KR20000022560A - Process for curing a polymerizable composition - Google Patents

Abstract

PURPOSE: A process for curing a polymerizable composition is provided to obtain coatings having good surface properties by combining thermal and UV curing. CONSTITUTION: Using compositions comprising (A) a coating system based on a polyacrylatepolyol or polyester polyol with melamine, or a polyacrylate polyol and/or polyester polyol with a blocked or unblocked polyisocyanate, or a carboxyl-, anhydride- or amino-functional polyester and/or polyacrylate with an epoxy-functional polyester or polyacrylate, (B) an OH-, NH2-, COOH-, epoxy- or NCO-functional resin containing, in addition, at least one ethylenically unsaturated double bond, which is separated from the functional group by a spacer group, and (C) at least one photoinitiator.

Description

Method for Curing the Polymerizable Composition

The present invention relates to a method and polymerizable composition in which the surface hardness of the cured surface coating is increased by irradiation of UV rays by curing the surface coating.

US Pat. No. 4,121,985 describes that the resistance of a thermoplastic polyurethane surface to solvent and abrasion is improved by treating the surface with a mixture of solvent and photoinitiator and then irradiating UV light. Derwent No. 94-252879 / 31 (Japanese Patent Laid-Open No. 6-184267) discloses a polyol mixture containing a chlorinated polyol and a polyol having a COOH group, a polyisocyanate and an unsaturated monohydroxy compound. And suitably, polyurethane resins obtained by reacting with photoinitiators are described. German Patent Publication No. 42 38 695 claims a surface coating composition which contains a functionalized resin having an α, β-unsaturated group and is heat cured. Derwent 87-331357 (Japanese Patent Laid-Open No. 62-236867) describes a curing step in which thermal curing and photochemical curing are combined. Derwent 85-188037 (JP-A-60-118271) describes a combined heat and UV curable composition. EP-A-600 262 claims photoresist compositions containing heat and UV curable components. In JP 33 32 004 and 247 563, UV curable surface systems comprising epoxide / amine based resins or polyol / isocyanate based resins have been prepared.

In the art, there is a need for coating and surface coating resins that exhibit excellent properties, particularly with regard to the durability of hardened surfaces.

Surprisingly, coatings with very good surface properties,

Polyacrylate polyols and / or polyester polyols (I) with melamine, polyacrylate polyols and / or polyester polyols (II) with blocked or unblocked polyisocyanates, epoxy-functional polyesters or polyacrylates Coatings based on carboxyl-, anhydride- or amino-functional polyesters and / or polyacrylates (III) or mixtures of (I), (II) (III) and / or (IV) System (A),

OH-, NH _2- , COOH-, epoxy- or NCO-functional resins containing one or more ethylenically unsaturated double bonds (B) {A spacer group of four or more linear linking atoms is formed between a double bond and a functional group. Need to be present}, wherein component (A) and component (B) contain no halogen] and

Obtainable by a method of curing the polymerizable composition by heat treating the polymerizable composition comprising at least one photoinitiator (C), followed by photochemical treatment with a light having a wavelength of 200 to 600 nm for the purpose of improving the surface properties. Turned out.

In addition, the present invention

Polyacrylate polyols and / or polyester polyols (I) with melamine, polyacrylate polyols and / or polyester polyols (II) with blocked or unblocked polyisocyanates, epoxy-functional polyesters or polyacrylates Coatings based on carboxyl-, anhydride- or amino-functional polyesters and / or polyacrylates (III) or mixtures of (I), (II) (III) and / or (IV) System (A),

OH-, NH _2- , COOH-, epoxy- or NCO-functional resins containing one or more ethylenically unsaturated double bonds (B) {A spacer group of four or more linear linking atoms is formed between a double bond and a functional group. Need to be present}, wherein component (A) and component (B) contain no halogen] and

A composition comprising at least one photoinitiator (C).

The component of component (A) is, for example, a surface coating component or coating system component conventional in the art.

