DE2243190A1 - PROCESS FOR CURING ACRYLIC ACID ADDUCTS WITH IONIZING RAYS - Google Patents

Description

Process for curing acrylic acid adducts with ionizing

.Beams.

It is known that the crosslinking of synthetic resin polymers by exposure to ionizing radiation, e.g. X-rays, gamma rays, beta particles or beams of strongly accelerated electrons. at Most of the technical applications of these radiation methods were electrons with an energy between 50 and 4000 KeV are used.

In French patent no. 1.5 ^ 9 * 956 is also the use of ionizing radiation to harden synthetic resin coatings, consisting of acrylic acid or Methacrylic acid adducts of bisphenol A diglycidyl ether, described. ■.

These known coatings obtained by radiation curing are generally good mechanical properties, but they also have some disadvantages for many technical applications, e.g.

309810/1126

insufficient flexibility or stretchability and poor abrasion resistance.

It has now surprisingly been found that one

Coatings with better elasticity and improved abrasion resistance are obtained if the known synthetic resin coatings are used instead from the in French patent no. 1 * 5 ^ 9 * 956 connections described Acrylic acid adducts that result from the addition of acrylic or methacrylic acid to certain polyester dicarboxylic acids pre-extended polyepoxide compounds are obtained, dissolved or optionally mixed with other mono- and / or polyolefinically unsaturated compounds are used.

The present invention thus relates in particular to a method for curing acrylic acid adducts in the form of thin layers or coatings, with ionizing rays, characterized in that acrylic acid adducts are used the general formula

CH ₂ \

C-C-O-CH-C

C - CH 0 - C

wherein R ^, R ₃ and R ₃ ¹ each independently represent a hydrogen atom "or the methyl group, R ₂ or R ₇ ¹ a hydrogen atom and A denotes the by separation of the 1,2-epoxy

309810/1126 ^iii:

SiGi '

A radical of a polyglyeidyl compound obtained from ethyl groups or in which A together with R _p or 'R * under a

OH OH end of grouping ^ ^^ -C-CH-

cyeloaliphatic ring or the cycloaliphatic ring system of a converted cyeloaliphatic polyepoxide compound mean, B means a long-chain polyester radical in which branched or unbranched alkylene and / or alkylene chains alternate with carboxylic acid ester groups, where the quotient Z / Q, where Z is the number of those present in the recurring structural element of the remainder B. Carbon atoms and Q is the number of recurring Structural element of the radical B is oxygen bridges present, be at least J and preferably at least 4 must, and furthermore the total number of carbon atoms present in radical B is at least 8, and η the number 1 or 2 denotes, alone or, if appropriate, in a mixture with other mono- and / or polyolefinically unsaturated ones Connections irradiated.

The acrylic acid adducts of the formula I can be prepared by adding 1 mol of a polyepoxide compound the general formula

= 0 M

-o c

-3 (II),

309810/1126 in which R ₂ , R ₂ ', R ₃₉ R ₃ ¹ , A, B and η have the same meaning as in formula I, η moles of acrylic acid and / or methacrylic acid are added in a manner known per se.

The addition reaction is preferably carried out in the melt; however, it is also possible to work in solution. The addition of acrylic or methacrylic acid is carried out at 20-18O ⁰ C, preferably at 90-1 ^ 0 C, without or in the presence of basic catalysts. The course of the addition reaction can easily be done by continuously checking the epoxide content of the reaction mixture or by titrating the unreacted acrylic acid.

Particularly suitable basic catalysts for the addition of acrylic or methacrylic acid to the polyepoxide compound of the formula II are tertiary amines, such as triethylamine, tri-n-propylamine, tribenzylamine, benzyidimethylamine, Ν, Ν ¹ -

Dimethylaniline and triethanolamine; quaternary ammonium bases, such as benzyl trinie thy latnonium hydroxide; quaternary ammonium salts, such as tetramethylamnionium chloride.,. Tetraäthyla.mmoniu: n-

Ehlorid, Donzyltriiriethylainmoniurnchlorid, EenzyltrimethylammoniiL'nacetat, Methyltriethylammoniumchlorid; also ion exchange resins with tertiary or quaternary amino groups; further Trialkylhydrazoniumsalze as hydrazoniuinjodid Trimcthyl. . . '

Low molecular weight thioethers and sulfonium salts are also suitable as further catalysts.

Such thioethers or sulfonium salts are mentioned *: Diethyl sulfide, ^ -hydroxyl?: Ethylethyl sulfide, / 3-hydroxypropyl-

309810/1 1 26

BAÖ'ÖRKirNÄL

ethyl sulfide, ß-hydroxy-tetramethylene ethyl sulfide, thio- · ':

diglycol, mono-ß-cyanoethylthioglycol ether, dibenzyl sulfide, benzylethyl sulfide, benzylbufcyl sulfide, trimethylsulfonium iodide, tris (A-hydroxyethyl) sulfonium chloride, dibenzylmethylsulfonium sulfonium, dibenzylmethylsulfonium sulfidyl, 2,2-epoxydylethylsulfonyl. · Methyl sulfide, dithiane. . -. - '·. . _'·; ... ...... ·;. . ■■

The reaction can also be carried out by adding other suitable alkaline reagents, such as sodium hydroxide, potassium hydroxide, barium hydroxide, Calcium hydroxide, sodium carbonate ,. Potassium carbonate or sodium acetate.

