DE2910714A1 - Radiation-curable synthetic resin coating compsn. - with excellent adhesion to polar surfaces is based on acrylo-urethane! resin and hydroxy-alkyl acrylate - Google Patents

Abstract

Radiation- curable synthetic resin coating compsn., with excellent adhesion to non-absorbent polar surfaces, consists of a (meth)acrylo-urethane resin (I) and a (meth)acrylate (II) with OH gps., which can copolymerise with the unsatd. terminal gps. of (I). (I) is prepd. by reacting (A) polyoxyalkylene-bisphenol A deriv(s). (IIIA) of the formula H(OR)m-O- -CMe2- -O (RO) nH (in which R is 2-4 (2-3) C alkylene. is a p-phenylene gp. with 0-2 halogen or Me substits. m and n are >=1 and m + n = 2-8, pref. 2-6) or OH-terminated cpds. (IIIB), obtd. by condensing (IIIA) with poly- (dr-)-carboxylic acids (IV) or anhydrides, (B) polyisocyanates (V) and (C)(II). The compsn. is specified for coating inks, glass, metals and polar surfaces of synthetic resins, (e.g. PVC, polystyrene, epoxy resins, polyesters, polyacrylonitrile, oxidised polyethylene, oxidised polypropylene, urea, melamine, phenolic, ketone, other HCHO, urethane and acrylic resins, polyvinyl esters, cellulose acetate and other modified cellulose resins, PVA, polyvinyl acetate resins, polyvinyl ethers and polyamide resins). It can be cured by UV or ionising radiation.

Description

RADIATION CURABLE RESIN COATING COMPOUND.

The present invention relates to a resin coating composition, caused by irradiation using energetic radiation, in particular ultraviolet radiation, or ionizing radiation, is rapidly cured and crosslinked, with a cured The result is a product that has excellent mechanical properties and flexibility possesses, for example, a coating composition that is excellent in its adhesive strength is, when the mass is used as a covering area.

Lately there has been a brisk development of solvent-free Resins used for curing by irradiation with energetic rays are suitable to save energy and labor in this way and to pollute the environment and there are already various solvent-free resins in the Practice has been used. These resins usually contain as the main component a polymerizable mixture of a suitable oligomer, monomer and / or a prepolymer which has polymerizable unsaturated groups, such as Acrylogl vinyl, and acrylamide groups, as well as a photosensitive substance that is added as needed. When such a resin composition is applied to a substrate and hardened by irradiation with high-energy rays, the adhesiveness stands on the substrate usually in inverse proportion to the cure rate.

When the hardening rate by increasing the son concentration of unsaturated groups increases or the amount of photosensitive substance in the resin mass is increased, tensions develop in the resulting coating, and thereby the elec- tricity on the substrate is reduced, and the flexibility is lowered. However, if the concentration of unsaturated groups or the amount of photosensitive If the bond is decreased, the adhesion to the substrate increases, but the cure rate increases is drastically reduced (see Japanese Patent Application Laid-Open No.

139189/75). Furthermore, the adhesion is determined by the type of used Substrates noticeably affected. Most common solvent-free, such Resin coating compositions do not have excellent hardening properties at the same time and excellent adhesion for commercially available solvent-based, through Oxidation-polymerized inks, metals (especially tin-plated Steel and aluminum), glass and synthetic resins. This is a serious obstacle in the practical use of radiation cured paints.

U.S. Patent No. 3,876,726 describes vinyl ester urethane resins which by reaction of a diisocyanate and a hydroxyl-terminated ester obtained from acrylic acid or methacrylic acid with a xondensation product, which in turn by reacting a polyoxyalkylenebisphenol A with an unsaturated, aliphatic dicarboxylic acid or its anhydride is produced. These resins are with vinyl or allyl monomers, such as styrene, calorstyrene, tertiary butylstyrene, divinylbenzene, Vinyl toluene, vinyl acetate, vinyl propionate, acrylic or methacrylic acid esters, diallyl phthalate, Diallyl fumarate and triallyl cyanurate, combined. Such masses have none acceptable adhesion to solvent-borne polymerisation-type paints or metals, glass and synthetic resins, at least if the masses are irradiated are hardened.

It has now been found a coating resin that is able to under Irradiation with high-energy rays in the air to harden quickly and one thing Coating mass results, which have an excellent adhesion to non-adsorbent, polar surfaces of paint, metal, glass or synthetic resins.

Specifically, according to the present invention, is one by irradiation curable coating resin composition which is excellent in adhesiveness on non-adsorbent polar surfaces. This mass contains as main components: (I) a methacrylic or acrylic urethane resin containing at least 2 acryloyl or contains nethacryloyl groups (hereinafter referred to as "methacrylic or acrylic groups" are designated); this resin is formed by the reaction of a hydroxyl end group send polyoxyalkylenebisphenols A derivative with (B) a polyisocyanate compound and (C) an acrylate and / or methacrylate containing hydroxyl groups; (II) Furthermore, the new composition contains a hydroxymethacrylate or a hydroxyacrylate monomer, that is copolymerizable with the unsaturated end group in the methacrylic or acrylic urethane resin (I) is.

The components used in the present invention can be described below.

The polyoxyalkylenebisphenol-A derivative (A) which can be used in the present invention are polyoxyalkylenebisphenol-A compounds and compounds containing a polyoxyalkylenebisphenol-A residue in their chemical structure and hydroxyl groups at the end of the molecule exhibit. The polyoxyalkylene bisphenol-A is obtained by reacting bisphenol-A with an alkylene oxide. Both. Appropriately used alkylene oxides are ethylene oxide and propylene oxide. Preferred examples of the polyoxyalkylenebisphenol-A suitable for the present invention are compounds represented by the following formulas (a) and (b): and In these, v denotes an alkylene radical having 2 to 4 carbon atoms, X is halogen or a methyl group; a represents the number 1 or 2; and m and n denote numbers with a value of at least 1 * and the sum of m plus n represents a numerical value from 2 to 8, preferably 2 to 6.

In the formulas (a) and (b) given above, the sum of m and n is determined based on the number of moles of alkylene oxide units involved with the hydroxyl groups of bisphenol A have reacted. To the extent that in as the number of moles of alkylene oxide residues increases, the properties change of the resin, i.e. flexibility and ductility are improved, but at the same time the deformation temperature and the tear strength are reduced. So let yourself be prepare a resin from polyoxyalkylenebisphenol A in which the sum of m and n larger than about 8, but the resulting resin is very soft and is not suitable to meet the requirements of the present invention.

Except for the polyalkylenebisphenol A compounds that are caused by the above Formulas (a) and (b) can be reproduced as poly oxyalkyl enbisphenol A derivatives (A) Reaction products obtained by condensation of these polyoxyalkylenebisphenol-A compounds are used with carboxylic acids and X or their anhydrides are obtained. In such a condensation reaction is the molecular ratio of the polyoxyalkylenebisphenol A compound to the acidic Component at least 3: 2, provided that the acid anhydride is to be regarded as such is that it contains 2 moles of carboxylic acid groups. When the above molecular ratio is less than 3: 2, the hardening speed of the resin is slow and it occurs the further disadvantage that the coating properties of the resin deteriorate. As component A you can also use a Use mixture that Condensation reaction product of the above-mentioned polyoxyalkylene bisphenol A compound contains in any desired ratio. As a polycarboxylic acid or acid anhydride reactant a dicarboxylic acid or its anndride is preferably used. For example, can aliphatic, saturated dibasic acids and their existing anhydrides are used such as malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid and sebacic acid; also aliphatic unsaturated dibasic acids and their existing anhydrides, such as maleic acid, maleic anhydride, Fumaric acid, citraconic acid and itaconic acid, and finally aromatic dibasic ones Acids and their available anhydrides, such as phthalic acid, phthalic anhydride, isophthalic acid and terephthalic acid.

In the preparation of the above-mentioned polyoxyalkylenebisphenol-A derivative (A) can in addition to the above-mentioned first acid component, i.e. to the above-mentioned dibasic acid and / or the anhydride of such an acid small amounts of a second acid component are used, e.g. a polycarboxylic acid, such as trimellitic anhydride.

This second acid component can be aromatic or aliphatic and be saturated or unsaturated. Of course, the acid component and / or the Polyoxyalkylenebisphenol A compound also mixtures of two or more of these Represent connections.

