JPS608047B2 - Photocurable polyester resin composition - Google Patents

Description

[Detailed description of the invention]

Many types of compounds have been reported as sensitizers for photopolymerization of unsaturated polyester resins (UP resins). Using asyloin, asyloin ester or asyloin ether as a UV sensitizer, UV curing of UP resins can be achieved at a relatively long distance; The molded product becomes yellowish due to finish hardening. This undesirable yellowing is restored when the molded product is stored in a refrigerator, but it is exacerbated again by storage under sunlight or artificial light, and can be a serious hindrance when painting light-colored wood or when manufacturing light-transparent boards and corrugated boards. come. The yellowing of molded articles produced from UP resins containing penzoin ether can be reduced by the binding of trivalent phosphorus as described in DE 2104972 (US Pat. No. 3,669,022). However, it is still unsatisfactory to provide protection strong enough to develop said applications for UV curing. Penzyl ketal also provides highly reactive UP resins that are storable and UV curable;
It does not provide any improvement in imparting a desirable color to the molded article. The object of the present invention is to provide a light-curable molding compound, impregnating material and paint coating material which exhibits an inherently higher reaction rate with a color of the molded article equivalent to or better than that of ultraviolet curing compared to the state of the art. The aim was to develop a polyester resin composition. This problem is solved by the present invention. The present invention provides that the ultraviolet sensitizer has the following formula [where RI is a linear or branched alkyl group having 1 to 6 carbon atoms, or a cyclohexyl group, a cyclobentyl group, an aryl group, a halogen atom,
means an aryl group substituted with an alkyl group or an alkoxy group or a 5- or 6-membered S- or N-containing heliocyclic group residue, R2 has the same meaning as RI, in which case RI and R2 are the same RI and R2 may also be different, or mean an alkoxy group or an aryloxy group or an arylalkokyl group having 1 to 6 carbon atoms, or RI and R2
may be combined to form one ring, and R3 is 2 to 18
a straight-chain or branched alkyl group having 5 carbon atoms,
It means an alicyclic residue having 3 to IN carbon atoms, a phenyl group, a naphthyl group, or a 5- or 6-membered heterocyclic residue containing S, 0 or N, in which case R3 further represents a substituent. or the following formula (RI and R2 have the meanings given above and x is a phenylene group or an aliphatic or aliphatic divalent residue having 2 to 6 carbon atoms) and one or more of the groups RI to R3 may be olefinically unsaturated.'a} at least one ethylenically unsaturated copolymerizable polyester, 'b} at least one
Ethylenically unsaturated copolymerizable monomeric compounds of species,'
c-inhibitor, 'd-ultraviolet sensitizer and optionally

[
e-rayraffin, pyrolytic initiator, filler, reinforcing agent,
A photocurable polyester resin composition containing a mixture of lubricants, inert solvents, shrinkage control additives and/or other auxiliaries used in unsaturated polyester materials. The polyester resin composition according to the present invention is suitable as a molding material, an impregnation material, and a paint (coating material) for producing molded products and coatings (coatings), and it It is excellent in that it shows high reactivity upon irradiation. The essentially reduced yellowing tendency of the cured moldings and the rapid and complete curing, especially in thick layer molding materials containing glass fibers, are particularly advantageous compared to molding materials containing acyloin derivatives or pendylketal. It is. This is particularly advantageous when UV curing laminates finished by hand, by the winding method, by the centrifugal method or by the fiber jetting method. Similar favorable effects can also be obtained when a kneadable molding material that does not contain glass fibers is cured by ultraviolet light. A particularly preferred UV sensitizer is an acylphosphine oxide compound of formula 1, in which R3 is a cycloalkyl group, phenyl group, naphthyl group, S, N, or 0-containing 5- or 6-membered heterocyclic group residue. , at least 2 for the carbonyl group
substituents A and B are bonded at ortho positions, in which case A and B may be the same or different; It is a cyan group or a halogen atom. "Substituents A and B are bonded and contained at two positions ortho to the carbonyl group" means that the substituents A and B are attached to two optionally substituted carbon atoms adjacent to the bonding position to the carbonyl group. It means that they are combined. This means, for example, that the substituents A and B are bonded in the Q-naphthyl group at least in the 2.8-1 position and in the 6-naphthyl group at least in the 1.3-position. UV sensitizers of this type, particularly preferred 2,4,6-trimethylbenzoyldiphenylphosphine oxide, are superior in reactivity to all known photoinitiators for unsaturated polyester resins. This high reactivity causes strong heat generation during curing of the laminate, making it possible to carry out irradiation curing with less energy application than conventionally. For example, rather than using expensive mercury vapor high-pressure radiation lamps, simple low-pressure lamps such as ordinary fluorescent tubes can be used instead. Moreover, with this excellent highly reactive UV sensitizer, the storage performance of sensitized molding compounds, impregnated materials and coatings is decisively improved, resulting in a single product that retains a constant curing activity over the entire storage period. It becomes possible to manufacture component-based products. The starting components [a}, no, and e] used for the production of the photocurable polyester resin composition are explained in detail below. {a} In the present invention, unsaturated polyester preferably means unsaturated polycondensation products of Jintong from dicarboxylic acids and glycols, as well as unsaturated polyesters containing urethane groups and unsaturated vinyl ester resins. As unsaturated polyesters, they are preferably bonded in ester form with polyhydric, especially dihydric alcohols and optionally additionally contain residues of -hydric carboxylic acids and/or residues of monohydric alcohols and/or polyhydric, especially divalent carboxylic acids containing residues of hydroxycarboxylic acids (in which case at least some of these groups are under the control of ethylenically unsaturated copolymerizable groups); Esterizable derivatives, especially common military condensation products from anhydrides, are suitable. Polyhydric, especially divalent, optionally unsaturated alcohols include the usual alkanediols and oxaalkanediols having especially acyclic groups, cyclic groups and both cyclic and acyclic groups, for example ethylene. Glycol, propylene glycol 1,2, propanediol 1,3,
Butylene glycol-1,3, butanediol-1,4
, hexanediol-1,6,2,2-dimethylpropanediol-1,3, diethylene glycol, triethylene glycol, polyethylene glycol, cyclohexanediol m1,2,2,2-bis-(p-hydroxycyclohexyl)-propane, Trimethylolpropane monoallyl ether or boudenediol-1,4
is suitable. Furthermore, monohydric, trihydric or higher alcohols such as ethylhexanol, fatty alcohols, benzyl alcohol, 1,2-di(allyloxy)propanol-
3. Glycerin, bentaerythritol or trimethylolpropane is used in small amounts. Polyhydric, especially dihydric alcohols are generally reacted with polybasic, especially dibasic carboxylic acids or condensable derivatives thereof in or near stoichiometric amounts. Suitable carboxylic acids or derivatives thereof are dibasic, olefinically unsaturated, preferably Q,8-
Olefinically unsaturated carboxylic acids such as maleic acid, fumaric acid, chloromaleic acid, itaconic acid, traconic acid, methylene glutaric acid and mesaconic acid and their esters, preferably their anhydrides. The polyesters can additionally contain further modifying dibasic unsaturated and/or saturated and aromatic carboxylic acids. Examples are succinic acid,
Glutaric acid, Q-methylglutaric acid, adibic acid, sebacic acid, pimelic acid, phthalic anhydride, o-phthalic acid, isophthalic acid, terephthalic acid, dihydrophthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, 3,6-endomethylene-1, 2,3,6-tetrahydrophthalic acid,
Endomethylenetetrachlorophthalic acid or hexachlorendomethylenetetrahydrophthalic acid, as well as monobasic, tribasic and more polybasic carboxylic acids such as ethylhexanoic acid, fatty acids, methacrylic acid, propionic acid. , benzoic acid, 1,2,4-benzoltocarboxylic acid or 1,2,4,5-benzoltetracarboxylic acid. Preferably maleic acid or its anhydride and fumaric acid are used. Since the highest crosslinking power present in this type of polyester plays a major role in the performance of low-shrinkage systems, for this field of application it is necessary to use a
must be unsaturated. Mixed unsaturated polyesters, including those which are poorly soluble in the vinyl monomer b and which crystallize easily, can likewise be used with advantage. Easily crystallizing unsaturated polyesters of this type can be composed of, for example, fumaric acid, adipic acid, terephthalic acid, ethylene glycol, butanediol-1,4, hexanediol-1,6 and neobentyl glycol.