The polyepoxide compounds of formula II can be prepared by attaching to 1 mole of a long chain polyester dicarboxylic acid the formula

HQOC -B- COOH. (III),

wherein B has the same meaning as in formula I, 2 moles of a polyepoxide compound with formation of an epoxide group-containing one Adduct accumulates. '' '■■ ""' ". ■ ...

The polyester dicarboxylic acids of the formula III used to prepare the adducts containing epoxy groups " are obtained by polycondensation of aliphatic dicarboxylic acids with aliphatic diols. The chain Such polyester is from the alternating basic building block of the dicarboxylic acids as well as from the alternating one. Foundation

309810/1126 BAOORfGiNAL

built up stone of diol. The recurring structural element, i.e. the smallest recurring chemical Grouping in the chain is done by the two together Basic building blocks linked by an ester bond from the dicarboxylic acid and from the dialcohol, and

has the formula · ■ · ■ ■

-O -ROCR ¹ -C-II II
0 0 '.

where R is the hydrocarbon radical of the diol and R ^{1 is} the hydrocarbon radical of the dicarboxylic acid. The dicarboxylic acid and the diol for the structure of the acidic polyester must be selected in such a way that the sum of the number of carbon atoms of the dicarboxylic acid and the number of carbon atoms of the diol divided by the two oxygen bridge atoms of the structural element is at least 3 and preferably at least 4

Furthermore, the aliphatic dicarboxylic acid and the aliphatic dialcohol for the polycondensation chosen in this way

.be that the sum of the "alternating structural elements." of the produced polyester chain occurring carbon

- atoms is at least 10. '"- , - ¹ V-" ~

■ The lowest definition in the present case is the shortest, acidic polyester made from 2 moles of succinic acid and 1 mole of ethylene glycol.

309810/1126 ORIGINAL BATHROOM

22A319Q

As alphatic dicarboxylic acids with at least 4 C atoms in the molecule, which can preferably be used to build up such acidic polyesters, may be mentioned: "-

Succinic acid, glutaric acid, adipic acid, trimethyladipic acid, Pimelic acid. Suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, Dodecanedicarboxylic acid, allyl succinic acid, dodecyl succinic acid, Dodeceny! Succinic acid, heptanedicarboxylic acid.

Can be used as aliphatic diols, aie preferred for construction of the present acidic polyesters are used, include: Aethylengiykoly propane-l, 2-diol, ^l,] i 3utanaiol, 1,3-butanediol, 1,5-pentanediol, NeopentylglykoJ, Ι, ο-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonaridiol, 1,10-decanediol,!, il-undecanediol, l _f 12-dodecanediol, 1,6-dihydroxy-2,2 , 4-trimethylhexane, Ι, β-dihydroxy- _ 2,4,4-triirethylhexane. ' · ".. .. - ' ^:

Of course, acidic polyesters can also be produced by condensing mixtures of different dicarboxylic acids with mixtures of different diols, provided that the conditions postulated above for the quotient Z / Q and the total number of carbon atoms in the polyester chain are observed » '■ ■'

The acidic polyesters used with preference thus generally correspond to the formula

HO-C-Rr -C-T-O-Pv -O-C-R-C j-OH

Il * ■ II. 5 "4 j,

0 0 L 0 0 ^J ia

3 0 9 8 10/1126 BAD ORiOINAU

wherein R ^ and R ^ are branched or unbranched alkylene or alkenylene chains, each of the two radicals R, and R ₅ must contain at least 2 carbon atoms, and wherein the number m is chosen so that the sum of the carbon atoms occurring in the polyester dicarboxylic acid at least 10 is.

Purely for the production of those containing epoxy groups Adducts are also those acidic polyesters which are formed by the addition of (a + b) moles of a lactone to 1 mole an aliphatic dicarboxylic acid according to the reaction equation.

(a + b) r-IL-C = 0 + KO-C-IL-C-OH

⁶ H ⁷ I!

ρ 0

-0

-C-R,

-C-R-C-

U '■ ι: 0 0

OR —C- .6 η-

-OK

'V)

are available, in which R, - is an alkylene chain at least and preferably denotes at least 5 carbon atoms, R ^ PJr is an aliphatic hydrocarbon radical, and wherein the numbers a and b are chosen so that the sum of the carbon atoms occurring in the polyester dicarboxylic acid ■ is at least 10. . .

309810/1126 BAD

In this class of compounds the alternating ■ basic building block is identical to the recurring structural t in the "chain, and sorr.it contains the structural element a 6InZiSe ₁ oxygen bridge. The quotient Z / Q in this case is therefore equal to the number of carbon atoms in the hydrocarbon residue of the lactone ,, 'from which -the "-acid polyester is made up. .