The component of component (A) is, for example, a polymer derived from an α, β-unsaturated acid or derivative thereof. Examples are polyacrylates, polymethacrylates, polymethylmethacrylates, polyacrylamides and polyacrylonitriles that are impact resistant modified with butyl acrylate. Also important is silicone acrylate, for example. Further components of component (A) are polyurethanes derived on the one hand from polyethers, polyesters and polyacrylates having free hydroxy groups and on the other hand from aliphatic polyisocyanates, aromatic polyisocyanates or their precursors. Can be. In addition, the components of component (A) include, for example, crosslinkable acrylic resins derived from substituted acrylic esters such as epoxy acrylates, urethane acrylates or polyester acrylates. Furthermore, melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates, alkyd resins, polyester resins, acrylate resins and modified products thereof crosslinked with epoxy resins are also components of component (A). Can be.

Component (A) is, for example, a film-forming binder which is generally based on a thermoplastic or thermosetting resin, but is mainly based on a thermosetting resin. Examples thereof are alkyds, acrylics, polyesters, phenols, melamines, epoxies, polyurethane resins and mixtures thereof. Examples of these are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, PP. 368-426, VCH, Weinheim 1991.

Component (A) may be a cold or thermoset binder, possibly adding a curing catalyst. Suitable catalysts that promote sufficient curing of the binder are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, p. 469, VCH Verlagsgesellschaft, Weinheim 1991.

Examples of coatings (A) using specific binders are as follows:

1.Surface coatings based on cold-crosslinkable or thermally crosslinkable alkyds, acrylates, polyesters, epoxies, melamine resins or mixtures of such resins (optionally adding a curing catalyst),

2. two-component polyurethane surface coatings based on hydroxy group containing acrylates, polyesters or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates,

3. One-component polyurethane surface coatings based on blocked isocyanates, isocyanurates or polyisocyanates which may be deblocked during stoving (may optionally add melamine resins),

4. one-component polyurethane surface coatings based on aliphatic or aromatic urethanes or polyurethanes and hydroxy group-containing acrylates, polyesters or polyester resins,

5. One-component polyurethane surface coatings based on aliphatic or aromatic urethane acrylates or polyurethane acrylates and melamine resins or polyether resins with free amine groups in the urethane structure (optionally adding a curing catalyst),

6. two-component surface coatings based on (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates,

7. two-component surface coatings based on (poly) ketimines and unsaturated acrylate resins or polyacetoacetate resins or methacrylamidoglycolate methyl esters,

8. two-component surface coatings based on carboxyl or amino group-containing polyacrylates and polyepoxides,

9. two-component surface coatings based on anhydrous group-containing acrylate resins and polyhydroxy or polyamino components,

10. two-component surface coatings based on acrylate-containing anhydrides and polyepoxides,

11. two-component surface coatings based on (poly) oxazolines and anhydrous group-containing acrylate resins, unsaturated acrylate resins, aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates,

12. two-component surface coatings based on unsaturated polyacrylates and polymalonates,

13. Thermoplastic polyacrylate surface coatings based on thermoplastic acrylate resins or native crosslinking acrylate resins in combination with etherified melamine resins, and

14. Surface coating system based on siloxane modified acrylate resin.

Blocked isocyanates that can be used in component (A) are described, for example, in Organischer Metallschutz: Entwicklung und Anwendung von Beschichtungsstoffen, pp. 159-160, Vincentz Verlag, Hannover (1993). Such compounds are compounds in which highly reactive NCO groups are "blocked" by reaction with certain radicals such as primary alcohols, phenols, ethyl acetoacetate, ε-caprolactam, phthalimide, imidazole, oxime and amines. to be. Blocked isocyanates are stable in liquid systems and also stable in the presence of hydroxy groups. Upon heating, the blocking agent is removed again and the NCO group is liberated.

Monocomponent (1C) and bicomponent (2C) systems are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, Paints and Coatings, pp. 404-407, VCH Verlagsgesellschaft mbH, Weinheim (1991).

For example, it is possible to optimize the composition by varying the binder / crosslinker ratio to make the formulation particularly suitable. Those skilled in the surface coating art will be well aware of this means.

In the curing process according to the invention, the composition is preferably a composition based on acrylate / melamine, bicomponent polyurethane, monocomponent polyurethane, bicomponent epoxy or monocomponent epoxy / carboxy. Also possible is a mixture of such systems, for example, by adding melamine to the monocomponent polyurethane.

Component (A) is preferably a polyacrylate-based binder containing melamine. Also preferred are systems based on polyacrylate polyols and / or polyester polyols having unblocked polyisocyanates.