Unsaturated polyesters with terminal double bonds are also particularly suitable. Unsaturated polyester is 10-200, preferably 20-8
Acid value of 5 and about 800 to 600 or about 1000
It has an average molecule of ~4000. Amorphous and optionally crystallizable unsaturated polyesters are generally prepared by melt condensation or condensation under azeotropic conditions.
It is produced from its starting components by continuous or discontinuous operations. Regarding the composition of unsaturated polyesters, see, for example, Boenitzig, "Unsaturated Polyesters: Structures and Properties" (1964).
Reference is made to the description in . As mentioned above, an unsaturated polyester containing urethane groups can also be used instead of the unsaturated polyester. For this purpose, organic polyisocyanates, preferably aliphatic, cycloaliphatic and especially aromatic diisocyanates, are reacted with the unsaturated polyesters mentioned above, thereby lengthening the chains of the unsaturated polyesters and increasing their molecular weight. For example, the following isocyanates are suitable for chain extension. Aliphatic isocyanates, such as 1,4-butane diisocyanate and 1,6-hexane diisocyanate, cycloaliphatic diisocyanates, such as 1,3- and 1,4-cyclohexane diisocyanate, 1-methyl-2,
4-1 and 2,6-cyclohexane-diisocyanate and the corresponding isomer mixtures, isophorone-diisocyanate and 4,4-1, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, and preferably aromatic diisocyanates, such as 2,4- and 2,6-tolylene diisocyanates and the corresponding isomeric compounds 4,4'-,
2,4- and 2,2'-diphenylmethane diisocyanates and the corresponding isomeric compounds and 1,5-naphthylene diisocyanates. In order to produce unsaturated polyesters containing urethane groups, the starting components are preferably reacted at a temperature of 0 to 120° C., in particular 15 to 6000° C., with active hydrogen atoms bonded to the OH and COO groups of the unsaturated polyester. The ratio of atoms to NCO groups of the polyisocyanate is 1:0.1 to 0. For cough relief, react at a ratio of 1:0.2 to 0.7. The obtained urethane group-containing unsaturated polyester has 2 to
3. Cough protection preferably with an acid value of 5-20 and about 1000-100
00 preferably has an average molecular weight of about 1500-6000. The unsaturated vinyl ester resin suitable for the present invention has a characteristic atomic group -CO-OCH2-CHOH-C
H20 and contains a polymerizable terminal unsaturated group. Pinylester resins are produced by reacting polyepoxide resins with approximately equivalent amounts of unsaturated monocarboxylic acids, for example, 2 equivalents of methacrylic acid with 2 equivalents of polyepoxide resin. Vinyl ester resins of this type are described, for example, in US Pat. No. 3,367,992, according to which dicarboxylic acid half esters of hydroxyacrylates or -methacrylates are reacted with polyepoxide resins. According to US Pat. No. 3,066,112 and US Pat. No. 3,179,623, vinylester resins are obtained from monocarboxylic acids such as acrylic acid and methacrylic acid. A further preparation method is also shown therein, according to which a dihydric phenol, such as the sodium salt of bisphenol A, is reacted with glycidimethacrylate or -acrylate.
Vinyl ester resins based on epoxy novolac resins are described in US Pat. No. 3,301,743. No. 3,256,226 describes vinylester resins in which the molecular weight of a polyepoxide is increased by reacting a dicarboxylic acid with a polyepoxide resin and acrylic acid. Furthermore, modified vinylester resins, such as German Patent Application No. 2534
The product described in No. 03 Minor Specification (same as U.S. Pat. No. 3,947,422) contains a half-ester group, and the second hydroxyl group of the atomic group -CO-OCH2-CHOH-CH20- is replaced by dicarboxylic anhydride. It can be obtained by reacting with anhydrides such as maleic acid, citraconic acid, phthalic acid, and tetrabromophthalic acid. The photocurable polyester resin composition according to the present invention comprises unsaturated polyester, urethane group-containing unsaturated polyester, unsaturated vinyl ester resin, or a mixture of these components 'a} in the total amount of components 'a} and {b' It generally contains from 10 to 8% by weight, preferably from 10 to 75% by weight. 'b) As copolymerizable ethylenically unsaturated monomer compounds, the following allyl compounds and preferably vinyl compounds, which are commonly used for the production of unsaturated polyester resin compositions, are used. For example, styrene, substituted styrene such as P-chlorostyrene or vinyltoluol, esters of acrylic or methacrylic acid with alcohols containing 1 to 18 carbon atoms, such as methyl methacrylate, butyl acrylate, ethylhexyl acrylate, hydroxyl ．． Cibropylacrylate, dihydrodicyclobentadienyl acrylate, phthanediol diacrylate, as well as acrylic (methacrylic) acid amides, allyl esters such as diallyl phthalate, and pinyesters such as ethylhexanoic acid vinyl ester, vinylpiparate, etc. Mixtures of these olefinically unsaturated monomers are likewise suitable. Suitable as component 'b) are styrene, Q-methylstyrene, chlorstyrol, vinyltoluol, divinylbenzole and diallylphthalate. Component {b}' In polyester molding materials, impregnation materials and paints, component ta
20 to 9% by weight, preferably 30 to 85% by weight, based on the total weight of } and (b). Examples are: phenolic inhibitors such as hydroquinone, substituted hydroquinones, blencatechin, tertiary butyl blencatechin, nuclear substituted blencatechin derivatives; For example, penzoquinone, naphthoquinone, chloranil, nitrobenzole, etc.
- dinitrobenzole, thiodiphenylamine, N-nitroso compounds such as the salts of N-nitrosodiphenylamine and N-nitroso-N-cyclohexylhydroxylamine and mixtures thereof. As an additional stabilizer,
Divalent copper salts such as naphthenic steel or copper octoate and the following formula [NR5R6R7R8] Suitable are quaternary ammonium salts having the structure of an aryl group having carbon atoms or an aralkyl group having 7 to 3 carbon atoms, and X meaning a halogen atom, preferably a chlorine atom. Addition of selected UV absorbers for photostability of the cured product often reduces the UV curing rate somewhat. But that's just enough to be a ninja. Those from the series of oxybenzophenones, ester salicylates and oxyphenylbenzotriazoles are suitable. The inhibitor is
In molding materials, impregnating materials and paints, components (a and {generally 0.005 to 0.5% by weight, preferably 0.005 to 0.5% by weight, based on the skin) are added.