As typical examples of a polyisocyanate compound (B), which according to The present invention can be used, the following may be mentioned: tolylene diisocyanate, Diphenylmethane-4,4'-diisocyanate, 3, f'-dimethyldiphenylmethane-4,4'-diisocyanate, naphthylin-1 , 5-diisocyanate, phenylene diisocyanate, xylylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate partially reacted with carboimide, and dimers of the aforementioned diisocyanates, as well as adducts of these diisocyanates with Compounds that contain active hydrogen, such as ethylene glycol, propylene glycol, Tetramethylene glycol, neopentyl glycol, butanediol, 1,6-hexanediol, polyethylene glycol, Trimethylolpropane, glycerol, pentaerythritol, or ethylene oxide and propylene oxide adducts von Bisphenol A. These polyisocyanate compounds can be used individually or in the form of Mixtures of two or more of these compounds can be used.

The polyisocyanate (B) is used in such an amount that the number of isocyanate groups is 1.8 to 5, preferably 2.0 to 3.0, per hydroxyl group in the polyoxyalkylene bisphenol A derivative (A). When the number of isocyanate groups is less than 1.8, the viscosity of the resulting resin becomes too high, and it there is the disadvantage of poor processability. On the other hand is found that an increase in isocyanate groups over 5 to one hydroxyl group no further improvement in the coating properties supplies.

As a hydroxyl group-containing methacrylate or acrylate (C), which according to Applicable to the present invention, compounds can be mentioned by the following formulas (C), (d) and (e) are given: R3 0 CH2 = C - C O (R²O) p -H (c) R30 (CH2 = C-C-O-CH2) q -C- (CH2OH) 4 -q (d) and R3 O R4 (CH2 = G - C - 0 - CH2) r-C- (CH2OH) 3-r (e) In these, R² denotes an alkylene radical with 2 to 10 carbon atoms; R³ denotes hydrogen or a methyl radical; R4 is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; p and q represents integers ranging from 1 to 3, and r represents a number ranging from 1 or 2.

The connections are made according to known methods.

In the formula (c), the value of p is given by the number of moles of one Moles of acrylic acid or methacrylic acid, alkylene oxide or glycol used. When the alkylene oxide or glycol is used in amounts greater than 3 moles, the resin obtained has decreased physical properties, in particular one low heat deformation temperature, low tear strength and low flexural strength.

As typical examples of the compounds of the formula (c), the following can be used are mentioned: hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, Hydroxypropyl methacrylate, polyoxyethylene acrylate with 2 ethylene oxide groups, polyoxyethylene methacrylate with 2 ethylene oxide groups, polyoxyethylene acrylate with 3 ethylene oxide groups, polyoxyethylene methacrylate with 3 ethylene oxide groups, polyoxypropylene acrylate with 2 propylene oxide groups and polyoxypropylene methacrylate with 3 propylene oxide groups.

As typical examples of methacrylate and acrylate esters, like them represented by formulas (d) and (e), the following can be mentioned: Trimethylolethane monoacrylate, trimethylolethane monomethacrylate, trimethylolethane diacrylate, Trimethylol ethane dimethacrylate, trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, Trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol monoacrylate, Pentaerythritol monomethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, Pentaerythritol triacrylate, and pentaerythritol trimethacrylate.

In addition, glycerine monoacrylate, glycerine monomethacrylate, Glycerine diacrylate and glycerine dimethacrylate can be used.

Adducts of acrylic acid and methacrylic acid with monoepoxy compounds can also be used can be used, such as butyl glycidyl ether, acrylic glycidyl ether, phenyl glycidyl ether, Glycidyl acrylate and glycidyl methacrylate.

These hydroxyl group-containing acrylate and methacrylate compounds (C) can be used individually or in the form of a mixture of two or more of these compounds be applied. The hydroxyl group-containing acrylate or methacrylate component (C) is used in such an amount that the following condition is met: c # (by-x) / z In this, c denotes the number of moles of the hydroxyl group-containing acrylate and / or methacrylate component (C); z means the number of hydroxyl groups of the Hydroxyl group-containing acrylate and / or methacrylate component (C); b means the number of moles of the polyisocyanate component (B); y is the number of isocyanate groups (NCO) contained in one molecule of the polyisocyanate component (B); and x means the number of hydroxyl groups in a molecule of component (A) which consists of a polyoxyalkylenebisphenol-A derivative.

The methacrylic or acrylic urethane resin (I) according to the present invention can be prepared by known methods.

Typical manufacturing processes can be single-stage and two-stage Reaction methods are mentioned in which the two components are initially connected to each other brought to reaction and the resulting prepolymer dsnn with the third component is implemented.

The resin (I) can be in the form of a melt without using any Solvent are produced. But one can also change the reaction in a suitable way Solvent or in the presence of a hydroxymethacrylate monomer or hydroxyacrylate monomer (II) perform.

In the one-step reaction process, the polyoxyalkylenebisphenol-A derivative (A) melted, and this melt with the hydroxyl group-containing methacrylate or acrylate (C) mixed. Then the polyisocyanate compound (B) becomes gradually added and the reaction temperature increased to at least about 12500. The reaction mixture is held at this temperature until essentially all of the isocyanate groups react to have. When a solvent or a hydroxymethacrylate monomer or hydroxyacrylate monomer is used, all components are added to the solvent or the monomer, and the mixture is heated to about 50 ° C. to about 85 ° C. until the reaction is complete is. The reaction temperature used may vary depending on the ones used Reaction participants and the reaction time can be changed in an appropriate manner.

The polymerizable compound containing a double bond (TI), which is used in the present invention consists of a monomer which has an unsaturated group identical to the methacrylic or acrylic urethane resin (I) is copolymerizable, preferably it is a plethacrylic or acrylic acid ester having a hydroxyl group. Preferred examples are the following: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, Diethylene glycol monoacrylate, diethylene glycol monomethacrylate, dipropylene glycol monoacrylate, Dipropylenglgcolmonomethacrylat, Trimethylolpropmonoacrylat, Trimethylolproppanmonomethacrylat, Pentaerythritol monoacrylate, pentaerythritol monomethacrylate, pentaerythritol diacrylate and Pentaerythritol dimethacrylate. The compounds can be used individually or in the form of niches of two or more of these compounds can be applied.

Part of the polymerizable compound having a double bond (II) used in the present compound can be replaced by a methacrylic acid ester or an acrylic acid ester which does not have a hydroxyl group, or by a common solvent.

The polymerizable, double bond-containing compound (II) is used in the present invention in such an amount that the weight ratio of the Hares (I) for polymerizable, containing a double bond Compound (II) on the order of 30:70 to 95: 5, preferably at 60 : 40 to 80: 20.

In the present invention, the term "is non-absorbent polar surface "means a non-absorbent surface that has a bond, such as a metal bond, an ionic bond, a coordination bond or has a polar bond. The composition of the present invention possesses excellent adherence to such non-absorbent polar ones Surfaces.

As such, non-absorbent polar surfaces can include the following the following are mentioned: metal surfaces, surfaces of printing inks, glass surfaces and surfaces of plastics such as polyvinyl chloride, polystyrene, epoxy resins, polyesters, polyacrylonitrile, oxidized polyethylene, oxidized polypropylene, urea resins, melamine resins, phenolic resins, Seton resins, other formaldehyde resins, urethane resins, acrylic resins, polyvinyl esters, cellulose acetate, and other modified cellulose resins, polyvinyl alcohols, polyvinyl acetal resins, Polyvinyl ethers and polyamide resins.

The present invention will now be described in detail with reference to FIG the following manufacturing methods and examples are described in which all Indications with regard to the "rush" mean parts by weight.

PREPARATION 1 (according to the invention) A bottle was made with 2 moles of an adduct of 2 moles of propylene oxide with bisphenol A and 1.01 moles of maleic anhydride loaded; the temperature was then heated to 220 ° C, and the reaction carried out, while blowing nitrogen gas into the bottle until the acid level fell below 8 was down. Then hydroquinone was calculated in an amount of 0.05% by weight on the entire batch, added (0.40 parts; 0.0037 moles). That way it was obtained a polyester glycol. This polyester glycol was cooled down to 10,000 and then with 2.02 moles of 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") mixed; then dehydration took place under reduced pressure, wherein the temperature was kept at 95 ° C until the water content decreased below 0.07% by weight was. The reaction mixture was then cooled to 7500 and now were while blowing air through 2 moles of tolylene diisocyanate (hereinafter referred to as "TDI" designated) added gradually; the conversion took place at 750 to 11500 within of 45 minutes. The reaction mixture was then heated to 1250bis for 4 hours Aged 12800, so that the remaining content of NCO groups 0.1 Ges.-fo or less fraud. In this way it became a slightly yellowish, transparent, solid Acrylic urethane resin obtained by an acid value (hereinafter referred to as "AV") of 4.9, an hydroxyl value (hereinafter referred to as "OHV") of 21.0 and Content of NCO groups (hereinafter referred to as "NCO%") of 0.08% was.