Examples include the addition products of (a + .b) moles of C-caprolactone, or sxaltolide (= lactone of 15-hydroxyheptadecanoic acid) to 1 mole of Bern- ... stinic acid, adipic acid or sebacic acid. '·

For the production of the adducts containing epoxy groups Polyepoxy compounds and the long-chain polyester dicarboxylic acids of the formula III are in principle all classes of epoxy compounds, provided that they contain more than one epoxy group contained in the molecule,

Particularly suitable polyepoxide compounds are those with an average of more than one glycidyl group or β-methylglycidyl group bonded to a heteroatom (eg sulfur, preferably oxygen or nitrogen); may be mentioned in particular Di or. Polyglycidyl ethers of polyvalent aliphatic alcohols, such as 1,4-butanediol, or polyalkylene glycols, such as polypropylene glycols; Di- or polyglycidyl ethers of cycloaliphatic polyols, such as 2,2-bis (4 ^f -hydroxycyclohexyl) propane; Di- or polyglycidyl ethers of polyhydric phenols, such as resorcinol, bis (p-hydroxyphenyl) methane, 2,2- To-

3098 10/11 26 '

(ρ-hydroxyphenyl) propane (= diomethane), 2,2-bis (4'-hydroxy-3 ', 5'-dibromophenyl) propane, 1,1,2,2-tetrakis- (p-hydroxyphenyl) - ethane, or of condensation products of phenols with formaldehyde obtained under acidic conditions, such as phenol novolaks and cresol novolaks; Di- or poly (β-methylglycidyl) ethers of the polyhydric alcohols or polyhydric phenols listed above; Polyglycidyl esters of polybasic carboxylic acids such as phthalic acid, terephthalic acid, A. Tetrahydrophthalic acid and hexahydrophthalic acid; N-glycidyl derivatives of amines, amides and heterocyclic nitrogen bases, such as N, N-diglycidylaniline, Ν, Ν-diglycidyl-toluidine, Ν, Ν, Ν ¹ , N ¹ -tetraglycidyl-bis (paminophenyl) -methane; Triglycidyl isocyanurate; N, N'-diglycidylethylene urea; N, N'-diglycidyl-5,5-dimethylhydantoin, N, N ¹ -diglycidyl-5-isopropylhydantoin; N, N ¹ -Diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydrouracil, 1-glycidyloxymethyl-3-glycidyl-5,5-dimethyl-5,6-dihydrouracil, 1-glycidyl-3- ( ß-glycidyloxyathyl) -5,5-dimethylhydantoin, bis (3-glycidyl-5,5-dimethylhydantoinyl-l) methane and 1,6-bis (I-5 ¹ -glycidyl ^1, 5'-dimethylhydantoinyl-3 ') -hexane.

Particularly suitable cycloaliphatic epoxy compounds are, for example, those of the formulas

CH,

CH HC-CO- CH ₀ - 'CH HC

o. , 9

² 30 9 8.10 / 11 / I ²

BATH ORIGINAL

( - J), ^ -Epoxycyclohexylir.ethyl- ^ ', * J' - epoxy cy clohexanecarboxylate) ,,

■ 'S

CH

HC

C Il O

/ X

O - CH ₂ - CH. HC

CH HC - CH_

X / ⁵

CH

-CH

(= 3,4-epoxy-6-yn6thylcyclohexy line thyl-3 ', 4 ¹ -epoxy-o'-methyl-

■. · ■ ' s-

cyclohexanecarboxylate). ' ".. - · _ ■

^CH

CH

2 CH- 0 \ / 2 \

O
\

CH

CH

CH - CH, - O ^J

CH,

CH,

dimethanol)

called.

HC
\

CH,

-y, ² ! - '-epoxycyclohexane-l!,! ¹ -

The adducts containing epoxy groups are generally produced by simply melting the polyepoxy compound together with the acidic polyester of formula 1 in the prescribed stoichiometric proportions. 200 ⁰ C, preferably 130 - - As a rule, one works in the temperature range 100 ° to 180 ° C.

3098 10/1126

ORIGINAL BATHROOM

The acrylic acid adducts of the formula I are colorless to slightly colored, highly viscous or solid resins, the acrylate group content of which can be determined, for example, by titration, hydrogenation or by NMR analysis. salts etc. can be prevented from premature polymerization. ...

The acrylic acid adducts of the formula I are valuable resins which polymerize alone or together with others monomers can be polymerized with ionizing radiation. The acrylic acid adducts are particularly suitable

also as a flexibilizer for known radiation-curable resins.

The proportion of polymerizable monomers in the curable mixture is advantageously 10 to 99 % based on the total amount of the mixture.

As monomers which can be added to the acrylic acid adducts of the formula I, there are above all compounds of Acrylic acid series, such as esters of acrylic acid or methacrylic acid and alcohols or phenols, e.g. methyl ticrylate, ethyl aerylate, Butyl acrylate, dodecyl acrylate, methyl methacrylate, ethylene glycol dimethacrylate; in B'rage. It is also possible to use other reactive olefinically unsaturated monomers, e.g. Acrylonitrile, methacrylonitrile, styrene, divinylbenzene, vinyl esters such as vinyl acetate, allyl bonds such as diallyl phthalate and the addition products of acrylic acid and methacrylic acid to e.g. bisphenol A-glycidyl ether, hexahydrophthalic

309810/1126

BAD ORIGINAL

Use acid diglycidyl ester or N, N '~ diglycidy! hydantoin

Those especially suitable for the production of coatings Acrylic acid adducts can also use flexibilizers, Fillers and preferably pigments, e.g. titanium dioxide.

The mixtures of acrylic acid adducts have good adhesion to the surface of the base material so that coatings on metals, Made of wood, plastics, glass, paper, leather, etc. can be. '·

The curing of the acrylic acid adduct mixture can be done with any ionizing radiation, preferably with a high-energy electromagnetic radiation, such as X-ray or gamma radiation, as well as accelerated Electrons are made. In the latter case, with an average electron energy of 50 KeV to 4OOO KeV worked. Is it about hardening thinner Layers such as coatings will have an average electron energy of 50 to 600 KeV and a curing dose of 0.5 to 5 * 0 megarads, preferably 1.0 to 5.0 megarads applied.

