CS233095B1 - Curable compositions based on unsaturated synthetic resins - Google Patents

Abstract

Curable compositions consist of unsaturated synthetic resins containing unsaturated polyester with a molecular weight of 700 to 2,000 obtained by polycondensation reaction, β-unsaturated dicarboxylic acids or their derivatives, optionally in a mixture with compounds from the group of ortho-, iso- and terephthalic acids, aliphatic acids and/or their derivatives with polyhydric alcohols and β,-ethylenically unsaturated ether alcohols. Furthermore, the synthetic resin contains an oligoester with a molecular weight of 400 to 2,500 based on acrylic and/or methacrylic esters of epoxy resins of the bisphenol type, optionally modified with -unsaturated dicarboxylic acids. Furthermore, the composition contains reactive vinyl monomers and optionally other additives.

Description

(54) Curable compositions based on unsaturated synthetic resins

The curable compositions consist of unsaturated synthetic resins containing an unsaturated polyester having a molecular weight of 700 to 2,000 obtained by the polycondensation reaction, β-unsaturated dicarboxylic acids or derivatives thereof, optionally in admixture with compounds from the group of ortho-, iso- and terephthalic acid, aliphatic acids and / or derivatives thereof with polyhydric alcohols and β, -ethylenically unsaturated ether alcohols. Further, the synthetic resin comprises an oligoester having a molecular weight of 400 to 2,500 based on acrylic and / or methacrylic esters of bisphenolic-type epoxy resins, optionally modified with unsaturated dicarboxylic acids. Further, the composition comprises reactive vinyl monomers and optionally other additives.

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The present invention relates to novel, claimed other compositions based on unsaturated synthetic resins, reactive monomers and optionally additives. They are applied primarily as radiation-cured coatings and casting compositions.

The preparation of unsaturated polyester resins modified with β, γ-ethylenically unsaturated ether alcohols has been known for several decades. These resins were first used as a binder for the preparation of the so-called non-inhibited polyester varnishes, i.e.. varnishes drying even in the presence of air oxygen to a hard, non-sticky, insoluble and non-fusible product for surface treatment of wooden furniture parts, especially highly profiled parts, where the sanding and polishing of classic paraffinic polyester varnishes has caused considerable difficulties for other applications, especially in the construction and automotive industry, namely for the preparation of flooring materials, resp. body sealants. More recently, these resins have established themselves as a binder base for the preparation of radiation-cured coating compositions, in particular ultraviolet.

The preparation of dianium-based oligomeric acrylic or methacrylic esters of epoxy resins, the so-called epoxyacrylate resins, has also been known for many years. Originally used for the preparation of glass laminates with higher chemical resistance, they are now also used as a binder for the preparation of radiation cured coatings.

Although both types of resins exhibit a number of excellent mechanical and thermal properties, they are not for many applications

233 09S advantageous. For example, polyester resins based on β, β-unsaturated ether alcohols are very soft and soft due to the relatively high content of these ethers, which has an adverse effect, for example, on the surface hardness of the lacquer films prepared on the basis of these resins. In contrast, epoxyacrylate resins exhibit high hardness associated with considerable brittleness and tendency to yellow, which are properties that do not meet, for example:

The foregoing drawbacks are substantially eliminated by the present invention, which are directed to curable compositions based on unsaturated synthetic resins, reactive monomers and optionally additives. The essence of the invention is that the curable compositions consist of 20 to 60 wt. parts of unsaturated synthetic resins containing 10 to 90% by weight of an unsaturated polyester having a molecular weight of 700 to 2 000 obtained by the polycondensation reaction of d., phenylenedic dicarboxylic acids or derivatives thereof, optionally in admixture with ortho-, iso- and terephthalic acid compounds %, aliphatic acids and / or derivatives thereof with polyhydric alcohols and β-ethylenically unsaturated ether alcohols and 90 to 10 wt. oligoesters having a molecular weight of 400 to 2,500 based on acrylic and / or methacrylic esters of bisphenolic-type epoxy resins having a starting content of 2.5 to 5.5 mol / kg of epoxy groups, optionally modified with β-unsaturated dicarboxylic acids ·

Further, the composition consists of 40 to 80 parts by weight of reactive monomers selected from the group consisting of styrene and its methyl derivatives, alkyl esters of acrylic and methacrylic acid having a carbon number in the alkyl group of 1 to 8. Optionally, the composition may contain up to 15 parts by weight of additives from the reactive group. solvents, thixotropic agents, photoinitiators, initiators, curing accelerators and matters.