PREPARATION 2 (according to the invention) The reaction was carried out in the same way Carried out as in preparation 1, with the difference that an adduct of 4 moles of propylene oxide on bisphenol A instead of the adduct of 2 moles of propylene oxide on bisphenol A, as used in preparation 1, was used. Man obtained a light yellow, clear, solid acrylic urethane resin obtained by the following Values was marked: AV, 6.0; OHV = 12.1; NCO% = 0.1.

PREPARATION 3 (according to the invention) The reaction was carried out in the same way Way carried out as in production 1, with the difference that instead of the HEA used in production 1, 2-hydroxyethyl methacrylate (HEMA) is now used became; a light yellow, transparent, solid methacrylic urethane resin was obtained, which was characterized by the following values: AV - 5.5; OHV - 20.3; NCO% = 0.10.

PREPARATION 4 according to the invention) The reaction was similar Way carried out as in production 1, with the difference that instead of the adduct of 2 moles of propylene oxide and bisphenol used in preparation 1 A now an adduct of 8 moles of ethylene oxide with bisphenol A was used; one received a light yellow, transparent, liquid acrylic urethane resin, which is characterized by the following values was characterized: AV = 7.3; OHV = 14.3; NCO% - 0.1.

PREPARATION 5 (according to the invention) The reaction was carried out in the same way Way carried out as in production 1, with the difference that instead of the adduct of 2 moles of ethylene oxide and bisphenol used in preparation 1 A this time an adduct of 6 moles of propylene oxide with bisphenol A was used; Farther was used instead of REA pentaerythritol triacrylate (PEXA), whereby a light yellow, transparent, liquid acrylic urethane resin with the following characteristic values the following was obtained: AV X 4.7; OHV NCO% = 0.01.

PREPARATION 6 according to the invention) A bottle was made with 1.05 moles Polyester glycol is charged, which is obtained in the same way as in preparation 1 was, with the difference that instead of the adduct used in preparation 1 of 2 moles of propylene oxide with bisphenol A now an adduct of 6 moles of propylene oxide on bisphenol A was used; dehydration was carried out under reduced pressure carried out at 9500 until the water content was reduced below 0.07% by weight. Afterward the reaction mixture was cooled to 75 ° C and while bubbling with air 2 moles of an adduct of trimethylolpropane with hexamethylene diisocyanate (2.016 Parts in the form of a 75% solution in ethyl acetate added gradually. (The adduct is manufactured by Nippon under the trademark "Coronate HL". Polyurethane K.K.) / -). The reaction was carried out at a temperature of 75 ° C to 85 ° C for 36 minutes. Subsequently was the class aged 4 hours at 125 ° to 12800, the ethyl acetate contained in the Coronate HL was removed until the NGO content was reduced to 0.1 wt% or less. The pressure was then reduced to remove the remaining ethyl acetate. A light yellow, transparent, obtained liquid acrylic urethane resin with the following characteristics: AV = 1.7; OHV = 11.5; 1m30 Vo - 0.07.

PREPARATION 7 (according to the invention) A bottle was made with 1.0 mol TDI and 0.15 part (0.0014 moles) of hydroquinone charged; then the Temperature increased to 70 ° C. With air bubbling through, 1.0 mole of HEA was gradually increased added; the reaction was carried out at 70 ° to 80 ° C. for one hour, and aging took place for one hour at 80 ° C .; a 1iCO end group-containing Acrylic urethane prepolymer obtained with an NGO content of 14.5% by weight. Separated of this was another bottle containing 1.05 of an adduct of 2 moles of propylene oxide charged with bisphenol A; then the pressure was reduced to 50 mm Hg and the mass heated to 95 ° C until the water content was reduced to below 0.07 wt .-%. After dehydration, the temperature was reduced to 75 ° C and while blowing from air were 2.0 moles of the above-mentioned NCO-terminated acrylic urethane prepolymer added gradually. The reaction was at 750 to 11500 within one hour carried out, then the mass was aged for 4 hours at 125 ° to 12800. It was found that the remaining NCO content fewer was than 0.1 wt%. In this way it became a light yellow, translucent, solid Acryl urethane resin obtained, which was characterized by the following values: AV - 1.4; OHV = 20.5; NCO% = 0.08.

PREPARATION 8 (according to the invention) A bottle was made with 1.0 mol an adduct of 4 moles of propylene oxide with bisphenol A charged. Under increase the temperature to 9500, the pressure was reduced to 50 mm Hg to reduce the water content to be depressed to below 0.07 wt%. The reaction mixture was cooled down to 75 ° C, and while blowing air therefrom, 2.0 moles of the NCO-terminated Acrylic urethane prepolymer obtained according to Preparation 7, step by step added. The reaction was carried out at 750 to 11500 for one hour. Afterward aging was carried out at 1250 to 12800 for 4 hours. It was determined, that the remaining N00 content was reduced below 0.1% by weight. That way it was a light yellow, clear, solid acrylic urethane resin with the following characteristics obtained: AV n 1.3; OHV = 32.9; NCO% X 0.09.

PREPARATION 9 (according to the invention) Leaves in a nitrogen gas stream to 2.0 moles of an adduct of 2 moles of propylene oxide with bisphenol A with a 1.0 Moles of succinic acid react at 220 ° C until the acid value has dropped below 8. Hydroquinone is then used in an amount of 0.05% by weight, calculated on the total Batch (corresponding to: 0.41 parts; or 0.0037 moles) to where-through a Polgesterglycol is obtained. The polyester glycol is then cooled to 100 ° C 2.02 moles of hydroxypropyl acrylate (HPA-) are added; the rest of the production takes place in the same way as described for production 1. One receives a light yellow, transparent, solid acrylic urethane resin with the following characteristics: AV = 4.3; OHV - 6.7; NCO% 5 0.05.

PREPARATION 10 (according to the invention) The reaction is the same Way as carried out in manufacture 9, with the difference that instead the succinic acid used in preparation 9 is now adipic acid. A light yellow, transparent, solid acrylic urethane resin is obtained with the following Mark. AV = 4.2; OHV = 8.9; NCO °% = 0.04.

PREPARATION 11 (according to the invention) 1.0 mole of that used in manufacture 9 obtained polyester glycol is cooled to 100 ° C; then 9.0 moles of HEA are added.

The dehydration takes place under reduced pressure at 95 ° C until the Water content is reduced to below 0.1 wt .-%. Then the mixture cooled to 7500, and 2.55 moles of TDI gradually become with air bubbling therethrough added dropwise. The reaction is carried out at 750 to 115 ° C for one hour. The mass is then allowed to age for 5 hours at 125 ° C. to remove the remaining NCO content to be reduced to below 0.1% by weight. You get a light yellow, transparent Acrylic urethane resin with the following characteristics: AV = 7.5; OHV = 157.6; NCO% = 0.03.

PRODUCTION 12 (comparative experiment) A bottle is made with 952 parts (2 epoxy equivalents) of an epoxy resin (dial code: "Epikote 1001") from Shell Chemical Co .; Epoxy equivalent 8,471) and 0.54 parts (0.0049 moles) Hydroquinone charged. The liquid is then heated to 11,000 in a stream of air. Separately, a mixture of 2.0 moles of acrylic acid with 5.4 parts (0.020 Moles) DMP-30 (Tridimethylaminomethylphenol, made by Rohm and Haas Co.) Room temperature established within a few minutes; this mixture will gradually added dropwise to the above epoxy resin while cooling the bottle; the reaction itself is carried out at 110 ° to 120 ° C. within one hour. The reaction mixture is then allowed to age at 12,000 for 4 hours. It resulted that the acid value was below 5. In this way you got a light yellow, clear, solid resin with an AV value of 5.5 and an oxirane oxygen content of 0.10% by weight.

MANUFACTURING 13 (comparative experiment) The method of making 12 was repeated in the same manner using 558 parts (3 epoxy equivalents) an epoxy resin sold under the name "Epikote 828" by Shell Chemical Co. and has an epoxy equivalent of 186; also became 0.39 parts (0.0035 Moles) hydroquinone, 3.9 parts (0.015 moles) DMP-30 and 216.3 parts (3.0 moles) acrylic acid added. The acid value found was below 5. This turned into a light yellow clear, viscous resin with an AV value of 0.54 and an oxirane oxygen content of 0.05% by weight.