The acrylic acid adduct mixture can advantageously before, during or after hardening, additional heat treatment is required, which in some cases In some cases, networking is facilitated.

■ · Curing is best carried out in the absence of oxygen. To do this, you turn

a protective gas atmosphere, e.g. nitrogen.

309810/1126. .

In some cases it is advantageous to add a small amount of a polymerization catalyst which forms free radicals, such as, for example, peroxides, azo compounds, persulfates, to ^{the acrylic acid: adduct mixture.}

In the following examples, unless otherwise stated, parts mean parts by weight and Percent weight percent; the temperatures are given in degrees Celsius.

309810/1126

Acrylic acid adduct A

a) 3OO S of an acidic polyester, which consists of 11 mol Sebacic acid and 10 moles of neopentyl glycol was prepared by the melt process and a. Acid equivalent of 1344 (theory: 1450), one with 300 g were Room temperature liquid diomethane diglycidyl ether with a ■ Epoxy content of 5 * 35 epoxy equivalents / kg mixed and Stirred for 3 hours at 140 C under nitrogen atmosphere. The pre-adduct obtained in this way had an epoxide content of 2.55 epoxide equivalents / kg, which is an epoxide equivalent weight of 392 corresponds.

b) 2156.0 g (5 * 5 epoxy equivalents) of the previously described pre-adduct were mixed with 396 * 0 g (5.5 mol) of acrylic acid and 2.0 g (0.78 %) of hydroquinone and increased to 90 with stirring and under a nitrogen atmosphere C heated. Then 7 * 0 g (2.75 % o ) triethylamine were added and the homogeneous mixture was heated to 100.degree.

The reaction mixture was then left for 17 hours held at 100 C. The result was a clear, orange, highly viscous mass with an acid equivalent weight of II500, an epoxy equivalent weight of 3 ° 15O and a hydroxyl equivalent weight of 495 (theory 464). The content of polymerizable double bonds was 2.25 equivalents / kg (Theory; 2.16).

3098 10/1126

Acrylic acid adduct B

a) 3600 g of an acidic polyester, which consists of 11 mol Sebacic acid and 10 moles of neopentyl glycol according to the Melt process was prepared and had an acid equivalent weight of 1080, were 1800 g Glycidyl hexahydrophthalate with an epoxide content of 6.2 epoxy equivalents per kg for 3 hours at 145 ° C under a nitrogen atmosphere. That so The pre-adduct obtained was a viscous liquid with an epoxy content of 1.40 epoxy equivalents per kg and an acid equivalent weight of > 20,000.

b) 2990 g (4.3 Epoxidä'quivalente) of the forward-described epoxy group-containing adduct were treated with 8.0 g (2.5 ° · L) hydroquinone and with stirring and under a nitrogen atmosphere at 80 ⁰ C heated. To this, 303.5 g (4.3 mol-2 7o) of acrylic acid and 16 g (0.5 %) of benzyldimethylamine were added and the homogeneous mixture was ^{heated to 100 °} C., a weak exothermic reaction occurring. The reaction mixture was then ^{kept at 100 °} C. for 6 hours. The acid equivalent weight became infinite. The reaction product was a brown viscous mass and had a polymerizable content. Double bonds of 1.40 equivalents / kg (theory: 1.305)

3098 10 / 1-126

Acrylic acid adduct C

a) 1600 g of an acidic polyester, which by polycondensation of 8 moles of adipic acid and 7 moles of neopentyl glycol obtained by the melting process and having an acid equivalent weight of 705 were found to be 800 g Tetrahydrophthalic acid diglycidyl ester with an epoxide content of 6.45 epoxy equivalents per kg and with 0.24 g a 50% aqueous solution of tetramethylammonium chloride stirred for 3 hours at 140 ° C. in a nitrogen atmosphere. The pre-adduct obtained in this way had an epoxide content of 1.04 epoxy equivalents / kg and an acid equivalent weight from> 20,000. ...

b) 2940 g (3.0 equivalents) of the preadduct described advance were mixed with 7.8 g (2.5 X ₃₎ of hydroquinone and heated with stirring and under a nitrogen atmosphere at 70 ⁰ C. For this purpose, 212g (3.0 mol - 2%) of acrylic acid and 16 g (0.5%) of benzyldimethylamine added and heated the homogeneous mixture to 100 ⁰ C. The reaction mixture was then ^{kept at 100 °} C. for 5 hours. The acid equivalent weight rose to 30,500. A yellow, clear, highly viscous, tough product with a polymerizable double bond content of 1.94 equivalents / kg (theory 1.96) resulted. ·.

30981 0/11 26 BAD ORIGINAL

Acrylic acid adduct D.

a) 1080 g of an acidic polyester, which was prepared by polycondensation of 11 mol of sebacic acid and 10 mol of neopentyl glycol by the melt process and had an acid equivalent weight of 1080, were with 582 g of triglycidyl isocyanurate with an epoxide content of 9 _; Stirred for 15 epoxide equivalents per kg for 3 hours at 140 ⁰ C in a nitrogen atmosphere. The resulting prepolymer thus obtained was a highly viscous liquid and had an epoxide content of 2 _ä 44 equivalents of epoxy per kg.

b) 1870 g (5.0 epoxide equivalents) of the preadduct described advance were mixed with 5.75 g (5 ^ 0 / = o) hydroquinone and heated with stirring and under a nitrogen atmosphere at 70 ⁰ C. To this was added 422 g (5.0 mol - 2%) of methacrylic acid and 11.0 g (0.5%) of benzyldimethylamine added together, the homogeneous mixture to 100 ⁰ C heated, and a weak exothermic and Pveaktion entered. The reaction mixture was then ^{kept at 100 °} C. for 4 hours. The acid equivalent weight rose to 80,000. A light brown, highly viscous product with a polymerizable double bond content of 2.03 equivalents / kg (theory: 2.17) resulted.