The advantage of the present invention lies above all in its simplicity, since it is essentially a mixture of two

233 09S unsaturated synthetic resins in ratios of 9: 1 to 1: 9 depending on the desired properties. The more components there are, the closer the resulting properties of the cured composition are to those of the predominant component. This results mainly in good mechanical properties, in particular bending strength, impact bending strength and very good temperature resistance of the lacquer films. In particular, polyhydroxyl glycol-type compounds, in particular ethylene glycol, are used as starting components to prepare the unsaturated polyester resins according to the invention. propylene glycol 4.2, propylene glycol-1.3, diethylene glycol, triethylene glycol, buthylene glycol-1.2, buthylene glycol-1.3, dipropylene glycol, neopentyl glycol, hexanediol-1.6 and xylylene glycols. Among the unsaturated dicarboxylic acids, these are in particular maleic anhydride, fumaric acid, citraconic acid, itaconic acid and mesaconic acid.

Of the unsaturated monocarboxylic acids, acrylic acid and methacrylic acid are particularly suitable. Among the modifying acids, phthalic anhydride, isophthalic acid, adipic acid, sebacic acid, tetrahydroftalanic anhydride endomethylenetetrahydrophthalic anhydride and, for example, benzoic acid and salicylic acid can be used.

The monoallyl and monomethallyl ethers of ethylene glycol, propylene glycol-1,2, butanediol-1,3, glycerine, trimethylolpropane and trimethylolethane, pentaerythritol, as well as the corresponding diallyl and dimetallyl ethers of glycerine can be used from / h, .beta.-ethylenically unsaturated ether alcohols. , trimethylolethane and pentaerythrite • Low molecular weight epian resins based on dianu of general formula can be used from epoxy resins

CBL - CH CH «O

OT ₃

CH ’3

OCIL · -CH-CH, l

OH

CH

CH

233 095 where ”n '* is 0 to 4 ·

Among the reactive monomers, styrene, vinyltoluene, methylraethacrylate and other acrylic and methacrylic esters of mono- and polyfunctional alcohols are used in particular. Ethylacetate, butyl acetate, isopropyl alcohol and others are used for non-reactive solvents. Potoinitiators are used on the basis of benzoin and its alkyl ethers, further on the basis of benzilketals and possibly other types. As the peroxide initiator of the hydroperoxide type, for example, methylcyclohexanone peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide and / or mixtures thereof can be used. Cobalt octtoate or cobalt naphthenate containing 1 to 6 wt. % cobalt. Among the thixotropic agents, for example, colloidal silicon dioxide and asbestos fibers of the chrisothiol type and, in particular, zinc and calcium stearate, can be used. The curable compositions of the invention are prepared by simply mixing the unsaturated polyester resin with an epoxy acrylate oligoester in a suitable homogenizer at the weight ratios defined by the invention at normal and / or slightly elevated temperature (up to 40 ° C) with optional addition of non-reactive solvents and other additives.

Some specific embodiments of the invention are set forth in the following examples.

Example 1

K 6 wt. 220 g of ethylene glycol, 270 g of propylene glycol, 250 g of trimethylolpropanially ether, 220 g of phthalic anhydride and 550 g of maleic anhydride having an acid number of 3? mg KOH / g and a molecular weight of 850 were added 4 wt. parts of styrene. 54 wt. parts of epoxyacrylate oligoester of molecular weight 420 prepared by the addition reaction of a dian epoxy resin and acrylic acid and 36 wt. parts of styrene.