PREPARATION 14 (comparative experiment) A bottle was made with 1.0 mol Acrylic acid, 1.0 mol of phthalic anhydride, 0.34 mol of Epikote 828 (epoxy equivalent = 186), 301.7 parts (0.0064 moles) D1EP and 0.17 parts (0.0015 moles) hydroquinone. With the gradual addition of 1.8 spars of propylene oxide, the reaction was stopped at 800 bis 90 ° C carried out with stirring. After completing the dropwise addition the mixture was aged at 850 to 90 ° C for 5 hours. Having established was that the acid value was decreased below 10 was blown with air unreacted propylene oxide removed; it became a light yellow, transparent, Viscous epoxy acrylate resin obtained by an AT value of 9.1 and an OHV value was marked by 117.6.

PREPARATION 15 (comparative experiment) A bottle was made with 2 moles HEA and 0.3 part (0.0027 mole) hydroquinone charged. While blowing through In air, the temperature was raised to 85 ° C and the reaction at 850 to 90 ° C for 30 minutes carried out with the dropwise addition of 1 mol of gDI. The reaction mixture was left 5 hours at 90 ° C age, being a light yellow, translucent Vinyl urethane resin obtained with an NCO content of less than 0.4% by weight that is still present became. The resin was found to have the following characteristics: AV - 3.4; 0H = 18.7; NCO% = 0.29.

PREPARATION 16 (comparative) A bottle was made with 2.0 moles of pentaerythritol triacrylate and 0.38 parts of C0.0035 moles) of hydroquinone. With air being blown through the temperature in the bottle was increased to 70 ° C. Then 1.0 ol hexamethylene diisocyanate was added slowly dropwise over a period of one hour at one temperature from 700 to 90 ° C added. The reaction mixture was allowed to age at 90 ° C for 7 hours, a light yellow, clear, viscous vinyl urethane resin was obtained with the following identifier received: AV = 3.2 :; OHV = 64.5; NCO i0 = 2.01.

PREPARATION 17 (comparative) A bottle was made with 1 mole of TDI and 0.15 Parts (0.0014 moles) of hydroquinone charged. The temperature was increased to 70 ° C. While bubbling air through the contents of the bottle became gradually dropwise 1 mole of HEA added. The reaction was carried out at 700 to 80 ° C for one hour. The reaction mixture was allowed to age at 80 ° C. for one hour and was recovered in the process Vinyl urethane prepolymer with NCO end groups and an NCO content of 14% by weight. One was slowly dropwise added to 0.75 moles of this vinyl urethane prepolymer melt of 0.25 Holmen of trimethylolpropane, which had been heated to 80 ° C., was added. The reaction was performed at 80 to 90 ° C for 30 minutes. Then the reaction mixture was left Age at 110 ° to 12500 for 3 hours. It turned out to be the NCO level reduced to below 0.4% by weight.

Thus, there was obtained a light yellow, transparent, viscous vinyl urethane resin obtained with the following characteristics: AV ^ 1.5; OHV B 23.0; NO% = 0.37.

PREPARATION 18 (comparative experiment) A bottle was filled with 1.0 mol Polyethylene glycol (molecular weight = 400), 2.0 moles of pentaerythritol triacrylate (PETA) and 0.67 parts (0.0061 moles) of hydroquinone. With air being blown through the temperature was increased to 120 ° C by the contents of the bottle. Under gradual dropwise addition of 2.0 moles of TDI, the reaction at 120 ° to 12500 a Performed for an hour. Then the reaction mixture was left at 12500 for 5 hours age long. As it turned out, the NCO content was less than 0.5% by weight reduced.

In this way, flan was given a light yellow, transparent, viscous color Vinyl urethane resin with the following characteristics: AV = 9.7; OHV = 25.7; NCO% = 0.48.

PREPARATION 19 (comparative experiment) While blowing air through charged a bottle with 2.0 moles of a vinyl urethane prepolymer which is like in trial 17; the mass was heated to 80 ° C.

Then there was 1.0 mole of hydroxyl-terminated poly-1,4-butanediol adipate (PBA) (Trademark: Nipporane 4009, manufactured by Nippon Polyurethane K.K.) gradually added dropwise.

The reaction was carried out at 750 to 900C for one hour, then the reaction mixture was aged at 90 ° C. for one hour. As stated was, the NCO content was reduced to less than 0.3 wt. i / o. One received on this way a light yellow, transparent, viscous vinyl urethane resin with the following Code: AV = 0.93; 01w = 11.1; NCO% = 0.28.

Production 20 (comparative experiment) A bottle was made with 1.5 spars Acrylic acid, 1.5 moles of phthalic anhydride, 0.35 parts (0.0032 moles) of hydroquinone and loaded 3.5 parts (0.013 batch) of DMP-30; then 5.4 thiols became propylene oxide gradually added dropwise to the mixture at 800 to 90 ° C with stirring to induce a response. After the completion of the dropwise addition, it was left age the reaction mixture at 80 ° C. for 2 hours. It was found to be the Acid value reduced to less than 10.

This was not done by blowing air through the contents of the bottle reacted propylene oxide removed, and a transparent, viscous polyester monoacrylate with hydroxyl end groups. The product was heated to 50 ° C cooled, and with the slow dropwise addition of 0.3 moles of hexamethylene diisocyanate the reaction was carried out at 50 ° to 0 ° for 2 hours. As stated was the residual content of SCO groups less than 0.1% by weight. In this way, a light yellow, transparent, viscous polyester urethane acrylate resin was obtained with the following characteristics: AV = 8.3; OHV = 102; NCO% = 0.08.

PREPARATION 21 (comparative) A bottle was filled with 1.0 moles of an adduct of 2 moles of ethylene oxide in bisphenol A, 5 '2 parts (0.032 moles) of dimethylaminoethyl methacrylate and 390 parts (3.05 moles) of butyl acrylate. Then 2.0 whey became hexamethylene diisocyanate dropwise under a stream of nitrogen of the mass over a period of Added for 2 hours at a reaction temperature of 50 ° C. Subsequently were another 0.21 moles of HEA dropwise over a period of 2 hours at 60 ° C added. After the completion of the dropwise addition, the mixture was left at 70 ° C Age for 3 hours and gave a light yellow, clear, liquid resin with the following characteristics: AV = 0.48; OHV n 1.3; NCO% X 6.8.

EXAMPLE 1 A resin composition obtained by adding 5 parts of benzoin isobutyl ether, a sensitizer, to the resin and monomer components shown in Table 1 was formed, was in a thickness of 5 μ with the help of an order rod on a Painted paper made with red and black inks of the oxidation polymerization type (Trademark: Super Gloria, manufactured by Toka Shikiso Kagaku Kogyo K.K.). The coated paper became one for a certain time Exposed to ultraviolet radiation from a high pressure mercury lamp operated with 2 KW originated at a distance of 80 mm from the coating. It took place hardening of the coating. After this treatment the coating was completely hardened, and there was no sticking to the surface of the coating. The results the adhesive test with a cellophane tape and the bending test at 180 ° are from the table 1 can be seen.

For comparison, resins outside the range of the present Invention lie, tested in the same way. The results obtained are also can be seen from table 1.

The coating properties described in Tables 1 to 9 were determined and assessed according to the following procedure.

1. Pencil hardness: Mitsubishi Uni pencils with a hardness from 43 to 6H were used to scratch the coating. The pencil hardness will expressed by the hardest pencil that does not scratch the coating.

2. Adhesive test with the oellophane tape: An adhesive gellophane tape of a Size of 25mm x 25mm (manufactured by Sekisui Sagaku) was based on the Cover pressed on and peeled off after a few moments. The condition of the coating was tested and rated according to the following scale: 3 = no change 2: partially peeled off 1: completely peeled off 3. Cross-cut cutting test: (so-called X-cut) At a distance of 1 mm in the longitudinal and the transverse direction eleven strokes on the coating applied to a depth that the surface of the substrate was achieved; 100 cut squares were obtained. A cellophane tape (manufactured by Sekisui Eagaku) was pressed onto the scribed cover and withdrawn after a few moments. The properties were evaluated according to the number of cut out squares that are not together with the duct tape were relieved; for example, 100/100 means that there is no square was peeled off, märend the indication O / 100 means that all squares were peeled off.

4. So-called Erichsen test: This test was carried out using a Erichsen shock tester carried out. The properties were evaluated according to the Impact force at which the formation of small cracks was observed for the first time.

5. Flexural properties: In all examples except the example 1 became a bending tester is used. The coated substrate was kinked with a radius of curvature of 2 mm and a bending angle of 1800, whereby the cover was on the outside. The condition of the coating has been checked, and rated according to the scale given below.

In Example 1, the coated substrate was fully bent 1800, with the coating on the outside, and the condition of the coating was rated on the following scale: 3: no change 2: partially torn 1: completely torn.