309810/1 126

BATH ORIGINAL Acrylic acid adduct E.

a) 667 g of an acidic polyester, which was obtained by polycondensation of 8 moles of adipic acid and 7 moles of neopentyl glycol by the melt process and an acid. equivalent weight of 705 (theory 822), had been with 333 g of a Diomethandiglycidyläthers having an epoxide content of 5.2 epoxide equivalents / kg · stirred for 8 hours at 140 ⁰ C in a nitrogen atmosphere. The adduct thus obtained, containing epoxy groups, was a dark yellow, highly viscous liquid with an epoxy content of 0.72 epoxy equivalents per kg (theory 0.79) and an acid equivalent weight of over 100,000.

b) 3058 g (2.2 equivalents) of the epoxy described above. . Group-containing adduct was admixed with 8.0 g (2.5 % ₉ ) of hydroquinone and heated to 70 ° C. with stirring and under a nitrogen atmosphere. Then "156.8 g (2.2 mol - 1%) of acrylic acid and 32.0 g (1.0%, based on the total amount) of triethylamine were added and- ·

• the homogeneous mixture is heated to 100 ° C. The reaction mixture vmrde for 4 hours at 100 ⁰ C. The acid equivalent weight rose to 8,500. The result was a light yellow, clear, highly viscous product with a content of polymerizable double bonds of 0.87 equivalents / kg (theory: 0.685).

3 0 9 8 10/1126 ORIGINAL BATHROOM *

a) 1000 g of an acidic polyester, which was prepared from 11 mol of adipic acid and 10 mol of Ilexanediol by the melting process and had an acid equivalent weight of 1070 (theory: 1213) and a melting point of 46 ° C, were with 1000 g of a diomethane diglycidyl ether with an epoxide content of 5.2 epoxide equivalents / kg for 2 hours at IAO ⁰ C under a nitrogen atmosphere. The preliminary addict obtained in this way had an epoxide content of 2.37 epoxide equivalents per kg.

b) 2744 g (7.08 equivalents) of the pre-adduct described above were mixed with 8.1 g (2.5%) of hydroquinone and heated to 70 ° C. with stirring and under a nitrogen atmosphere. For this purpose, 494 g (7.0 mol - 2%) of acrylic acid and 16.0 g (0.5%) of benzyldimethylamine added and heated the homogeneous mixture at 10O ⁰ C. The reaction mixture was then ^{kept at 100 °} C. for 4 1/2 hours. The acid equivalent weight rose to 27 825. The result was a brown, clear, highly viscous product with a content of polymerizable double bonds of 2-15 equivalents / kg (theory: 2.16).

3098 10/1126

^ ORIGINAL

Acrylic acid adduct G

a) 1080 g of an acidic polyester, which was obtained by polycondensation of 11 moles of sebacic acid and 10 moles of neopentyl glycol by the melting process and had an acid equivalent weight of 1080 (theory: 1450), were mixed with 390 g of 3,4-epoxyhexahydrobenzal-3'4 ¹ -epoxycyclohexanedimethanol with an epoxide content of 6.4 epoxide equivalents / kg and 2.94 g of a 6% solution of a sodium alcoholate, which is obtained by dissolving 0.28 parts of sodium metal in 100 parts of 2,4-dihydroxy-3-hydroxymethylpentane, while Stirred for 3 hours at 140 ° C. under a nitrogen atmosphere. The adduct thus obtained, containing epoxy groups, was a dark yellow, highly viscous resin with an epoxy content of 0.84 epoxy equivalents / kg (corresponding to an epoxy equivalent of 1190) and an acid equivalent weight of over 150,000.

b) 595.0 g (0.5 epoxy equivalents) of that previously described 1.6 g (2.5% o) of hydroquinone were added to the pre-adduct and the mixture was heated to 110 ° C. with stirring and under a nitrogen atmosphere warmed up. 35.7 g (0.5 mol - 1%) of acrylic acid and 3.2 g of (0.57o) benzyldimethylamine were added to this and the homogeneous mixture held at 110 ° C for 11 hours. The acid equivalent weight rose to 9910. The result was a yellow color

. clear, highly viscous tough mass with a content of polymerizable Double bonds of 1.118 equivalents / kg (theory:

'0.793).

309810/1126

Example 1

90 πιμ thick films of acrylic acid adducts A to G according to Table 1 and mixtures of these acrylic acid adducts and polymerizable monomers according to Table 2 were applied to electrolytically yor-treated iron sheet (sheet thickness 0.3 mm). After about 1 minute, these films were exposed to accelerated electrons with an average energy of 400 KeV by passing the metal sheets lengthwise through an electron beam (radiation intensity: 4 megarads / second). The experiments were carried out at room temperature. However, the irradiations were carried out in a nitrogen atmosphere (maximum oxygen concentration 0.2 %) . The films were then immediately examined for surface tack and their surface hardness was tested using a simple test method with a steel blade. The resistance of the synthetic resin films to chemical solvents was tested by applying a drop of toluene. The insoluble fraction was determined in a Soxhlet extraction apparatus by extraction with toluene for 24 hours. Tables 1 and 2 below show the results obtained. The curing dose represents the minimum radiation dose which is necessary to produce a tack-free film with good surface hardness.