It is contained in an amount of 0.01 to 0.2% by weight. [d' Ultraviolet sensitizer [d-] is an acylphosphine oxide compound of the following formula according to the present invention. Examples of the acylphosphine oxide compound include acylphosphine oxide and acylphosphinic acid ester. Specific examples for Equation 1 are as follows. RI I~ Straight-chain or branched alkyl groups having 6 carbon atoms, such as methyl, ethyl, i-propyl, n-propyl, n-butylthoamyl, n-hexyl, cyclobentyl, cyclohexyl, aryl groups such as phenyl, naphthyl, halogen Substituted aryl groups such as mono- or dichlorophenyl, alkyl-substituted phenyl groups such as methylphenyl, ethylphenyl isopropylphenyl, tertiary butylphenyl, dimethylphenyl, alkoxy-substituted aryl groups such as methoxyphenyl, ethoxyphenyl, dimethoxyphenyl, S
or N-containing 5- or 6-membered residues such as thiophenyl, pyridine. R2 Same as RI, plus 1 more
alkoxy groups having ~6 carbon atoms, such as methoxy, ethoxy, i-propoxy, butoxy,
Ethoxyhexy group, aryloxy group such as phenoxy, methylphenoxy, benzyloxy. RI may be combined with R2 to form a ring, as in, for example, acyl-phosphonic acid-o-phenylene ester. R3 Ethyl, i-propyl, n-propyl, n-butyl, j-butyl, tertiary-butyl, i-amyl, n-hexyl, hebutyl, n-octyl, 2-ethylhexyl, i-nonyl, dimethylheptyl, lauryl, stearyl, cyclo Propyl, cyclobutyl, cyclobentyl, 1-methyl-cyclobentyl, cyclohexyl, 1-methylcyclohexyl, norbornadienyl, adamantyl, phenyl, methylphenyl, tertiary-butylphenyl, isobropylphenyl, methoxyphenyl, i-propoxyphenyl enyl, thiomethoxyphenyl, Q- and 8
Naphthyl, thiophenyl, pyridyl, 8-acetoxyethyl or 8-carpoxyethyl. R1, R2 and R3 additionally contain a C--C double bond, which allows a UV sensitizer to be polymerized into the binder. Examples of UV sensitizers according to the present invention include the following. Isobutyryl-methylphosphinate methyl ester, Isobutyryl-phenylphosphinic acid methyl ester, Piva. p-phenylphosphinate methyl ester, 2-ethylhexanoyl phenylphosphinic acid methyl ester, pivaloylphenylphosphinic acid isoproyl ester, p-tonoreyl phenylphosphinic acid methyl ester, o-tolylphenylphosphinic acid Methyl ester, 2.4-dimethylbenzoyl-phenylphosphine acid methyl ester, p-tertiary-butylbenzoyl-phenylphosphinic acid isoproyl ester, acryloyl-phenylphosphinic acid methyl ester, isobutyl-diphenylphosphine oxide, 2- Ethylhexanoyldiphenylphosphine oxide, o-toluyldiphenylphosphine oxide, p-tertiary butylbenzoyldiphenylphosphine oxide, 3-pyridylcarbonyldiphenylphosphine oxide, acryloyldiphenylphosphine oxide oxide, benzoyl-diphenylphosphine oxide, di-/di-methyl-bis-diphenylphosphine acid vinyl ester, adipoyl-bis-diphenylphosphine oxide. Particularly preferably, the following are used. pivaloyroudiphenylphosphine oxide, p-tolyroudiphenylphosphine oxide, 4-(tertiary butyl)-benzoyldiphenylphosphine oxide, terephthaloyroudiphenylphosphine oxide,
2-methylbenzoyl-diphenylphosphine oxide, versatoyl-diphenylphosphine oxide, 2-methyl-2-ethylhexanoyl-diphenylphosphine oxide, 1-methyl-cyclohexanoyl-diphenylphosphine oxide, pivaloylphosphine oxide Enylphosphinic acid methyl ester and pivaloyl-phenylphosphinic acid isopropylester. This type of compound is made by converting an acid acid halide of the following formula (X in the formula is CI, Br) to the following formula (
R4 in the formula is produced by reacting a straight or branched C, to C5-alkyl group or a cycloalkyl group having 5 or 6 carbon atoms with a phosphine. The reaction is carried out in a solvent such as a hydrocarbon or a mixture of hydrocarbons such as petroleum ether, toluene, cyclohexane, ethers or other common inert organic solvents or in the absence of a solvent, from 130 to 111,000, preferably from 10 to 70
It is carried out at a temperature of 0.00. The product can be crystallized directly from the solvent, left after evaporation, or distilled under vacuum. The acid halides R3COX and the substituted phosphines RIR-like OR4 can be prepared by methods known to the expert from the literature (for example as described in Hopenweil, Volume 12/1, pages 208-209). The method for producing phosphine oxide used in the present invention is illustrated by the formula below. Examples of suitable phosphines are: . Methyldimethoxyphosphine, butyldimethoxyphosphine, phenyldimethoxyphosphine, tolyldimethoxyphosphine, phenyldiethoxyphosphine, tolyldiethoxyphosphine, phenyldiisopropoxyphosphine, tolyldiisopropoxyphosphine, enyldibutoxyphosphine, tolyldibutoxyphosphine or dimethylmethoxyphosphine, dibutylmethoxyphosphine, dimethylbutoxyphosphine, diphenylmethoxyphosphine, diphenylethoxyphosphine, diphenilph. Ropoxyphosphine, diphenylisof. Ropoxyphosphine, diphenylbutoxyphosphine or similar starting materials from which compound {1}' is derived. As acid halides, chlorides and bromides are suitable, but acid chlorides are particularly preferred. Examples of Compound 1 are shown in the table below. (However, this does not limit the invention). Military S quantity 4o ship ship insult S ink. Funafune Ren Q Sumido Funafune S Sumi 4o Particularly suitable as UV sensitizers for unsaturated polyester resins are acylphenylphosphinic acid esters and azildiphenylphosphine oxides, the acyl group of which is Secondary- or tertiary-substituted fatty acid carboxylic acids such as pivalic acid, 1-methylcyclohexanecarboxylic acid, norbornenecarboxylic acid, Q,Q-dimethylalkanecarboxylic acid (commercially available versatic acid with 9 to 1 carbon atoms) ) or from 2-ethylhexanecarboxylic acid, or substituted aromatic carboxylic acids such as p-methylbenzoic acid, c-methylbenzoic acid, 2,4-dimethylbenzoic acid, p-tertiary butylbenzoic acid, 2,4,5 - derived from trimethylbenzoic acid, p-methoxybenzoic acid or p-thiomethylbenzoic acid. A particularly excellent highly reactive UV sensitizer is R
3 has the following meaning. R3 cycloalkyl group, aryl group, naphthyl group, S
, N or ○-containing 5- or 6-membered heterocyclic group residue, such as furyl group, pyrrolyl group, chenyl group, pyranyl group or pyridyl group, substituents A and B are bonded to at least two ortho positions to the carbonyl group (A and B may be the same or different) and may be branched 1 to 6
an alkyl group preferably having 1 to 4 carbon atoms,
For example, methyl group, ethyl group, propyl group, im propyl group, butyl group, i-phthyl group and tertiary butyl group; optionally substituted cycloalkyl group, such as cyclohexyl group, optionally substituted aryl group, such as phenyl group. or tolyl, alkoxy or thioalkyl groups having 1 to 6, preferably 1 to 4 carbon atoms in the alkyl group, such as methoxy, ethoxy, propoxy, i-propoxy, n-ptoxy, methylthio , ethylthio, propylthio, i-propylthio, n-butylthio, secondary butylthio and tertiary butylthio; carbalkoxy groups having 1 to 6, preferably 1 to 4 carbon atoms in the alcohol group, e.g. Methoxy, carbethoxy, carbopropoxy, carbisopropoxy, carpobutoxy and carbo-secondary butoxy groups, cyanide or halogen atoms such as chlorine, bromine or iodine. An example of an acylphosphine oxide compound containing R3 bonded is shown by the following structural formula. In this formula, X is a substituent that is optionally present in a cycloalkyl group, an aryl group, a naphthyl group, or a polycyclic group residue, and has the same meaning as A or B. Examples of this type of highly reactive ultraviolet sensitizer include the following. 2,6-dimethylbenzoylphenylphosphinic acid methyl ester, 2,6-dimethoxybenzoylphenylphosphinic acid methyl ester, 2,6-
dimethylbenzoyl-diphenylphosphine oxide,
2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphine methylester, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3
, 6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-trilphosphinic acid methyl ester, 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlor Benzoylphenylphosphinate ethyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2-chloro-6-methylthio-penzoyldiphenylphosphine oxide, 2,6-dimethylthio-penzoyldiphenylphosphine Inoxide, 2
, 3,4,6-tetramethylbenzoyl-diphenylphosphine oxide, 2-phenyl-6-methylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,4,
6-trimethylbenzoylnaphthylphosphinic acid ethyl ester, 2,6-dichlorobenzoylnaphthylphosphinic acid ethyl ester, 1,3-dimethylnaphthalene-2-carbonyl diphenylphosphine oxide,
2,8-Dimethylnaphthalene-1-carbonyl diphenylphosphine oxide, 1,3-dimethoxynaphthalene-2-carbonyl diphenylphosphine oxide, 1,3-dichlornaphthalene-2-carbon rubonyl-diphenylphosphine oxide, 2,4,6-trimethylpyridine-3-carbonyldiphenylphosphine oxide, 2,4-dimethylquinoline-3-carbonyldiphenylphosphine oxide, 2,4-dimethylfuran-3
- Carbonyl diphenylphosphine oxide, 2,4
-dimethoxyfuran-3-carbonyl-diphenylphosphine oxide, 2,4,5-trimethyl-thiophene-3-triponylphenylphosphine methyl ester, 2,4,5-trimethyl-thiophene-3-power Luponyl-diphenylphosphine oxide. The following are used with particular advantage: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethyl -Penzoyl-difhenylphosphine oxide, 2,4,6-trimethylbenzoyl-benzoylphosphine acid methyl ester. Particularly excellent highly reactive UV sensitizers are those whose acyl groups are di-ortho-substituted aromatic carboxylic acids, such as 2,4,6
-trimethylbenzoic acid, 2,6-dimethoxybenzoic acid,
These are acylphenylphosphinic acid esters and acyldiphenylphosphine oxides derived from 2,6-dichlorobenzoic acid or 2,3,5,6-tetramethylbenzoic acid. The acylphosphine oxide compound used in the present invention is 0.005 to 5% by weight based on the weight of the unsaturated polyester [a} and the ethylenically unsaturated monomer compound {b'.