TABLE 1 (Substrate = art paper, printed with red and black Oxidation polymerization type ink) Resin parts monomer and parts hardener hardening time peel test with bending Stand and solution in adhesive cello own part medium seconds phan tape ink shafts Red Black Present Invention: Manufacture- 2-hydroxy- 40 ultraviolet- 0.40 3 3 3 lung 1 thylacrylate irradiation Manufacture 70 - "- 30 -" - 0.50 3 3 3 ment 2 Manufacture- 60 - "- 40 -" - 0.80 3 3 3 ment 3 Manufacture 75 - "- 25 -" - 1.75 3 3 3 ment 4 Manufacture 60 - "- 40 -" - 0.25 3 3 3 ment 5 Manufacture 75 - "- 25 -" - 0.25 3 3 3 ment 5 Manufacture 70 - "- 30 -" - 0.25 3 3 3 ment 7 TABLE 1 (continued) Resin parts monomer and parts hardener hardening time peel test with bending Stand and solvent in adhesive cello-own part seconds phanband ink: shafts Red Black Present Invention: Manufacture- 70 2-hydroxyä- 30 ultraviolet- 0.25 3 3 3 lung 8 thylacrylate irradiation Manufacture 70 2-hydroxyä- 30- "- 0.25 3 3 3 lung 9 thylacrylate Manufacture 70 - "- 30 -" - 0.25 3 3 3 ment 10 Manufacture 70 "and 15" 0.30 3 3 3 ment 10 trimethylolpro- pantriacrylate Manufacture 100 nothing 0 - "- 0.25 3 3 3 ment 11 Comparison: Hestel- 60 2-hydroxyethyl- 40 ultraviolet- 0.25 1 1 3 ment 12 acrylate irradiation Manufacture 80 - "- 20 -" - 0.25 1 1 2 ment 13 TABLE 1 (continued) Resin parts monomer and parts hardener hardening time peel test with bending stand- solvent in adhesive cello- own- partial seconds phan tape / ink shafts Red Black Comparison: Manufacture- 85 2-hydroxyethyl- 15 ultraviolet- 0.25 2 1 2 treatment 15 acrylate irradiation Manufacture 60 - "- 40 -" - 0.25 2 1 3 ment 17 Manufacture 70 - "- 30 -" - 0.25 1 2 1 lung 18 Manufacture 70 - "- 30 -" - 2.5 ... not hardened ... lung 19 EXAMPLE 2 Using the resin compositions shown in Table 2, coating was carried out in the same manner as in Example 1, except that instead of the art paper printed with an oxidation polymerization type ink, a tin plate printed with a red oxidation polymerization ink ink (trademark: Super Gloria SG-G Red A-31, manufactured by Toka Shikiso Kagaku Kogyo EK) was used as a substrate. The obtained coatings were subjected to the pencil hardness test, the peeling test with the adhesive cellophane tape, the Erichsen test and the bending test in the same manner as in Example 1. The results obtained are shown in Table 2.

For comparison, resin compositions that are outside the range of present invention are tested in the same way.

The results given in Table 2 were also obtained.

TABLE 2 (Substrate: tin plate printed with oxidation polymerization type red ink) Resin Com- Monomer and Cure Time Coating Properties Parts Parts Hardeners component solvent in lead peel-off Erich bending seconds hardness test m.d. Sen-Eigen-Cellophane-Test (mm) shaft.

band present invention: Manufacture 60 2-Hydroxyä- 40 ultraviolet 0.50 F 3 6.9 3 treatment 1 thyacrylate irradiation manufacture 70 - "- 30 -" - 0.75 F 3 6.9 3 manufacture 2 manufacture 60 - "- 40 -" - 1.00 H 3 6.0 3 manufacturing 75 - "- 25 -" - 5.00 3B 3 6.9 3 manufacturing 4 manufacturing 75 - "- 25 -" - 0.40 F 3 6.5 3 production 5 production 60 - "- 40 -" - 0.30 HB 3 7.0 3 production 6 production 70 - "- 30 -" - 0.40 H 3 5.0 2 tion 7 TABLE 2 (continued) Resin component monomer and curing time properties of the coating Parts parts hardeners component solvent in lead- peel- erich- bending- Seconds hardness test md sen- intrinsic Cello test shaft. phanband (mm) Present Invention: Manufacture 70 2-hydroxy- 30 ultraviolet 0.50 F 3 7.4 3 lung 8 thylacrylate irradiation Manufacture- 70- "- 30-" - 0.40 F 3 6.8 3 ment 9 Manufacture 70 - "- 30 -" - 0.50 B 3 6.9 3 ment 10 Manufacture 100 nothing 0 - "- 0.40 H 3 6.8 3 ment 11 Comparison: Manufacture- 60 2-hydroxy- 40 ultraviolet- 0.40 H2-3 lung 12 thylacrylate irradiation Manufacture 80 "- 20" - 0.40 H 2 - 1 ment 13 Manufacture 70 "- 30" - 0.75 H 2 - 1 ment 14 Manufacture 85 - "- 15 -" - 0.50 2H 1 1.2 1 ment 15 TABLE 2 (continued) Resin component monomer and curing time properties of the coating Parts parts hardeners component solvent in lead- peel- erich- bending- Seconds hardness test md sen- intrinsic Cello test shaft. phanband (mm) Comparison: Manufacture 75 2-Hydroxy- 25 Ultraviolet 0.75 2H 2 0.6 1 lung 16 thylacrylate irradiation Manufacture 70 - "- 30 -" - 0.25 B 1 - 3 lung 18 Manufacture 70 - "- 30 -" - 2.5 4B ... nothing hardened .... lung 19 EXAMPLE 3 Using the resin compositions shown in Table 3, the coating was carried out in the same manner as in Example 1, except that an acetone-treated tin plate (manufactured by Taiyu Eizai; Japanese Industrial Standard = JIS G-3303 COIL) was used as the substrate. The coatings obtained were subjected to the pencil hardness test (using pencils from Nitsubishi Uni), the peeling test with the adhesive cellophane tape, the peeling test after cross-cutting, the Erichsen test and the bending test in the same manner as indicated in Example 1. The results given in Table 3 were obtained.

For comparison, resin compositions that are outside the range of the present Invention are tested in a similar manner. Here, too, were those from the table Obtained 3 apparent results.

TABLE 3 (substrate: acetone treated tin plate) Resin Com- Monomer Hardness- Hardening Time Properties of the coating Share parts components and solvents in lead. Peel-off Cross Erich Bending medium seconds hardness test with cut- own- Cello test shank. phanband (mm) Present Invention: Manufacture- 60 2-Hydroxy- 40 Ultravio- 0.50 F 3 100/100 6.8 3 ment 1 ethyl bed acrylate radiation Manufacture 70 - "- 30 -" - 0.70 F 3 100/100 7.0 3 ment 2 Manufacture 60 - "- 40 -" - 1.00 H 3 100/100 6.2 3 ment 3 Manufacture 60 - "- 40 -" - 0.30 HB 3 100/100 6.9 3 ment 6 Manufacture 60 - "- 40 -" - 0.30 F 3 100/100 6.9 3 ment 9 Manufacture 60 - "- 40 -" - 0.50 2B 3 100/100 6.8 3 ment 10 Manufacture 70 - "- 30 -" - 0.50 B 3 100/100 6.8 3 ment 10 TABLE 3 Resin Com- Monomer Hardness- Hardening Time Properties of the coating Share parts components and solvents in lead. Peel-off Cross Erich Bending medium seconds hardness test with cut- own- Cello test shank. phanband (mm) Present Invention: Manufacture- 60 2-Hydroxy- 40 Ultravio- 1.25 F 3 100/100 7.0 3 treatment 10 ethyl meth- acrylate radiation Manufacture 70 70 2-Hydroxy- 20 Ultravio- HB 3 100/100 7.0 3 treatment 10 ethyl acrylate propyl alcohol 10 Manufacture 100 nothing 0 - "- 0.30 H 3 100/100 6.0 3 ment 11 Comparison: Manufacture- 60 2-Hydroxy- 40 Ultravio- 0.40 H 3 100/100 7.5 3 ment 12 ethyl lettuce acrylate radiation Manufacture 80 - "- 20 -" - 0.40 H 3 100/100 6.8 3 ment 13 Manufacture 75 - "- 25 -" - 0.70 HB 3 75/100 6.9 3 ment 14 Manufacture 85 - "- 15 -" - 0.50 2H 3 0/100 7.0 3 ment 15 TABLE 3 (continued) Resin components, monomers, hardness, hardening time, properties of the coating, parts, components and solvents in pencil, peelable, cross, erich, bending agent, seconds hardness test with cut, self-cello test, shaft.

phanband (mm) comparison: poor production 75 2-hydroxyä- 25 ultravio- 0.75 2H 2 0/100 1 surface

treatment 16 thylacrylate irradiation Manufacture 60 - "- 40 -" - 0.40 H 3 0/100 1.1 1 production 17 production 80 - "- 20 -" - 0.25 H 3 0/100 4.6 1 production 18 production 70 - "- 30 -" - 2.50 ..... not hardened ................

manufacturing 19 manufacturing 75 - "- 25 -" - 1.75 H 3 25/100 7.2 3 manufacturing 20 manufacturing 100 nothing 0 - "- 2.50 3B 2 0/100 7.1 3 lung 21 EXAMPLE 4 Under Using the resin compositions given in Table 4, the coating was carried out in the same way Way as indicated in Example 3, with the difference that instead of of the acetone-treated tin plate, an acetone-treated aluminum plate (manufactured from Burma Taiyu Eizai; Japanese industrial standard JIS H-400O AlO50P) is used became.