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2 wt. parts of photoinitiator and 0.5 wt. % of colloidal silica. The prepared composition can be used as a coating for wood surface treatment. It is cured by UV-radiation (high-pressure discharge lamp with an output of 80 W / cm) and the cured coating exhibits the following properties:

flexural strength 110 MPa E-module 3 200 MPa impact bending strength 0.65 J / cm -1 resistance to temperature changes 25

Example 2

K 36 wt. 54 parts by weight of the unsaturated polyester prepared according to Example 1 were added. parts by weight of styrene and 4 wt. parts by weight of epoxyacrylate oligoster according to Examples 1 and 5 wt. parts of styrene and 1 wt. part of methyl methacrylate. After homogenization, the composition is cured with 3 wt.% Methylcyclohexanone peroxide and 0.5 wt. % cobalt naphthenate dissolved in toluene, with a metal content of 4% by weight The cured composition exhibits the following properties:

MPa 2,800 MPa 0.95 J / cm ² yield strength, flexural modulus E-modulus impact strength flexural stability

Example 3

K 10 wt. 40 parts by weight of an unsaturated polyester based on trimethylolpropanially ether having a molecular weight of 1850 and an acid number of 25 mg KOH / g are added. parts of styrene. 10 wt. parts by weight of 2,400 epoxyacrylate oligoester prepared by reacting a diane epoxy resin with raethacrylic acid and 35 parts by weight of styrene and 5 parts by weight; parts of ethylene glycol diacrylate. 3 wt.

233 095 photoinitiator parts, 1 wt. 2 parts by weight of colloidal silica; parts of isopropyl alcohol. The composition is used as a gloss primer cured by pulsed UV radiation. The cured coating has the following characteristics:

pendulum hardness / 23 ° C pencil hardness no.

- 55% 7-8 temperatures 25 cycles

180

Example 4

K 15 wt. 35 parts by weight of the unsaturated polyester based on trimethylolpropane monoallyl ether having a molecular weight of 1200 and an acid number of 30 mg KOH / g are added. parts of styrene. 15 wt. 900 parts by weight of the epoxyacrylate oligoester 0, prepared by polyaddition reaction of a diane epoxy resin with a 1: 1 mixture of acrylic acid and methacrylic acid in a weight ratio of 1: 1 and 35 wt. parts of styrene. Further, 2 wt. % photoinitiator, 10 wt. % ethyl acetate, 3 wt. a zinc stearate matting agent. The prepared composition is used as a matting lacquer for a UV-curing primer (from Example 3). The cured coating film exhibits the following characteristics:

pendulum hardness / 23 ° C 60 - 65% pencil hardness No. 8 gloss% 40

Ί

233 095

SUBJECT OF THE INVENTION

Claims (1)

Curable compositions based on unsaturated resins of synthetic _t-reactive monomers, and optionally additives, characterized in that they consist of 20 to 60 wt. parts of unsaturated synthetic resins containing 10 to 90% by weight of unsaturated polyester having a molecular weight of 700 to 2 000 _t obtained by the polycondensation reaction of (1,2-unsaturated dicarboxylic acids or their derivatives, optionally in admixture) with compounds of the ortho- , iso- and terephthalic acids, aliphatic acids and / or derivatives thereof with polyhydric alcohols and?, -ethylenically unsaturated ether alcohols and 90 to 10% by weight of oligoesters having a molecular weight of 400 to 2 500 based on acrylic and / or methacrylic esters of bisphenolic epoxy resins from 40 to 80 parts by weight of reactive monomers from the group comprising styrene and its methyl derivatives, alkyl esters of acrylic and methacrylic acids with a carbon number of atoms in the alkyl group of 1 to 8; up to 15 wt. parts of additives from the group of reactive «tive solvents, thixotropic agents, photo © initiator, and curing accelerators and dulling agents ·