It was found that at the specified curing dose, the films obtained a high degree of crosslinking can be. The cured films described above

were rubbery.

309810/1126

BATH ORIGINAL Table 1 :

Curing dose and percentage of insoluble content of acrylic acid adducts,

CD CO

cn

Acrylic acid adduct C = C double bond
content / kg Hardening dose
(Megarad) 'Insoluble part
in {%) A. 2.5 2.0 100 B. 1.40 1.0 g4 C. 1.94 3.0 93 D. 2.03 ' 3.5 100 E. 0.87 3.5 89 2.45 2.0 98- - ■

AG

N) K)

JO «OJ

CD CD

Table 2 ; Hardening dose and percentage of insoluble content of mixtures of acrylic acid adducts and polymerizable monomers.

^: Acrylic acid
adduct - " Monomer Weight ratio
Kara: monomer 30th
30th
30th Hardening dose
(Megarad) Insoluble part
in (fo) A. Butyl acrylate
Methyl methacrylate
Styrene 70:
70:
70: 30th
30th
30th 2.0
'. 3.5
• 4.5 94
99
09 . ■. · ' I.
B. Butyl acrylate
Methyl methacrylate
■ styrofoam '. 70:
. -70:
70: 30th
30th
30th 1.5
4.0 92
90
89 C. Butyl acrylate
Methyl methacrylate
Styrene ■ 70:
70:
70: 30th
30th
: 30 . '3.5,
4.0
5.0 91. '
'90 D. Butyl acrylate
Methyl methacrylate
Styrene • 70:
70:
70 : 30.
: 30
: 30 ' 3.0 ·
4.0
4.0 97 '
100
94 E. Butyl acrylate
Methyl methacrylate
Styrene 70
70
70 : 30
: 30
: 30 4.5
5.0
6.5 ■ 88
82
84 ... Butyl acrylate
Methyl methacrylate
Styrene 70
70
70 2.0
2.5
". 5.5 94 ■ ■
91
90

Continuation of table 2

Curing dose and percentage of insoluble content of mixtures of acrylic acid adducts and polymerizable monomers

Acrylic acid adduct * Monomer Weight ratio
Resin: monomer Hardening dose
(Megarad) Insoluble part
in % CaJ
O Butyl acrylate 70:30 5.0 94 CD
OO G Methyl methacrylate 70:30 5.0 76 10 / ' Styrene 70:30 10.0 88

Example 2

There were βΟ πιμ thick films of a curable mixture, which consists of 10 parts of acrylic acid adduct B, 67 parts of an acrylic acid adduct of diglycidyl hexahydrophthalate and 23 parts of butyl acrylate with zinc phosphate pretreated steel sheets ("Granodine 6ΟΟ5", Sendzimir galvanized steel sheet thickness 0.75 mm) applied. These Steel sheets were irradiated as described in Example 1. The films were then immediately checked for their surface tack and their surface hardness according to the method described in Example 1 was investigated. It was determined, that the films can be cured with a radiation dose of 2.0 megarads.

After a few days, the films were examined further. The determination of the dry film thickness became non-destructive according to VDI 24-51 (Association of German Engineers) carried out. The film thickness was 35 μm. The hardness of the The paint was tested with the hardness test rod (after Erichsen; type certainly. The films achieved a value of 225 p on the Erichsen scale. The determination of the. Adhesion strength was determined by cross-cut, according to DIN 53 * 151 (with subsequent removal of adhesive tape). It the result was a cross-cut 0. The behavior of the paint when the material was bent was determined by means of the mandrel bending test tested according to DIN 53 * 152. When bending around the 2 mm - the mandrel tore through the coating. Deformability '

309810/1 126

BATH ORIGINAL

the composite material was made by deep drawing according to DIN 53'156 established. After the deepening of 8 mm, the coating was cracked. The pendulum hardness of the films was determined according to DIN 53'157 (König) certainly. The films achieved a pendulum hardness of 145 seconds.

Example 3 ■ · ■

• 60 πιμ thick films consisting of a synthetic resin mixture from 15 parts of acrylic acid adduct B with 62 parts of an acrylic acid adduct of bisphenol A diglycidyl ether (which under the protected brand name "STYPOL 46-4001" from the FKEEMAN Corp. commercially available) and 23 parts Butyl acrylate was applied to steel sheets pretreated with iron phosphate ("Granodine 1107", cold-rolled steel, Sb. 1405, Sheet thickness 0.75 now) applied and irradiated and examined in the same way as described in Example 1. It has been found that the films can be cured with a radiation dose of 3> j0 megarads.

After a few days, the films were examined further using the method described in Example 2. the Dry film thickness was 4θΐημ according to VDI 2451 (Verein Deutscher Engineers). The films achieved a hardness of 275p according to Erichsen (Erichsen hardness test rod; type 318).

When bending around the 10 mm mandrel, the coating tore. The films achieved a pendulum hardness according to DIN 53 * 157 of 170 seconds.

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\ ^r comparison example

A synthetic resin mixture of 70 parts was used for comparison "Stypol 46-4001" and 30 parts of butyl erylate. There were 60 ηιμ thick films of this mixture with iron phosphate Applied pretreated steel sheets and - as described above - irradiated and then examined. the necessary curing dose was 3 * 5 megarads.