The coatings obtained were subjected to the pencil hardness test, the peel test with the adhesive cellophane tape, the peel test after cutting crosswise, and subjected to the Erichsen test in the same way as in Example 3. There were those evident from Table 4: Results obtained.

For comparison, resin compounds that are outside the range of the present Invention lie, tested in the same way.

The results shown in Table 4 were also obtained here.

TABLE 4 (Substrate: aluminum plate treated with acetone) Hazrkom Monomer Hardness Hardness Time Properties of the coating Share parts components and solvents in lead- peel- cross- erich- bending medium seconds hardness test with cut- own- Cello test shank. phanband (mm) Present Invention: Manufacture- 60 2-Hydroxy- 40 Ultravio- 0.50 H 3 100/100 6.1 ment 1 ethyl bed acrylate radiation Manufacture 70- "- 30-" - 0.70 F 3 100/100 6.5 ment 2 Manufacture 60- "- 40-" - 1.00 2H 3 100/100 6.0 ment 3 Manufacture 60 "- 40" - 0.30 F 3 100/100 6.4 ment 9 Manufacture 60 - "- 40 -" - 0.50 HB 3 100/100 6.7 ment 10 Manufacture 70 - "- 30 -" - 0.50 HB 3 100/100 6.9 ment 10 Manufacture- 60 2-Hydroxy- 40- "- 1.25 F 3 100/100 6.0 ment ethyl meth- acrylate TABLE 4 (continued) Resin Com- Monomer Curing Time Properties of the coating Parts parts hardeners component and solution in lead pull-off test cross-Erichsen Average seconds hardness with cello cut test (mm) phanband test Present Invention: Manufacture- 70 2-Hydroxy- 20 Ultravio- 0.50 HB 3 100/100 6.6 treatment 10 ethyl acrylate and radiation Isopropel 10 alcohol Manufacture- 100 nothing 0- "- 0.30 H 3 100/100 6.4 ment 11 Comparison: Manufacture- 60 2-Hydroxy- 40 Ultravio- 0.40 2B 3 0/100 6.6 ment 12 ethyl lettuce acrylate radiation Manufacture 80 - "- 20 -" - 0.40 B 3 0/100 6.9 ment 13 Manufacture 75 "- 25" - 0.70 HB 3 90/100 6.3 ment 14 Manufacture 85- "- 15-" - 0.50 2H 3 0/100 6.5 ment 15 Make 75- "- 25-" - 0.75 2H 3 0/100 bad ment 16 surface. Manufacture 60 - "- 40 -" - 0.40 2H 3 0/100 1.0 ment 17 TABLE 4 (continued) Resin Com- Monomer Curing Time Properties of the coating Parts parts hardeners component and solution- in lead- peelable- cross- erich- medium seconds hardness test with cutting Cello test test phanband (mm) Comparison: Manufacture 80 2-Hydroxy-20 Ultravio-0.25 H 3 0/100 4.8 18 ethyl lettuce acrylate radiation Manufacture 70 - "- 30 -" - 2.50 ..... not hardened ........... lung 19 Manufacture 75 "- 25" - 1.75 H 3 90/100 6.4 ment 20 Manufacture 100 nothing 0 - "- 2.50 3B 2 0/100 6.5 ment 21 EXAMPLE 5 Using the resin compositions shown in Table 5, coating was carried out in the same manner as in Example 3 except that an acetone-treated ordinary glass plate (Japanese Industrial Standard: JIS R-3201) was used in place of an acetone-treated tin plate . The resulting coating was subjected to the pencil hardness test, the peel test with the cellophane tape and the peel test after cross-cutting, in the same manner as in Example 3. The results shown in Table 5 were obtained.

For comparison, resin compositions that are outside the range of the present Invention lie, tested in the same way.

The results shown in Table 5 were also obtained here.

TABLE 5 (Substrate = ordinary glass treated with acetone) Resin monomer and hardness properties of the coating Parts parts hardeners mass solvent time in lead peel test cross Seconds hardness m / cello cut phanband test According to the invention: # Manufacture- 60 2-hydroxyethyl- 40 ultraviolet- 0.50 HB 3 100/100 treatment 1 acrylate irradiation Manufacture 70 - "- 30 -" - 0.70 HB 3 100/100 ment 2 Manufacture- 60- "- 40-" - 1.00 F 3 100/100 ment 3 Manufacture 60 - "- 40 -" - 0.30 B 3 100/100 ment 7 Manufacture 60 - "- 40 -" - 0.40 HB 3 100/100 lung 8 Manufacture 70 - "- 30 -" - 0.50 F 3 100/100 lung 8 Manufacture 60 - "- 40 -" - 0.30 2B 3 100/100 ment 9 Manufacture 60 - "- 40 -" - 0.50 F 3 100/100 ment 10 TABLE 5 (continued) Resin monomer and hardness properties of the coating Parts parts hardeners mass solvent time in lead peel test cross hardness m / cello cut phanband test According to the invention: Manufacture 70 2-hydroxyethyl 30 ultraviolet 0.50 F 3 100/100 treatment 10 acrylate irradiation Manufacture 60 "- 40" - 1.25 H 3 100/100 ment 10 Manufacture 70 "and Isopro 20" - 0.50 F 3 100/100 lung 10 pyl alcohol 10 Manufacture- 100 nothing 0- "- 0.30 F 3 100/100 ment 11 Comparison: Manufacture 60 2-hydroxyethyl 40 ultraviolet 0.40 B 3 35/100 ment 12 acrylate irradiation Manufacture 80 - "- 20 -" - 0.40 H 3 0/100 ment 13 Manufacture 75 - "- 25 -" - 0.70 HB 3 10/100 ment 14 Manufacture 85 - "- 15 -" - 0.50 2H 3 0/100 ment 15 TABLE 5 (continued) Resin parts, monomer and hardness properties of the coating Parts hardener mass solvent time in lead peel test cross Seconds hardness m / cello cut phanband test Comparison: Manufacture- 75 2-hydroxyethyl- 25 ultraviolet- 0.75 2H 2 0/100 treatment 16 acrylate irradiation Manufacture 60 - "- 40 -" - 0.40 H 3 0/100 ment 17 Manufacture 80- "- 20-" - 0.25 F 3 0/100 lung 18 Manufacture 70 - "- 30 -" - 2.50 .... not hardened ........ lung 19 Manufacture 75 - "- 25 -" - 1.75 HB 3 90/100 ment 20 Manufacture 100 nothing 0- "- 2.50 3B 2 0/100 ment 21 EXAMPLE 6 Using the resin compositions shown in Table 6, coating was carried out in the same manner as in Example 3, with the difference that instead of the acetone-treated tin plate, a synthetic resin plate washed with a neutral detergent (trade mark : Family, manufactured by Kao Sekken EE).

The resulting coatings were subjected to the pencil hardness test, the peel test with the cellophane tape and the peel test after cutting crosswise into the same Way as in Example 3 subjected. In doing so, those shown in Table 6 became apparent Get results.

For comparison, resin compositions that are outside the range of present invention are tested in the same way.

The results shown in Table 6 were also obtained here.