Preferably it is used in an amount of 0.01 to 3% by weight. {e} Additive components for polyester and vinylester resins which belong to this category include, for example, reinforcing agents, mold release agents, inert solvents, shrinkage control additives and/or other auxiliaries that can be used in unsaturated polyester materials. Medications can be given. The paraffin used in the photocurable polyester resin composition of the present invention is preferably 25 to 90 qo, preferably 45 to 60 qo.
It has a melting point of qo. Since it is known that a melting point of 46 to 48 qo is good, paraffin having this melting point is particularly preferably used. Instead of paraffin, other waxy substances can also be used, such as paraffin oxidation products known as montan wax or its esters, carnauba wax, long silver fatty acids such as stearic acid, stearyl stearate, ceresin, etc. In order to suppress the scattering of the monomers and form a non-tacky surface, the unsaturated molding composition contains 0.01 to 5% by weight of paraffin, preferably 0.01% by weight, based on the total weight of components {a} and {b}. 05
It contains ~1% by weight, especially 0.1-0.5% by weight. Suitable thickening agents are, for example, those based on alkali metal oxides such as calcium oxide, calcium hydroxide, magnesium hydroxide, particularly preferably magnesium oxide and mixtures of these oxides or hydroxides. . This may be partially replaced by subsalt oxide.
The thickener content of the polyester molding material or vinylester molding material of the invention is generally 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the mixture of components [a} and {b).
It is. In the present invention, in addition to the acylphosphine oxide compound, the following may be used as an additional initiator. Peroxides such as peresters such as tertiary butyl peroctate, tertiary butyl perpivalate, percarbonates such as pis-(41tertiary butylcyclohexyl)
- peroxydicarbonates, diacyl peroxides such as penzoyl peroxide, dialkyl peroxides such as di-tertiary butyl peroxide and dicumyl peroxide, hydroperoxides such as dicumyl peroxide. Hexanone peroxide, methyl ethyl ketone/gu oxide, cumol hydroxide/gu oxide, tertiary butyl hydroperoxide optionally in combination with metal promoters such as ethylhexanoic acid or cobaltolo salts of naphthenic acid; and azo compounds such as azodisosuccinic acid. Dinitrile "tetraphenyluethanediol and/or the Q,Q,Q,Q'-tetra-substituted dibenzyl compounds described, for example, in Kunststoffe Vol. 66 (1976), p. 693.Glass fibers and quartz sand. Thick laminate structures, such as those for pipes, which contain, in addition to the acylphosphine oxide compound according to the invention, additionally a small amount of a thermally decomposable initiator, e.g. Weight% preferably 0.1-0.3% by weight
Curing can be particularly advantageously achieved by combined use of ultraviolet irradiation. This initiator is decomposed into radicals by the heat generated during photopolymerization and can therefore exert a curing effect even in deep layers that are insufficiently reached by ultraviolet light. Acyl phosphine oxide compounds according to the invention and known photoinitiators such as aromatic ketones such as penzyl ketals such as penzyl dimethyl ketal, benzoyl ethers and penzoyl esters such as penzoyl isopropyl ether, Q-hydroxyisobutylophenone, It is also particularly advantageous to use a combination of photoinitiators from diethoxyacetophenone or p-tert-butyltrichloroacetophenone, aromatic disulfides or naphthalenesulfonyl chloride. With this combination of photoinitiators, ``the acylphosphine oxide compound alone can be cured for comparable irradiation times, even though in many cases the curing activity (measured by the temperature rise of the test resin during irradiation) is reduced.'' It is possible to lower the residual styrene content in UP resin moldings than when using a combination photoinitiator, preferably 15-85% by weight of an acylphosphine oxide compound, especially 25-75% by weight of an aromatic 15-85% by weight of group ketones, especially 25-75
% by weight (weight % of aromatic ketone is relative to the total weight of the mixture). This formulation is used in an amount of 0.005 to 7% by weight, preferably 0.01 to 4% by weight, based on the weight of component {a' and others. In addition, customary fillers, reinforcing materials, mold release agents, inert solvents, shrinkage-inhibiting additives and other auxiliaries are often added to the curable resin compositions according to the invention. Fillers can be, for example, ordinary finely divided or granular inorganic or organic fillers transparent to long-wave UV radiation, such as hydrated aluminum oxide, quartz sand,
These are finely divided silicic acid, asbestos, talc, barium sulfate, gypsum (calcium sulfate), and mica. Reinforcements include inorganic or organic fibers or flat structures optionally woven from them, such as mats, such as glass, asbestos, cellulose and synthetic organic polymers such as polyamides, polyacrylonitrile and polyesters such as terphthalates. used. Fillers and reinforcing agents are used in amounts ranging broadly from 5 to 20% by weight, preferably from 10 to 70% by weight, based on the total weight of components 'a} and [b}. In many cases, for example in container manufacturing, it is preferred to use a combination of powdered and fibrous fillers. According to the lamination method, the laminate is coated with a film transparent to UV radiation and fluorescent lamps (for example TAK40W/
For relatively long periods of time, low-energy ultraviolet irradiation from a mercury vapor high-pressure lamp (HO
It can be cured in an extremely short time using K6.80W/skin, Philips). As mold release agents, for example, zinc, magnesium or calcium salts of stearic acid and polyalkylene ether waxes are used. Furthermore, ketones, esters or hydrocarbons are used as inert solvents, which are optionally used in combination, in amounts of up to 10% by weight, based on component [a}. Shrinkage-reducing additives which may additionally be used include, for example, thermoplastic polymers such as polystyrene, styrene copolymers, polyvinyl acetate or poly(meth)acrylates in combination with component {a
- Used in amounts up to 1 to about 3% by weight per weight. Irradiation sources for curing molding materials, impregnation materials and paints include, for example, fluorescent lamps, mercury high-pressure lamps and direct sunlight. The polyester resin composition of the present invention is used in many industrial fields as a molding material, impregnating material, and coating material, and is suitable for, for example, the following uses. 1 Thin Layer Resin A thin layer of only about 0.5 willow thick serves to protect the laminate behind it which has glass fibers that are sensitive to hydrolysis. The resins must meet high demands on curing activity, and the moldings are only allowed to show slight yellowing.
