cut and, for example, stamped in button making. With the renewed exposure, the final curing takes place in the second stage: a 0.1% solution of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (XX) in resin A was irradiated in a 2 mm thick layer between two polyester foils for 1 min with fluorescent tubes (TL-AK 40 W / 05 , Philips). The distance between the radiator and the top surface of the resin was 10 cm.

A flexible semi-finished product was obtained which could be easily cut with a sharp knife and simply molded by hand. The barcol hardness on both sides was 0 (Barcol-Impressor 935).

After 24 hours of storage at room temperature, protected from light, the unchanged flexible semi-finished product was cured again by fluorescence (exposure time: 15 min). The barcol hardness of the mold after cooling to room temperature was 87-89; it had become hard.

To avoid greater heat loss, the semi-finished product was on a foam sheet during exposure.

Claims (8)

55 68857 Claims. i. Photocurable molding, dipping and coating compositions comprising a mixture of a) at least one ethylenically unsaturated copolymerizable polyester, b) at least one ethylenically unsaturated copolymerizable monomer compound, c) an inhibitor, and optionally UV) d) paraffins, thermally decomposable initiators, fillers, reinforcing agents, glidants, inert solvents, shrinkage reducing agents and / or other unsaturated auxiliaries for use in polyester compositions, characterized in that the UV sensitizer consists of at least one PC of the formula R ^ L 0 \ » ), O 1! R 0 of an acylphosphine oxide compound wherein R 1 represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a cyclohexyl, cyclopentyl, aryl, halogen, alkyl or alkoxyl-substituted aryl, S or N-containing five - or a six-membered heterocyclic group; R 17 has the same meaning as R, wherein R and R may be the same or different from each other, or an alkoxy group having 1 to 6 carbon atoms, an aryloxy or arylalkoxy group, or R 1 and R 2 are bonded to a ring; 3 R denotes a straight-chain or branched alkyl group having 2 to 18 carbon atoms, a cycloaliphatic group having 3 to 10 carbon atoms, a phenyl or naphthyl group, an S-, O- or N-containing five- or six-membered heterocyclic group, where ... 3 the group R may optionally have other substituents, or the group 56 6 8 8 5 7 o, * 1 -XCP ^ ^ O ^ 'R2 1 2 wherein R and R: 11a have the meanings given above and X represents a phenylene group or 2 An aliphatic or cycloaliphatic divalent group containing -6 carbon atoms and 1 3 optionally one or more of the groups R to R are olefinically unsaturated. Photocurable molding, dipping and coating compositions according to Claim 1, characterized in that the UV sensitizer consists of one of the acylphosphine compounds of the formula I. . . 1 2 oxide compound, wherein R and R: 11 have the meaning given above 3 and R is a tertiary aliphatic group. Photocurable molding, dipping and coating compositions according to Claim 1, characterized in that the UV sensitiser consists of a single acylphosphine oxide-12 compound of the formula I, in which R and R 11a have the meaning given above and R represents a cycloalkyl group, a phenyl group, a naphthyl group, an S-, N- or O-containing five- or six-membered heterocyclic group containing substituents A and B bonded to at least both ortho positions relative to the carbonyl group, wherein A and B are the same or different, and mean alkyl, cycloalkyl, aryl, alkoxy, thioalkyl, carbalkoxy, cyano or halogen atoms. Photocurable molding, dipping and coating compositions according to Claim 1, characterized in that the UV sensitizer consists of an acylphosphine oxide compound of the formula I, wherein R and R 11a have the meanings given above and R is 2.4, 6-trimethylphenyl group. Photocurable molding, dipping and coating compositions according to Claim 1, characterized in that the acylphosphine oxide compounds are used in amounts of 0.005 to 5% by weight, based on the total weight of components a) and b). Photocurable molding compounds, dipping and coating compositions according to Claim 1, characterized in that they contain, as UV sensitisers, the acylphosphine oxide compounds of the formula I in combination with aromatic ketones, aromatic disulfides or naphthalenesulfonyl chlorides in a weight ratio of 85:15 to 15:85. 57 6 8 8 5 7 Photocurable molding, dipping and coating compositions according to Claim 6, characterized in that benzyl ketals, benzoin ethers or benzoin esters are used as aromatic ketones. Moldings and coatings, characterized in that they are made of the photocurable mold, dip and coating compositions according to claim 1. 68857 5 8