TABLE 6 (substrate: synthetic resin plate, washed with a neutral detergent) Synthetic resin. Hardness-hardness properties of the coating mass parts monomer parts resin plate medium time lead peel test cross (Sec.) Hardness m / cello cut phanband test Manufacture 70 2-hydroxyethyl 30 FRP sheet Ultra 0.50 HB 3 100/100 ment 1 acrylate made of un- violet- (according to the invention) saturated irradiated Polyester lung Manufacture 70 - "- 30 -" - - "- 0.50 HB 3 100/100 ment 10 (According to the invention) Manufacture 85 - "- 15 -" - - "- 0.50 2H 2 0/100 ment 15 (Comparison) Pentaery- 75 - "- 25 -" - - "- 1.00 4H 3 0/100 thrittri- acrylate (PETA) (Comparison) Manufacture 70 - "- 30 Acrylic- -" - 0.50 HB 3 100/100 lung 1 plate (according to the invention) Manufacture 70 - "- 30 Acrylic- -" - 0.50 HB 3 100/100 lung 10 plate (according to the invention) Manufacture 85 - "- 15 -" - - "- 0.50 2H 2 0/100 ment 15 (Comparison) TABLE 6 (continued) Resin parts monomer parts syntheti. Hardness-hardness properties d. Coating mass resin plate medium time lead peel test cross (Sec.) Hardness m / cello cut phanband test PETA 75 2-hydroxyethyl 25 acrylic sheet Ultravio- 1.00 2H 3 40/100 (Compare) acrylate radiation Manufacture 70 - "- 30 polyvinyl -" - 0.50 HB 3 100/100 lung 1 chloride (Invention) plate Manufacture 70 - "- 30 -" - - "- 0.50 HB 3 100/100 ment 10 (Invention) Manufacture 85 - "- 15 -" - - "- 0.50 2H 1 0/100 ment 15 (Cf.) PETA 75 - "- 25 -" - - "- 1.00 H 2 0/100 (Cf.) Manufacture 70 - "- 30 ABS- -" - 0.50 HB 3 100/100 lung 1 plate (Invention) Manufacture 70 - "- 30 -" - - "- 0.50 HB 3 100/100 ment 10 (Invention) Manufacture 85 - "- 15 -" - - "- 0.50 2H 3 0/100 lung 15 (cf.) PETA (comp.) 75 - "- 25 -" - - "- 1.00 2H 3 50/100 EXAMPLE 7 A resin composition containing the resin and the monomer components according to Table 7 was applied to a tin plate treated with acetone in a thickness of 5 μm with the aid of a coating bar; then the plate was subjected to an electron beam irradiation of 30 Mrad / sec at room temperature. and a voltage acceleration - of 300 KV irradiated with a dose of 5 nrad. The coating was completely cured. The coating obtained was subjected to the pencil hardness test, the peeling test with the cellophane adhesive tape, the peeling test after cross-cutting, the Erichsen test and the bending test. The results shown in Table 7 were obtained.

For comparison, resin compositions that are outside the range of present invention are tested in the same way.

The results shown in Table 7 were also obtained here.

Table 7 (substrate = tin plate treated with acetone) Resin parts monomer and parts hardener properties of the coating Mass Solvent Lead Removal Cross Erich Bending pen test cut sen- own hardness w / cello test shafts phanband (mm) Invention: Manufacture- 60 2-hydroxyethyl- 40 electrons- H 3 100/100 6.3 3 lung 1 acrylate jet Hest- 70 - "- 30 -" - H 3 100/100 6.5 3 ment 2 Manufacture 60 "- 40" - 2H 3 100/100 6.2 3 ment 3 Manufacture- 60- "- 40-" - H 3 100/100 6.2 3 ment 6 Manufacture 60 "- 40" - 2H 3 100/100 6.0 3 ment 9 Manufacture- 60- "- 40-" - F 3 100/100 6.3 3 ment 10 Manufacture 70 - "- 30 -" - F 3 100/100 6.3 3 ment 10 Manufacture 60 2-hydroxyethyl 40- "- 2H 3 100/100 6.5 3 lung 10 methacrylate TABLE 7 (continued) Resin parts monomer and parts hardener properties of the coating Mass Solvent Lead Peel-off Cross Erich Bending pen test cut sen- own hardness m / cello test test sheep phanband (mm) th Invention: Manufacture 70 2-hydroxyethyl 20 electrons 2H 3 100/100 6.3 3 ment 10 acrylate and jet Isopropyl alcohol 10 Manufacture- 100 nothing 0- "- 2H 3 100/100 6.5 3 ment 11 Comparison: Manufacture 60 2-hydroxyethyl 40- "- 3H 3 0/100 6.2 3 ment 12 acrylate Manufacture 80- "- 20-" - 3H 3 0/100 5.8 2 ment 13 Manufacture 75- "- 25-" - H 3 0/100 5.9 3 ment 14 Manufacture 85 - "- 15 -" - 3H 3 0/100 5.9 1 ment 15 Manufacture- 75- "- 25-" - 3H 2 0/100 bad 1 16 surface Manufacture- 60- "- 40-" - 2H 3 0/100 0.9 1 lung 17f TABLE 7 (continued) Resin parts monomer and parts hardener properties of the coating Mass Solvents Lead Abrasion Cross Erich Bending pen test cut sen- own hardness m / cello test test sheep phanband (mm) th Comparison: Manufacture 80 2-hydroxyethyl 20 electrons 2H 3 0/100 4.8 3 lung 18 acrylate jet Manufacture 70 - "- 30 -" - F 3 25/100 6.5 3 lung 19 Manufacture- 75- "- 25-" - 2H 3 40/100 6.3 3 ment 20 Manufacture 100 - "- 0 -" - B 2 0/100 6.5 3 ment 21 EXAMPLE 8 Using the resin compositions shown in Table 8, coating was carried out in the same manner as in Example 7 except that an acetone-treated ordinary glass plate (Japanese Industrial Nomenclature: JIS R-3201) was used in place of the acetone-treated tin plate . The resulting coverings were subjected to the pencil hardness test, the peel test with the adhesive cellophane tape, and the peel test after cross-cutting in the same manner as in Example 7. The results shown in Table 8 were obtained.

For comparison, resin compositions that are outside the range of present invention are tested in the same way.

The results shown in Table 8 were also obtained.

TABLE 8 (substrate = common glass treated with acetone) Resin parts Monomers and parts Hardeners Properties of the coating bulk solvent pencil peel test cross hardness m / cello cut phanband test Invention: Manufacture 60 2-hydroxyethyl 40 electron beam F 3 100/100 ment 1 acrylate Manufacture- 70- "- 30-" - F 3 100/100 ment 2 Manufacture- 60- "- 40-" - 2H 3 100/100 ment 3 Manufacture- 60- "- 40-" - F 3 100/100 ment 7 Manufacture- 60- "- 40-" - F 3 100/100 lung 8 Manufacture 70- "- 30-" - 2H 3 100/100 lung 8 Manufacture- 60- "- 40-" - H 3 100/100 ment 9 Manufacture- 60- "- 40-" - H 3 100/100 ment 10 TABLE 8 (continued) Resin parts monomer and parts hardener properties of the coating mass solvent pencil peel test cross hardness m / cello cut phanband test Invention: Manufacture 70 2-hydroxyethyl 30 electron beam H 3 100/100 ment 10 acrylate Manufacture 60 2-hydroxyethyl 40- "- 2H 3 100/100 lung 10 methacrylate Manufacture 70 2-hydroxyethyl 20- "- 2H 3 100/100 ment 10 acrylate and Isopropyl alcohol 10 get Manufacture- 100 nothing 0- "- H 3 100/100 ment 11 Comparison: Manufacture 60 2-hydroxyethyl 40- "- H 3 0/100 ment 12 acrylate Manufacture 80- "- 20-" - 2H 3 0/100 ment 13 Manufacture 75 - "- 25 -" - H 3 20/100 ment 14 Manufacture 85- "- 15-" - 4H 3 0/100 ment 15 TABLE 8 (continued) Resin parts monomer and parts hardener properties of the coating mass solvent pencil peel test cross hardness m / cello cut phanband test Comparison: Manufacture 75 2-hydroxyethyl 25 electron beam 4H 3 0/100 ment 16 acrylate Manufacture- 60- "- 40-" - 3H 3 0/100 ment 17 Manufacture 80- "- 20-" - H 3 0/100 lung 18 Manufacture- 70- "- 30-" - F 3 5/100 lung 19 Manufacture- 75- "- 25-" - F 3 50/100 ment 20 Manufacture- 100 nothing 0- "- B 3 0/100 ment 21 EXAMPLE 9 The influence of the absorbency of the surface of a substrate on the adhesiveness of the resin to the substrate was tested. As the non-absorbent substrate, the acetone-treated tin plate used in Example 3 and the acetone-treated ordinary glass plate used in Example 5 were used; Art paper and a wooden board were used as the absorbent substrate. The coating was carried out in the same way as in Example 3, and the coatings obtained were subjected to the peeling test after cross-cutting and the peeling test with the adhesive cellophane tape. The resin compositions used and the results obtained are shown in Table 9.

For comparison, resin compositions that are outside the range of present invention were tested in a similar manner.

The results shown in Table 9 were also obtained.

As can be seen from the results given in Table 9, the Adhesion to the substrate in a considerable way depends on the absorption capacity of the Affected substrate surface; but the resin compositions of the present invention also have excellent adhesiveness to non-absorbent substrates.