The transparent thin layer is applied onto the mold by spraying or painting, then gelled or hardened by UV radiation and finally applied to the glass-filled molding compound. 2. Fiber-reinforced molded product'a - Light-transmitting boards used in the architectural field are excellent in terms of high transparency and slight yellowing. Continuously operating machines are used to produce flat plates, longitudinally corrugated plates or transversely corrugated plates. The glass fiber mat between the coatings is impregnated with photostabilized UP resin, degassed and finally solidified by cooling. By using the acylphosphine oxide initiators according to the invention, curing can be carried out more economically by ultraviolet irradiation using mercury vapor high-pressure lamps or so-called blue light lamps (Reference on the production of light-transparent plates: Published by Schuplinger GmbH, 1967). (Gräsferselferstelkte Kunststoszław, by Soelden, p. 610). {b- Processes for the discontinuous production of fiber-reinforced, in particular glass-fibre-reinforced, moldings used for UV curing are manual lamination, fiber jetting, centrifugation and winding (see Zelten, supra). ). Examples of practical objects that can be produced by these methods are boats, container boards (chipboard or joinery board with glass fiber reinforced synthetic resin on both sides), pipes and containers. [c--UP resin thin layer for glass fiber-containing moldings (GFK) and paper laminates; the surface quality of GFK and paper laminates is significantly improved by applying a thin layer, with the following advantages: I GFK laminates, for example corrugated boards: a. Retains gloss for a long time when exposed to open air, thus reducing staining. b Due to the protection of the glass-resin interface, there is only a slight decrease in transparency when exposed to open air. 2. Paper laminates based on unsaturated polyester resin, urea resin or melamine resin: a. Improved surface gloss. b Less sensitive to finger touch on the surface than is the case with melamine resins. The high transparency of the c UP thin layer gives a light sensation, for example like a surface coated with a transparent varnish. The thin layer itself must be formed on a support (eg, a sheet) prior to laminate manufacture. For this purpose, a UP resin layer with a thickness of 20 to 200 cm is applied onto the separation sheet, and then this coating layer is cured by ultraviolet light. Complete curing then occurs during curing of the laminate. Formation of thin layers by known methods exhibits the following drawbacks. 'a} When curing with organic peroxides under heat, a large amount of styrene is lost and therefore there is a risk of insufficient curing. (b) When curing with peroxide and accelerator under heat, the loss of styrene can be reduced, but the processing time is short (30-6 min) and the accelerator (Co salt) A drawback is the inherent coloration of the molded parts caused by UV curing with known photoinitiators resulting in a yellowish thin layer, and this yellowing is further exacerbated by exposure to open air. With molding compositions, the above-mentioned drawbacks of other methods do not occur; on the contrary, the rapid curing by ultraviolet light results in an almost colorless thin layer, which does not yellow either in sunlight or under artificial light.3 Mounting The novel sensitizers are particularly suitable for incorporation into casting resins which can be used, for example, for the embedding of electronic components. When embedding light-opaque articles care must be taken for uniform and all-directional exposure. Unless otherwise specified, parts and percentages in the following examples are based on weight, and parts by volume are relative to parts by weight. Examples and comparative examples were carried out using the following unsaturated polyester resins. Resin A: an unsaturated polyester obtained from maleic acid, o-phthalic acid, ethylene glycol and propylene glycol-1,2 in a molar ratio of 1:2:2.4:0.7 using o.ol% hydroquinone. Stabilized 65% styrene solution. The unsaturated polyester has an acid number of 50. Resin B Unsaturated polyester obtained from maleic acid, tetrahydrophthalic acid and diethylene glycol in a molar ratio of 1:0.5:1.5 , a 67% styrene solution stabilized with 0.01% hydroquinone, an unsaturated polyester of 4
It has an acid value of 3. Resin C: 66% of an unsaturated polyester obtained from maleic acid, o-phthalic acid and propylene glycol-1,2 in a molar ratio of 1:0.5:1.5, stabilized with 0.01% of hydroquinone. styrene solution. The unsaturated polyester has an acid number of 50. Resin D maleic acid, isophthalic acid, propylene glycol-1,
2 and diethylene glycol in a molar ratio of 1:0.67:
A 65% styrene solution of the unsaturated polyester obtained at 0.72:1, stabilized with 0.01% of hydroquinone, the unsaturated polyester has an acid number of 26. Resin E fumaric acid, adipic acid, neobentyl glycol and propylene glycol-1,2 in molar ratio 1:1
:1.7:0.35 of the unsaturated polyester obtained,
6.5% stabilized with Hydroquine 0.01%
styrene solution. The unsaturated polyester has an acid number of 17. Resin F maleic acid, adipic acid, propylene glycol day 1, 2
and diethylene glycol in a molar ratio of 1:0.5:0.
Styrene solution of unsaturated polyester obtained at 55:1, stabilized with 0.01% of hydroquinone 4
5% and ~55% resin A with an acid value of 30. Resin G Maleic acid, o-phthalic acid, propylene glycol-1,2, and diethylene glycol in a molar ratio of 1:
6 of the unsaturated polyester obtained at 0.25:1:0:25 stabilized with 0.012% of hydroquinone
5% styrene solution. The unsaturated polyester has an acid number of 43. Resin date maleic acid, o-phthalic acid and propylene glycol-1
, 2 in a molar ratio of 1:1:2, stabilized with 0.01% of hydroquinone,
65% styrene solution. The unsaturated polyester has an acid number of 52. Resin J A 65% styrene solution of an unsaturated polyester obtained from maleic acid, o-phthalic acid and propylene glycol-1,2 in a molar ratio of 1:2:3, stabilized with 0.01% of hydroquinone. The unsaturated polyester has an acid number of 30. Resin K Commercially available ordinary vinyl ester resin (Dow Chemical Company product,
Name Delakaine 411-45). The following compounds belonging to the state of the art were used as UV stabilizers for comparative examples. 1 Penzyl dimethyl ketal n Benzoin methyl ether m Benzoin isopropyl ether W Methylol benzoin ether ether Examples of the present invention were carried out using the following acylphosphine oxides and acylphosphinates. X pinoyloyl diphenylphosphine oxide illusion
p-Toluyl-diphenylphosphine oxide fine 4-(tertiary butyl)-benzoyl-diphenylphosphine oxide Enylphosphine oxide X 2-Methyl-2-ethylhexanoyl-diphenylphosphine oxide Valoylphenylphosphine acid isopropyl ester The following acylphosphine oxide was used as the highly active UV stabilizer. XX 2,4,6-trimethylbenzoyl-diphenylphosphine oxide X phantom 2,6-dimethoxybenzoyl-diphenylphosphine oxide
2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide XXW 2,4,6-trimethylbenzoyl-phenylphosphine acid methyl ester The acylphosphine oxide compound used in the present invention was produced by the following method. Pivaloyl diphenylphosphine oxide ■): Petroleum ether (boiling range 40-7000) 135 parts by volume,
N. 225 parts of diphenylchlorophosphine dissolved in 22 parts of petroleum ether are added to a mixture of 18 parts by volume of N-jethylaniline and 67 parts by volume of methanol at 0 DEG C. while stirring. The mixture was then kept at room temperature for another 2 hours and then heated to about 15°C.
The precipitated amine hydrochloride is subjected to a suction furnace, and the furnace liquid is first distilled at 10 to 20 Hg to remove all low-boiling substances. Then, at 0.1-1 Hg, the boiling point is 120-1
175 parts of methoxym diphenylphosphine (yield 80% based on diphenylchlorophosphine) of 2400/0.5 side Hg is fractionated. 64.8 parts of methoxydiphenylphosphine is added dropwise at 30 to 6000 while increasing the volume by 36.2 parts of pivaloyl chloride. After the addition is complete, the three powders are reacted again, cooled to 0-10 qo, and the precipitated product is recrystallized from cyclohexane. Pivaloyldiphenylphosphine oxide 69.5
(81% of the theoretical value). Melting point: 110-11
〆0. Nuclear magnetic resonance (CDC13,6): 1.33 (s)
;7.4-8.0(m) Elemental analysis: C, 7th, 903P
(286) Calculated value 0 71.33 days 6.64 PI
O. 84 actual value 0 70.0 days 6.5 P
II. 0p-Toluyludiphenylphosphine oxide (phantom): 108 parts of methoxydiphenylphosphine (eg, as described above) dissolved in 20 volume parts of toluene are added to 77 parts of tolylic acid chloride. After flooding with 50 qo for 60 minutes, the mixture is cooled, and the precipitate of tolyldiphenylphosphine oxide is filtered through a suction oven and recrystallized from cyclohexane. Yield 117 parts (73% of theory), melting point 10500. Cough magnetic resonance (CDC13,6): 2.35 (s); 7.2
~8(m) Elemental analysis: C2 Rainbow, 702P (320) Calculated value 0 75.00 days 5.31 P 9.69
Actual value 0 75.3 days 5.8 P 9.34
-(Tertiary butyl)-penzoyl diphenylphosphine oxide (fox): 41.3 parts of p-tert-butylbenzoic acid chloride was dissolved in 20 parts of toluene in the same machine as compound x, and methoxydiphenylphosphine 45 .4 parts and 5
000 for 90 minutes. After evaporating the solvent using a rotary evaporator, it is recrystallized from cyclohexane. Yield 63 parts (83% of theory), melting point 13600. Nuclear magnetic resonance (CDC13,6): 1.3(
s); 7.3-8.1 (m); 8.8d) Elemental analysis: C
23rd day 2302P (362) Calculated value 076.24th day 6.35P 8.56 Actual value 0 76.0th day 6.5P 8.7 Terephthaloyru-bis-diphenylphosphine oxide (Xm): Same as compound Beni Terephthaloyl-bis-diphenylphosphine oxide is produced from 52 parts of terephthalic acid dichloride and 108 parts of methoxydiphenylphosphine dissolved in 200 parts of toluene. Yield 46 parts (35% of theory), melting point 205 qC. Nuclear magnetic resonance (CDC13,6): 6.8-8.2 (m) Elemental analysis: C32nd 2404P2 (534) Calculated value 0 7
1.91 days 4.49 PII. 61 Actual value 0 71
．． 8 days 4.8 PII. 02-Methylbenzoyl-diphenylphosphine oxide (XW): 2-Methylbenzoyl-diphenylphosphine oxide is produced from 77 parts of 2-methylbenzoic acid chloride and 108 parts of methoxydiphenylphosphine in the same manner as in the compound phantom. Yield 134 parts (84% of theory), melting point 10,700. Nuclear magnetic resonance (CDC13,6): 2.5 (s); 7.2~
8 (m): 8.8 (m) Elemental analysis: C2 rainbow, 702P (
320) Calculated value 0 75.00 days 5.31 P 9.69
Actual value 0 74.7 days 5.4 P 9.5 Versitrodiphenylphosphine oxide (XV):
Toxidiphenylphosphine 43. Moribe, 2,2-dimethyl-heptane-carboxylic acid chloride (versatic acid chloride) 35.