After a few days, the films were examined further as described above. The dry film thickness was 40 ιημ. During this test it was found that very slight bending around a 32 mm mandrel of the coating rips. The comparison shows that when using acrylic acid adduct B for the production of coatings, substantial improvement in the ductility or elasticity of the coatings is achieved.

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example H

Hardenable mixtures of 5 parts of acrylic acid adduct Bj HO parts of an acrylic acid adduct of hexahydrophthalic acid diglycidyl ester, 15 parts of butyl acrylate and 50 parts of titanium dioxide ( ¹¹ RCR-3 ^M ) were available on hard wood fiber boards, many under the protected brand name "Pavatex" from Papierfabrik Cham AG, Applizlert (Pilir.dicke 80 μm) and irradiated in the same way as described in Example 1. The necessary curing dose was 2.5 megarads. The dry layer thickness was approx. 55 μm.

The properties of the films were examined further after 2 hours. The surface hardness was determined in accordance with SNV 37'113 (Swiss Association for Standardization; pencil hardness) and DIN 53'153 (Buchholz). The films achieved a pencil hardness of ^ E-HE and a Buchholz penetration resistance of 85 degrees. The scratch hardness (according to Taber) was 225 g. A grid section 1 was measured (according to DIN 53 '15.1 with subsequent adhesive tape removal). The abrasion resistance was measured using a Taber test apparatus (jig, grinding stones CS-I7, 2 × 500 g load). carried out. An abrasion of 12 mg / 50 ° revolutions was found. The coating has good chemical resistance; none of the common household liquids such as soda solution or soap solution - will damage the coating. In addition, the Beechichtuhg was found to have good key strength.

309810/1126 ORIGINAL BATHROOM

Example 5

There were 60 ιημ thick films of a curable mixture, which from 10 parts of acrylic acid adduct B, 67 parts of a Acrylic acid adduct consists of hexahydrophthalic acid diglycidyl ester and 23 parts of butyl acrylate on ABS (acrylonitrile-butadiene-styrene) plastic sheets applied and irradiated in the same way as described in Example 1. The necessary curing dose was 2.5 megarads.

The subsequent examination of the surface properties of the films showed that the films achieved a pencil hardness of H-2H (according to SNV 37'113) and a penetration resistance according to Buchholz (DIN 53 * 153) ^of & 5 degrees. The scratch hardness (with Erichsen hardness test stick; type 318) was 150 p. A cross-cut O (in accordance with DIN 53Ί5Ι with subsequent Tesa film removal) was measured. The films also achieved a pendulum hardness (in accordance with DIN 53 * 151) of 155 seconds.

Compared to the untreated ABS plastic sheets, the lacquer coatings are characterized by improved abrasion resistance Scratch resistance. The untreated panels have a scratch hardness of 50 ρ (measured according to the Erichsen scale). The adhesion of the films was excellent.

309 8 10/1126 BATH ORIGINAL

Example 6 ,

Acrylic acid adduct B and mixtures of acrylic acid adduct B and polymerizable monomers (according to Table 3) were filled into tubes with a diameter of 1.25 cm to a height of approximately 2.5 cm and exposed to the gamma radiation of a Co radiation source. These tests were carried out at about JtO C and in the presence of oxygen. After the irradiation, the degree of crosslinking was determined by extraction with toluene according to the method described in Example 1.

All attempts were made with one radiation intensity of 0.9 megarads / hour. Table 3 gives the percentage insoluble fraction · again, that of acrylic acid adduct at radiation doses of 0.25, 0.5, 0.75, 1.0 and 1.25 megarads B alone or in admixture with polymerizable Monomers was obtained. The following table shows that the tested acrylic acid adduct B and its mixtures with polymerizable monomers can be crosslinked to a high degree by irradiating with gamma rays.

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Table 3: Percentage of insoluble content of hardened at different hardening doses Mixtures of acrylic acid adduct B and polymerizable monomers.

Acrylic acid Monomer Weight ratio 0.25 Mrad Insoluble part {%) 0.75 Mrad " 1.0 Mrad 1.25 Mra adduct - Polyacrylate: monomer 88 0.5 Mrad 92 94 96 B. Styrene 100: O fluid 92 56 86 92 3 Butyl acrylate 70: 30 fluid 34 92 93 94 B. Methylmetha-
crylate 70:30 fluid 79 93 94 94 B. 70:30 87

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CD CD

Claims (3)