TABLE 9 (Non-absorbent substrates = tin plate and glass; absorbent substrates = art paper and stacked wood boards) Resin parts monomer parts hardness non-absorb. Substrate absorbent. Substrate mass and solvent hardness peel test n / hardness peel cross time cross-wise time test with cut (Sec.) Incision (sec.) Cello test Tin-phane tape plate glass art print wood paper plate Invention: Manufacture- 60 2-Hydroxy- 40 Ultra- 0.50 100/100 100/100 0.25 3 100/100 lung 1 thylacrylate violet irradiate lung Manufacture 70 - "- 30 -" - 0.70 100/100 100/100 0.30 3 100/100 ment 2 Manufacturer- 60 - "- 40 -" - 1.00 100/100 100/100 0.60 3 100/100 ment 3 Manufacture 60 - "- 40 -" - 0.30 100/100 100/100 0.25 3 100/100 ment 9 Manufacture 60 - "- 40 -" - 0.50 100/100 100/100 0.25 3 100/100 ment 10 Manufacture 70 - "- 30 -" - 0.50 100/100 100/100 0.25 3 100/100 ment 10 Manufacture- 60 2-hydroxy- 40- "- 1.25 100/100 100/100 0.75 3 100/100 ment 10 ethyl meth- acrylate TABLE 9 (continued) Resin parts monomer parts hardness non-absorb. Substrate absorbent. Substrate mass and solvent hardness peel test n / hardness peel cross time cross-wise time test with cut (Sec.) Incision (sec.) Cello test Tin-phane tape plate glass art print wooden paper plate Invention: Manufacture 70 2-Hydroxy- 20 Ultra- 0.50 100/100 100/100 0.25 3 100/100 ment 10 ethyl acrylate violet and isopropyl 10 irradiate alcohol lung Manufacture 100 nothing 0 - "- 0.30 100/100 100/100 0.25 3 100/100 ment 11 Comparison: Manufacture 80 2-hydroxy-20- "- 0.40 0/100 0/100 0.25 3 100/100 ment 13 ethyl acrylate Manufacture 85 - "- 15 -" - 0.50 0/100 0/100 0.25 3 100/100 ment 15 Manufacture 60 - "- 40 -" - 0.40 0/100/0 100 0.25 3 100/100 ment 17 Manufacture 80 - "- 20 -" - 0.25 0/100 0/100 0.25 3 100/100 lung 18 Manufactured 70 - "- 30 -" - 2.50 not hardened. 2.25 3 100/100 lung 19 TABLE 9 (continued) Resin Parts Monomer Parts Hardness Non-absorb. Substrate absorbent. Substrate mass and solvent hardness peel test after hard peel cross mean time cross time test with cut (sec.) Incision (sec.) Cello-tin-phane tape plate glass art print wood paper plate comparison: Manufacture 70 styrene 30 Ultra 0.75 50/100 0/100 0.30 3 100/100, treatment 10 violet-ray production 70 Trimethylol 30 development 0.75 0/100 0/100 3 100/100, treatment 10 propane triacrylate - " -Manufacture- 60 glycidyl- 40 - "- 0.40 20/100 0/100 0.25 3 100/100 production 10 acrylate

Claims (16)

PATENT CLAIMS 1. Radiation-curable synthetic resin coating which has excellent adhesion to non-absorbent polar surfaces, consisting of: 1. A methacrylic or acrylic urethane resin, which is formed by the reaction of three compounds, namely (A) a polyoxyalkylenebisphenol A derivative or mixtures of this compound according to the following formulas: in which R1 is an alkylene radical with 2 to 4 carbon atoms, 1 halogen or a methgl group, a is an integer with the value 1 or 2 and m and n each time a number with the value at least 1, and the sum of m plus n is an integer Number is in the value of 2 to 8; or compounds containing hydroxyl end groups which are obtained by condensation reaction of the compounds of the formulas (a) and (b) with polycarboxylic acids or their anhydrides; with (B) polyisocyanate and (C) an acrylate and / or methacrylate containing hydroxyl groups, with II. a hydroxyl group-containing methacrylate or acrylate which is copolymerizable with the unsaturated end groups in methacrylic or acrylic urethane resin 1.. 2. Irradiation-curable resin composition according to claim 1, characterized in that that R¹ is propylene or ethylene. 3. Irradiation-curable resin composition according to claim 1, characterized in that that the polycarboxylic acid or its anhydride is an I) icarboxylic acid or a dicarboxylic anhydride represents. 4. Irradiation-curable resin composition according to claim 1, characterized in that that the sum of m and n is an integer from 2 to 6. 5. Resin composition curable by radiation according to claim 1, characterized in that that the polyoxyalkylenebisphenol derivative (A) is an ester formed by condensation a compound of formula (a) or (b) with a polycarboxylic acid in a molecular ratio over 3: 2 is obtained. 6. Irradiation-curable resin composition according to claim 1, characterized in that that the polyisocyanate (B) from tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate or hexamethylene diisocyanate. 7. Irradiation-curable resin composition according to claim 1, characterized in that the hydroxyl group-containing acrylate or methacrylate (C) is a compound or a mixture of compounds of the formulas (c), (d) or (e): or where R2 is an alkylene radical with 2 to 10 carbon atoms, R3 is hydrogen or a methyl radical, R4 is hydrogen or a hydrocarbon group with 1 to 6 carbon atoms, p and q each time an integer from 1 to 3 and r an integer from 1 to 2 mean. 8. Irradiation-curable resin composition according to claim 1, characterized in that that the methacrylic or acrylic resin 1. by reaction of a polyoxyalkylenebisphenol A derivative (A) with a polyisocyanate (B) and an acrylate containing hydroxyl groups and / or Methacrylate (C) is obtained in such amounts that the ratio of isocyanate groups of the polyisocyanate (B) to the hydroxyl groups of the polyoxyalkylenebisphenol-A derivative (A) is on the order of 1.8: 5 while the amount of hydroxyl group-containing Acrylate and / or methacrylate (C) per mole of the polyoxyalkylenebisphenol A derivative (A) corresponds to the following formula: c # (by-x) / z in which c is the number of moles of the hydroxyl group-containing Acrylate and / or methacrylate (C); z is the number of hydroxyl groups of the hydroxyl group-containing Means acrylate and / or methacrylate (C); b is the number of moles of the polyisocyanate (B), y is the number of isocyanate groups contained in one molecule of the polyisocyanate (B), and x represents the number of hydroxyl groups contained in one molecule of the polyoxyalkylene bisphenol A derivative () are present. 9. Irradiation-curable resin composition according to claim 1, characterized in that that the weight ratio of the methacrylate or acrylic urethane resin I to the hydroxyl group-containing Methacrylate or Acrylate II is on the order of 30:70 to 95: 5. 10. Irradiation-curable resin composition according to claim 1, characterized characterized in that the non-absorbent, polar surface is an ink surface, represents a glass surface, a metal surface or a polar plastic surface. 11. Radiation curable resin composition according to claim 3, characterized in that the dicarboxylic acid is made from malonic acid, succinic acid, Glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, Sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, phthalic acid, Isophthalic acid or terephthalic acid. 12. Radiation curable resin composition according to claim 7, characterized in that the hydroxyl group-containing acrylate or methacrylate (c) is a compound of the following type: hydroxyethyl acrylate, Hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylolpropane diacrylate, Trimethylolpropane dimethacrylate, pentaerythritol triacrylate or pentaerythritol trimethacrylate. 13. Irradiation-curable resin composition according to claim 1, characterized characterized in that the hydroxyl-containing methacrylate or acrylate II, the copolymerizable with the unsaturated end group in methacrylic or acrylic urethane resin I. if there is a compound or mixtures of these compounds of the following type: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, Diethylene glycol monomethacrylate, dipropylene glycol monoacrylate, dipropylene glycol monomethacrylate, Trimethylolpropane monoacrylate, Trimethylolpropane monomethacrylate, pentaerythritol monoacrylate, pentaerythritol monomethacrylate, Pentaerythritol diacrylate and pentaerythritol dimethacrylate. 14. Radiation curable resin composition according to claim 9, characterized characterized in that the weight ratio of the methacrylic or acrylic urethane resins s I to the hydroxyl group-containing methacrylate or acrylate II in the order of magnitude from 60:40 to 80:20. 15. A method for producing a coating on a substrate, characterized in that there is a coating film of the composition according to claim 1 applies to the substrate, and then the wet by applying irradiation hardens. 16. The method according to claim 15, characterized in that it is the substrate is an ink, a glass surface, a metal surface or a polar surface of a synthetic resin.