Add dropwise to 3 parts. After cooling at 50°C for 3 hours, the mixture was cooled to 1500°C, and the mixture was poured into a suspension of 60°C of silica gel in 350°C of toluene, and the mixture was cooled on ice for 1 hour. The mixture is then placed in a suction furnace and the solvent is distilled off under reduced pressure, leaving versitru diphenylphosphine oxide as a viscous oil. Yield: 62 yen (90% of theoretical value). Nuclear magnetic resonance (CDC13,6): 0.4-2.3 (m); 7.
2-8.1 (m) Elemental analysis: C2, day 2702P (34
2) Calculated value 0 73.68 days 7.89 P 9.
06 Actual value 0 73.6 days 8.1 P 8.
62-Methyl-2-ethylhexanoyl-diphenylphosphine oxide (XW): 2-methyl-3-ethyl- 165 parts of hexanoyl diphenylphosphine oxide are obtained as an oily crude product. The desired product is obtained as a pale yellow oil by column chromatography (silica gel 60, developing solvent toluol/ether 3:1). Yield: 154 parts (90% of theoretical value)
) Nuclear magnetic resonance (CDC13,6): 1.2 (s); 0.
5-2.2 (m); 7.3-8.1 (m) Elemental analysis: C
2, day 2702P (342) calculated value 0 73.68
Day 7.89 P 9.06 Actual value 0 73.9
Day 8.1 P 9.41-Methyl-cyclohexanoyl diphenylphosphine oxide (X skin): From 8 parts of 1-methyl-1-cyclohexanecarboxylic acid chloride and 108 parts of methoxydiphenylphosphine in the same manner as the compound phantom, a solvent 1-Methylcyclohexanoyl diphenylphosphine oxide is obtained as an oily crude product. This is purified by chromatography on silica gel (developing solvent: toluene). Yield 42 marks (theoretical value 26
%), melting point 80qo. Nuclear magnetic resonance (CDC13,6):
14(s); 1.1-1.6(m); 2.1-2.4(
m); 7.3-8.0 (m) Elemental analysis: C2 Nagi 2302
P(326) Calculated value 0 73.62 days 706 P
9.51 Actual value 0 73.3 days 7.1 P
9.6 pivaloyl phenylphosphinate methyl ester (X leg): 100 tsubo volume parts of toluene, N. To a mixture of 421 parts by volume of N-jethylaniline and 10 parts by volume of methanol are added at 0 DEG C. 214 parts of phenyldichlorophosphorine. The mixture is then incubated at room temperature for another hour, and the precipitate of amine hydrochloride is filtered through a suction oven and fractionated. Dimethoxyphenylphosphine is distilled on the 46-503○/0.2-0.3 side with a yield of 1
9 parts (93% of the theoretical value). Pivaloyl chloride 78.
7 parts lyo dimethoxyphenylphosphine 110.
Add 5 parts dropwise. The reaction mixture is then distilled after flooding to 50°C for another 30 minutes. Pivaloylphenylphosphinic acid methyl ester is 104-107o0/0.
Crab comes out with 3 ribs. Yield: 101.3 parts (65% of theoretical value)
. Nuclear magnetic resonance (CDC13,6): 1.3 (s); 3.
75(d): 7.4-8(m) Pivaloylphenylphosphinic acid isopropyl ester (XK): 60 parts by volume of petroleum ether, 263 parts of N,N-jethylaniline, and Isof. To the mixture from 12 parts of Lopanol are bottled 143 parts of phenyldichlorophosphine at 0° C. within 1 hour. It is then allowed to stand for another hour at room temperature and distilled using the same working-up procedure as in Example 1. Diisopropoxyphenylphosphine is distilled at a total of ~7〆○/0.3 skin. Yield: 126 copies (
69% of the theoretical value). 158 parts of diisopropoxyphenylphosphine is gradually added to 84 parts of pivalic acid chloride at a concentration of 50 to 6000, while increasing the amount frequently. After leaving it for another 2 hours and fractionating it in vacuum, 119
-12100/0.5 side gives pivaloylphenylphosphinic acid inpropyl compound. Yield 112
(60% of the theoretical value). Nuclear magnetic resonance (CDC13,6)
:125(s);1.33(t);4.5(m);7.
3-8 (m) Elemental analysis: C, 4 days 2,03P (268)
Calculated value () 62.68 days 7.84 PII. 57 Actual value 0 63.0 days 8.0 P II. 42
, 4,6-Trimethylbenzoyl-diphenylphosphine oxide (XX): 648 parts of methoxydiphenylphosphine was dissolved at 50-5500 in a container equipped with a reflux condenser and a dropping funnel. , 547.5 parts of 6-trimethylbenzoyl chloride. Incubate for another 4 to 5 hours at 50℃, and then drain the contents of the container for 30℃.
Dissolve in ether at 0.00 and mix with petroleum ether until turbidity begins to appear. When cooled, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (melting point 80~
8100) precipitates as pale yellow crystals. Yield 91
Ikari County (87% of the theoretical value). 2,6-dimethoxybenzoyl-diphenylphosphine oxide (X illusion): Compound X
In the same apparatus as in case X, suspend 2 parts of 2,6-dimethoxybenzoyl chloride in 20 parts by volume of toluene,
21.6 parts of methoxydiphenylphosphine is added dropwise to this mixture while increasing the volume. After incubation for 3 hours at 50:00 am, the mixture is directly recrystallized from toluene to obtain 32 parts of the desired compound having a melting point of 124-12 o as yellowish crystals. Other highly active initiators synthesized by similar manufacturing methods are shown in Table 2. Table 2 Examples of highly active acylphosphine oxide derivatives Ultraviolet curing activity To measure the curing activity, temperature changes over time during the ultraviolet irradiation period in unsaturated polyester resin (Up resin) or vinylester resin were recorded. . Therefore, a temperature recorder (Tastetherm Sfript, Standard Führer T3 manufactured by Chengleton, Germany) was used.
00), the heat sensitive body with a wax layer applied thereto is 5cm in diameter (the thickness of the UP resin layer is 4.8cm),
It was inserted into a tin plate lid filled with 100% of UP resin. The lid was embedded in polyurethane rigid foam during UV irradiation to avoid heat loss. As the irradiation source, an ultraviolet field consisting of five crab light tubes (TLAK40W/0.5, manufactured by Philips) was used. Irradiator and UP
The distance to the resin surface was 8.5 skins. From the temperature-hour curve recorded, the characteristic values for the curing activity are the curing time HZ5°C - Tmax and the highest curing temperature T reached.