Claims> '' 2 2 A 3 1 9 O __ 1. Process for hardening acrylic acid adducts, especially in the form of thin layers or coatings, with ionizing Rays, characterized in that acrylic acid adducts of the formula I " / O ■ OH \ CTL = C - C - ο - mi - π V— ₂ S = CCO-CH-C- ^ A-A-C-CH-O-CV R ₁ ^ ₂ ^R 3 ' ⁿ ■ ^R 3 · V 3- ' ⁿ ■ ^R 3 where R ₁ , R- and R ~ 'independently of one another each denote a hydrogen atom or the methyl group, R- or R " ^! is a hydrogen atom and A is the radical of a polyglycidyl compound obtained by separating off the 1,2-epoxyethyl groups, or in which A together with R "or R"'including the group OH OH II -CH-C- or -C-CH- the eyeloaliphatic ring or the cycloaliphatic ring system of a converted cycloaliphatic ^^ polyepoxide compound mean, B means a long-chain polyester radical in which branched or unbranched alkylene and / or Alkenylene chains alternate with carboxylic acid ester groups, the quotient Z / Q, where Z is the number of recurring Structural element of the radical B present carbon atoms and Q is the number of oxygen bridges present in the recurring structural element of radical B, "at least 3 and must preferably be at least 4, and furthermore the total number of carbon atoms present in radical B at least 8, and η denotes the number 1 or 2, irradiated. 3 0 9 8 10/1126. BATH ORIGINAL 2. The method according to claim 1, characterized in that that acrylic acid adducts of the formula I are mixed with other mono- and / or polyolefinic unsaturated ones Connections irradiated. 3. The method according to claims 1 or 2, characterized in that the curing of the acrylic acid adducts with ionizing radiation by electrons with an average energy of at least 50 KeV and causes a maximum of 4 MeV. 4. The method according to claims Γ or 2, characterized in that one'die hardening of the acrylic acid adducts with an isonizing radiation by electrons with an average energy of 50 to 600 KeV causes. 5. The method according to claims 1 or 2, characterized in that the curing of the acrylic acid adducts caused by ionizing radiation in the form of x-rays or gamma rays. 6. The method according to claims 1 to 5 * thereby characterized in that the acrylic acid adducts before, during or after exposure to ionizing radiation additionally subjected to a heat treatment. 7. The method according to claims 1 to 6, characterized in that the action of ionizing radiation on the acrylic acid adducts in an acidic 309810/1126 BATH ORIGINAL low-carbon atmosphere. 8. A process according to claims 1 to 7> characterized in that acrylic acid adducts of the formula I used, in which A is the radical of a cycloaliphatic aliphatic / obtained by separation of the 1,2-Epoxyäthylgruppen means or aromatic polyglycidyl ether. 9 · Method according to claim 8, characterized in that that acrylic acid adducts are used in which the radical A is the radical of a diomethane diglycidyl ether or the Means residue of a hydrogenated diomethane diglycidyl ether. 10. The method according to claims 1 to "J, characterized in that acrylic acid adducts of the formula I are used, \ tforin A denotes the" radical of an aliphatic, cycloaliphatic or aromatic "polyglycidyl ester obtained by separating off the 1,2-epoxyethyl groups. 11. The method according to claim 6, characterized thereby ' draws that acrylic acid adducts are used, in which the radical A is the radical of the phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester or denotes hexahydrophthalic acid glycidyl ester. 12. The method according to claims 1 to 7, characterized in that acrylic acid adducts of Formula I used, in which the radical A is separated by separation dsr 1,2-epoxyethyl groups obtained from an N-hetero-cyclic radical Means polyglycidyl compound. 3 0 9 8 10 / 1- 12G Ij5 · Process according to claim 12, characterized in that acrylic acid adducts are used in which the radical A is the radical of the triglycidyl isocyanurate or N, N ^f - I! Iglycidyl-5j5-dlmethylhydantoin means. 14. The method according to claims 1 to 7, characterized in that acrylic acid adducts of the formula I are used in which the radical A together with R ₉ and / or R ₉ 'below OH ^ll inclusion of the group _ _c "1 that after the implementation of "ι" Γ
3,4-epoxycyclohexylmethyl-R ^ 3'4 * -epoxycyclohexane carboxylate ring system obtained means. 15. The method according to claims 1 to 7 * characterized in that acrylic acid adducts of the formula I are used, wherein B denotes by separating the two Carboxyl groups obtained residue of a polyester dicarboxylic acid the formula HO-CR.-C-PO-R.-OCR. -CA -OH J 4 JT 5 u 4 -V- 0 0 .00 denotes, wherein R ₁ and R 1 - denote branched or unbranched alkylene or alkenylene chains, each of the both radicals R, and R _c at least 2 carbon atoms ent-4 5 must hold and in which the number m is chosen so that the sum of the carbon atoms occurring in the polyester dicarboxylic acid is at least 10. 16. The method according to claims 1 to 7, characterized characterized in that acrylic acid adducts of the formula I are used, viorin B by separating the two CarboxyIr.ri'l'pi'rj obtained Rc; nt of a polymer; terri: j carboxylic acid 309810/1126 is formula KO-E-c-R -ο -} - C - R -cHr-o-R ~ c 3--0H a H 6 a "7 j, ₆ " b ■ o ^k 0 0 o means, in which R ^ is an alkylene chain with at least 4 Carbon atoms means, R for an alix ^ hatischen hydrocarbon radical and in which the numbers a and b are chosen such that the product of (a-fb) and the sum of the carbon atoms in R., - is at least 10. 17. 'A process according to claims 2 Ms 16, characterized in that the curable Acrylsäureadduktraisellung as mono- or polyolefinically unsaturated compounds Methylacrylatj Butylaerylat, -Methyl- methacrylate, acrylonitrile, styrene, ethylene glycol dimethacrylate, divinylbenzene, vinyl acetate, diallyl o-phthalate, or adducts of acrylic acid or methacrylic acid on bisphenol A diglyeidyl ether, hexahy-. contains drophthalsäurediglycidylester or Ν, Ν-diglycidylhydantoin. -IB. Method according to claims 1 to 17, there, characterized in that the curable synthetic resin mixture in addition fillers, pigments and / or flexibilizers contains. FO 3.35 (Sta) Sta / sg 3rd September 1971 309810/1126 ORIGINAL,