Nagi x was chosen. The time required for the sample temperature to rise to Tmax at 2,500 ℃ is defined as the curing time. Example 1 Preparations from Resin C containing 0.2% of various sensitizers were cured with UV light as described above. According to the comparison of the curing activities (Table 3), the furthest curing is possible with the initiator X according to the invention;
Next to this, penzyl dimethyl ketal m was found to be the most advantageous of the substances known in the literature and partly commercially available. Therefore, this initiator x was mainly used in other comparative tests as well. Table 3 UV Curing Examples of Resin C in a 4.8 willow thick layer containing 0.2% of various sensitizers Table 4 Sensitization according to the invention compared to penzyl dimethyl ketal {11 UV Curing Activity of Agents Example 3 UP resins containing UV absorbers were used to produce UV-stable moldings, for example for thin layers or for light-transparent plates. This additive can affect the UV cure rate. The test below shows how strongly this effect can be tinted. A preparation of Resin A, a commonly available UV absorber (0.1%) and sensitizers 1 and 0.2% each was cured using a crab light tube according to the activity assay described above. The results are shown in Table 5. This shows that preparations containing UV absorbers react less actively than those that are not UV stabilized, as expected, but at the same time the preparations according to the invention are much faster than the preparations with sensitizer 1. It is clear that it hardens. Table 5 UV Curing Examples of Photostabilized Preparations from Resin A 4 To determine the effect of mineral filler additives on the UV cure rate, initiator XO. Resin A sensitized using 2% was cured by ultraviolet light (irradiation source: light material tube TUV40W/
05, Fili *manufactured by Hairups Co., Ltd.). The temperature-time curve recorded according to the measurement method described above gives the values for the curing time and the maximum curing temperature Tx. The test results are shown in Table 6. Table 6 UV curing of preparations from resin A containing fillers 1) The layer thickness of the molded article (disk) was 4.8 mm 2) Martin Swerke product example 5 Resin A The curing activity of the preparations according to the invention was determined by long-wave irradiation using a lamp (HR1, 2000 W "Powerstar") equipped with sodium iodide. For the above operating method, the distance of the lamp from the substrate surface is 60
It was the skin. Table 7 UV curing of molding materials according to the invention with an initiator content of 0.2% Moldings made from the materials according to the invention are
Unlike molded products containing benzyl dimethyl ketal [1], it does not yellow. Example 6 Manufacture of U old molding material reinforced with glass fiber (GF) {a
} Resin A Preparation with addition of 0.15% penzyl dimethyl ketal (mixture 1) or preparation with addition of 0.15% pivaloyl diphenylphosphine oxide (mixture 2)
), a glass fiber mat laminate (glass fiber content 25%) of 5 sides and 1 rib thickness was produced, which was irradiated with ultraviolet light (crab light tube TUV40W/05 manufactured by Philips) from a distance of 11 skins. . After a certain irradiation time, the Barcol hardness (Barcol Impresa Model 934-1) of the laminate on the side opposite to the light source was measured. The results are shown in Table 8. Table 8: UV curing of GF-UP bond products [b - Mat laminates of thickness 9 willow (glass fiber content 39%) on polyester sheets from mixtures 1 and 2 for curing with mercury vapor high pressure irradiation lamps was prepared and rotated on a rotating table at a distance of 35 skin under a UV illumination lamp. The effective irradiation time was 3 minutes, and the thickness of the laminate was 9 skins. After cooling the molded product, the Barcol hardness was measured on the opposite side of the irradiation lamp. In this case as well, the initiator pivaloyl diphenylphosphine oxide (X) of the present invention was superior to penzyl dimethyl ketal [1]. was known. The Barcol hardness of Mixture 2 was 50 and that of Additive 1 was 0. Example 7 Ultraviolet curing of a block made of UP resin A A glass plate mold (1
6 x 11 Crab light tube (TUV4)
0W/0. (manufactured by Philips). The test apparatus was such that the ultraviolet light (from an 87 x 49 cm irradiation chamber with one solid lamp placed side by side) could penetrate the wood preparation from below through the glass bottom plate. The distance between the lamp and the block is 1.7 arcs, the thickness of the layer to be cured is 9
It was the skin. This test revealed that the sensitizer system of the present invention allows a much more complete cure than with penzyl dimethyl ketal. When penzyl dimethyl ketal was used, a yellow molded product with a liquid surface layer was produced after 9 hours of irradiation, whereas
The preparation according to the invention gave completely cured, clear moldings after 1.5 hours of irradiation. 'b' In another test, the thickness of the cured layer of various resin preparations was determined depending on the irradiation time. For this purpose, the sensitized mixture of resin A and the photoinitiator is heated from above in a crystallizing dish (a Petri dish with a diameter of 9 arcs) whose side walls are covered with UV-impermeable paper (Tesacrep). Each was irradiated with a tube (TUV40W/05 manufactured by Philips). The distance between the irradiation source and the resin surface was 11. Narrow vertical observation holes in the wall deposits made it possible to track and measure the progress of hardening into deep layers. The boundary between the cured layer and the uncured resin layer was easily recognized because the rupture coefficients were different from each other. The results are summarized in Table 9. Penzyl dimethyl ketal cured only 18 of 62 sides in 80 minutes, whereas pivaloyl diphenylphosphine oxide (
When using X), up to the 62 side, that is, the entire block was cured. By adding tertiary butyl peroctate, the curing time was reduced to 30 minutes. Table 9. Examples of UV curing of resin preparations in thick layers. 8 Thicknesses from various resins sensitized with 0.2% UV initiator for evaluation of photo-induced yellowing of UP resin moldings. 4.8 sails, a 5-ga diameter disk, Koji light tube (TUV4 skin/
05, manufactured by Philips Corporation), and then irradiated with an ultraviolet irradiation castle consisting of 10 crab light tubes of the above type for 4 minutes at room temperature. The distance between the irradiation source and the circular plate surface was 11 skins. Yellowing is A
Judgment was made by yellowing index according to STMDI925-67. Measurements were carried out using transmitted light using a device DMC25 from Ice. From the results shown in Table 1, it can be seen that in all cases the molded articles made from the preparations of the present invention show less yellowing than those made using the known preparations (containing sensitizers 1 to W). It was done. Table 10: Example of bag modification of UV-cured molded products from various UP resins 9 It was confirmed that the sensitizer according to the present invention similarly produced products with less rhombic discoloration during UV-curing of peroxide-containing molding materials. To do this, a preparation of Resin A, tertiary butyl peroctoate and sensitizers 1, B and Tube (TU
It was irradiated for 25 minutes from a distance of 15 degrees using a V40W/05 (manufactured by Philips). The cooled moldings were then treated for 1 hour in the same crab light tube at room temperature. Molded articles with sensitizer X exhibit the lowest yellowing index and therefore the least yellowing. Table 11 Examples of yellowing of peroxide-containing UV-irradiated moldings made of resin A 10 Production of thin layers that can be pressed onto paper laminates or on GFK surfaces For example, resin A, sensitizer XO. 5% and 1% penzoyl peroxide to a thickness of approximately 100% on the sheet.
Apply a film of 1 m/lm under a mercury vapor high pressure lamp.
It passed at a speed of 1 minute. The distance between the lamp and the film was 25 skins. The thus cured film was pressed onto a hot paper laminate or onto a GFK surface. The thin layer did not yellow. Examples 11-
In No. 17, a particularly excellent highly reactive ultraviolet sensitizer was used. Example 11 Preparations consisting of UP resins A, C, G, B and vinylester resin K and containing 0.2% of various sensitizers were cured by UV radiation in the manner described above. A comparison of the curing activities (Table 12) showed that the most rapid curing was possible with initiators XX to XXW. Pivaloyl-diphenylphosphine oxide X
reaches the activity of 2,6-dichlorobenzoyl-diphenylphosphine oxide, but of course its activity decays over time upon storage in the UP resin. Table 12: Examples of UV curing of sensitized UP resins and vinylester resins by light tube irradiation The curing activity was then measured in the same manner as in Example 11 at room temperature. The measurement results before and after storage of the first box thin shavings are shown in comparison. This result showed that the initiators XX to XXW kept their activity constant under the test conditions. A longer storage test at room temperature showed the same trend (Table 14).
Table 13 Curing activity test of UV sensitized UP resins after storage at 60C Example 13 Preparations from UP resin A or B and various UV initiators were stored in a dark closed container at room temperature and Cure activity was measured from time to time by the method described in 11. From Table 14 it is seen that with initiator XX a storable and UV-curable UP resin is obtained. No.
Table 14 Example of curing activity test of UV-sensitized UP resins after storage at room temperature A disk with a thickness of 4.8 mm and a diameter of 5 mm, which has been sensitized by
AK40W/05, manufactured by Philips) and then irradiated with the same light source for 6 seconds or 120 minutes at room temperature (5 crab light tubes arranged in sequence). The distance between the light source and the disc was 8.5 skins. Yellowing was evaluated by the yellowness index (ASTM DI 925-67), and the measurements were carried out in transmitted light using a device DMC25 from ISS. The results are shown in Table 15. It is clear that the moldings from the preparations according to the invention exhibit less yellowing in all cases than the moldings from the known preparations containing benzyl dimethyl ketal 1. Table 15 Yellowing Example of Ultraviolet Curing UP Resin Molding 15 Ultraviolet Curing of UP Resin Molding Material [a} Ultraviolet initiator XXO. Preparation 6 from UP resin G containing 1% or 10.1% penzyl dimethyl ketal
The foundation part was filled with Multinal BM2 (AI203/General 2).
40 parts (manufactured by Martinswerke) and 1.5% of vertical magnesium oxide (product of Merck) (based on UP resin)
mixed with. This mixture was mixed into a multilayer glass fiber mat (Vetrotex Textile) having dimensions of 10 x 12 cm.
123-40-450) and polyester seaweed.
Concentrate for 3 days at room temperature between tubes and finally
The molding material was cured by irradiation with LAK40W/05), during which time the temperature change in the molding material was tracked using a thermal element. The distance from the surface of the molding material to the irradiation source (five crab light tubes arranged in sequence) was 8 degrees, and the irradiation time corresponded to the time when the molding material reached its highest curing temperature. After cooling the molded article, Barcol hardness (Impressor 935) was measured on the lower and upper sides. The first degree results clearly show the superiority of the preparation according to the invention containing UV initiator XX. In order to achieve sufficient curing of the molding material, three layers of glass fiber mat (corresponding to layers with a side thickness of 3.8 to 4.5) are required.
In this case, 5 minutes and 19 minutes of sand was sufficient, whereas a layer with a thickness of 6.6 to 7.2 layers (glass fiber mat ≦7 layers) required approximately 13 minutes of irradiation time.Pendyl dimethyl ketal 1 In the case of molding materials based on UP resin G.AI2, complete curing of the laminate with 7-layer glass fiber mats was not achieved despite doubling the irradiation time.Table 16 UP resin G.AI2
UV curing of resin mat based on glass fiber mat
M2) 32.1 *Glass fiber mat (Betrotesox
Textile glass mat M123-40-450) 1
9.8 Purple 'b' A UP resin molding material that does not contain glass fibers that can be bonded is mixed with UP resin G, filler AI203/pan 20 (Martinal BM2, manufactured by Martinswerke), light magnesium oxide 1. Preparations from 5% (based on UP resin) and 0.1% each of UV initiator XX or penzyl dimethyl ketal 1 (based on HP resin) were prepared by thickening for 3 days. The weight ratio of UP resin to filler was 60:40. Inside the tin plate lid, each layer is 2cm thick, and the crab light tube (TLAK4
0W/05 (manufactured by Philips) for 3 minutes, and temperature changes over time were tracked using a heating element immersed in the molding material to a depth of one skin. The distance between the irradiation source and the surface of the molding material was 6 cm. After cooling, the lower layer of uncured molding material was mechanically separated and removed, and the Barcol hardness (Impressor 935) of the new surface thus created was measured after cleaning. In the molding material of the present invention, the thickness on the 12.6 side was hardened, whereas in the known molding material containing penzyl dimethyl ketal 1, only a layer with a thickness of 7° was hardened (the first layer was hardened). See Table. Table 17 UV Curing Examples of Concentrated Resin-Filler Mixtures It was irradiated with a crab light tube (TL-AK40W/05 manufactured by Philips).The UP resin sample was placed on a cork plate (
It was placed in a tin plate lid with a diameter of 5 skins, placed on a 5-wall plate (5 ribs thick). The distance between the crab light tube and the resin surface was 8 skins. After irradiation and cooling, rods were sawn out from each molding, the total layer thickness was determined, and the residual styrene content was determined using the bottle method according to Dm 16945. The obtained results are summarized in the first box table. According to this, it is known that the amount of residual styrene of the molded product sample having the sensitizer combination of XX and 1 is smaller than that of the sample with sensitizers XX and 1 alone. Table 18
Residual styrene content of UP resin moldings from UV-irradiated resin A Example 17 Photocuring of unsaturated polyester resins was carried out in two stages using the photoinitiators of the invention. In the first step, after a short irradiation time, a malleable, storable semi-finished product was produced, which could be shaped and cut, and could also be drilled with holes, for example for the production of buttons. By irradiating again in the second stage, curing was finally completed. Resin A of 2,4,6-trimethylbenzoyl diphenylphosphisooxide XX
The 0.1% solution was made into a 2-thick layer between two polyester sheets, and a crab light tube (TL-AK40W/05
(manufactured by Philips) for 1 minute. The distance between the halo tube and the resin surface was 10 degrees. A flexible semi-finished product is obtained, which can be cut with a sharp knife,
Moreover, it could be easily deformed by hand. The Barcol hardness on both sides was 0 (Barcol Impresa 935).
After storage for 2 hours at room temperature, the unaltered flexible semi-finished product was again exposed to light tube irradiation for 15 minutes.

Claims (1)

[Claims] 1. The ultraviolet sensitizer has the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 is a linear or branched alkyl group having 1 to 6 carbon atoms. , or a cyclohexyl group, a cyclopentyl group, an aryl group, an aryl group substituted with a halogen atom, an alkyl group, or an alkoxy group, or a 5- or 6-membered heterocyclic residue containing S or N,
R^2 has the same meaning as R^1, in which case R^1 and R
^2 may be the same or different, or means an alkoxy group, an aryloxy group, or an arylalkoxy group having 1 to 6 carbon atoms, or R^1 and R^2 are combined to form one ring. may be formed, and R^3 is 2 to 18
a straight-chain or branched alkyl group having 5 carbon atoms,
means an alicyclic residue having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a 5- or 6-membered heterocyclic residue containing S, O or N, in which case R^3 further represents It may have a substituent, or it may have the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R^1 and R^2 have the above meanings, and X is a phenylene group or 2 to 6 carbon atoms is an aliphatic or alicyclic divalent residue having a radical R
One or more of R^1 to R^3 may be olefinically unsaturated. (a) at least one ethylenically unsaturated copolymerizable polyester; (b) at least one ethylenically unsaturated copolymerizable monomeric compound; (c) an inhibitor; (d)
) a UV sensitizer and optionally (e) paraffin;
Photocurable polyesters containing mixtures of pyrolytic initiators, fillers, reinforcing agents, lubricants, inert solvents, shrinkage control additives and/or other auxiliaries used in unsaturated polyester materials. Resin composition. 2. The ultraviolet sensitizer is characterized in that it consists of an acylphosphine oxide compound in formula 1, in which R^1 and R^2 have the above meanings, and R^3 is a tertiary aliphatic residue. , a photocurable polyester resin composition according to claim 1. 3. The ultraviolet sensitizer is a formula 1 in which R^1 and R^2 have the above meanings, and R^3 is a cycloalkyl group,
means a phenyl group, naphthyl group, S, O or N-containing 5- or 6-membered heterocyclic residue containing substituents A and B bonded at least in two ortho positions to the carbonyl group, in which case A and B may be the same or different, and are characterized by consisting of an acylphosphine oxide compound, which is an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a thioalkyl group, a carbalkoxy group, a cyan group, or a halogen atom, Claim 1
The photocurable polyester resin composition described in 1. 4. The ultraviolet sensitizer consists of an acylphosphine oxide compound in formula 1, in which R^1 and R^2 have the above meanings, and R^3 is a 2,4,6-trimethylphenyl group. The photocurable polyester resin composition according to claim 1, which is characterized by: 5. Photocuring according to claim 1, characterized in that the acylphosphine oxide compound is used in an amount of 0.005 to 5% by weight based on the total weight of components (a) and (b). polyester resin composition. 6 An acylphosphine oxide compound of formula 1 as a UV sensitizer is mixed with an aromatic ketone, an aromatic disulfide or a naphthalene sulfonyl chloride from 85:15 to 15:
characterized by containing in combination in a weight ratio of 85,
A photocurable polyester resin composition according to claim 1. 7. The photocurable polyester resin composition according to claim 6, wherein benzyl ketal, benzoin ether, or bensoin ester is used as the aromatic ketone.