Component (B) is monomeric and / or oligomeric with ethylenically unsaturated bonds containing one or more OH, NH ₂ , COOH, epoxy or NCO groups capable of reacting with the binder and / or crosslinker of component (A) It consists essentially of the compound (prepolymer). After coating and heat curing, the ethylenically unsaturated bonds are converted to crosslinked high molecular weight forms by UV radiation. Examples of component (B) are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pp. 451-453 or S. Urano, K. Aoki, N. Tsuboniva and R. Mizuguchi in Progress in Organic Coatings, 20 (1992), 471-468 or H. Tershima and O. Isozaki in JOCCA 1992 ( 6), 222. (B) is OH group containing unsaturated acrylate (for example, hydroxyethyl acrylate, hydroxybutyl acrylate, or glycidyl acrylate). Component (B) may have a specific desired structure (for example, it may contain units such as polyesters, polyacrylates, polyethers, etc.), provided that ethylenically unsaturated double bonds and additionally free OH, COOH, NH 2, epoxy or NCO groups.

(B) can also be obtained, for example, by reacting an epoxy functional oligomer with acrylic acid or methacrylic acid.

Typical examples of OH functional oligomers having vinyl double bonds include CH ₂ = CHCOOH. Obtained by reaction with to be.

A further possible method of preparing component (B) is, for example, the reaction of oligomers containing only one epoxy group and having free OH groups at different positions in the molecule.

Also suitable as component (B) are, for example, siloxane group-containing polymers containing free double bonds and further OH groups. These polymers can be obtained, for example, by reacting epoxy functional polysiloxanes with acrylic acid, methacrylic acid or derivatives thereof, examples of which are CH ₂ = CHCOO-CH ₂ CH (OH) CH ₂ O- (CH ₂ ) _m- [Si (CH ₃ ) ₂ -O] n-Si (CH ₃ ) _2- (CH ₂ ) m-OCH ₂ CH (OH) CH ₂ OC (O) CH = CH ₂ . Such products are commercially available.

Suitable spacer groups of four or more linear linking atoms located between the double bond and the functional group in component (B) are, for example, in the following structure:

-(CH ₂ ) _y- (where y is 4 or more), (Where y is 2 or more) or Where x is 1 to 3 and y is 2 or more. Is preferred. The number of spacer atoms is at least 4, for example 4 to 16, 6 to 16, preferably 4 to 12.

The composition contains, for example, 1 to 50% (for example 5 to 30%), in particular 10 to 25%, of component (B), based on 100 parts of component (A).

According to the invention, certain known compounds which can initiate radical polymerization when irradiated with light can be used as photoinitiators (C).

Examples of this are:

Benzophenones, benzophenone derivatives, acetophenones, acetophenone derivatives such as 1-hydroxy-cyclohexyl-phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy 2-methyl-1-propane-1-one or 2-hydroxy-2-methyl-1-phenyl-propane, dialkoxyacetophenone, α-hydroxy-acetophenone, α-amino-acetophenone, eg For example, (4-morpholino-benzoyl) -1-benzyl-1-dimethylamino-propane or (4-methylthiobenzoyl) -1-methyl-1-morpholino-ethane, 4-aroyl-1 , 3-dioxolane, benzoin alkyl ether and benzyl ketal, for example 2,2-dimethoxy-1,2-diphenylethan-1-one, monoacylphosphine oxide, for example 2,4 , 6-trimethylbenzoyl-diphenylphosphine oxide, bisacylphosphine oxide, for example bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide, bis (2, 4,6-trimethylbenzoyl)-(2-methylprop-1-yl) -phosphine oxa Id, bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide and trisacylphosphine oxide. In some cases, a mixture of two or more photoinitiators, for example bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide or bis (2,4,6-trimethylbenzoyl ) -Phenyl-phosphine oxide with 1-hydroxycyclohexyl-phenyl ketone or hydroxy-2-methyl-1-phenyl-propane or 2-methoxy-1-phenyl-ethane-1,2-dione It may be advantageous to use mixtures of.

Component (C) is preferably a compound of formula I, a compound of formula Ia, a compound of formula Ib, a compound of formula II or a compound of formula III, or a compound of formula I, a compound of formula Ia, a compound of formula Ib or a formula Mixture of a compound of Formula II and a compound of Formula III.

In Formula I above,

R ₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, —OCH ₂ CH ₂ —OR ₅ , group Or group Where I is an integer from 2 to 10 and A is a radical )

R ₂ and R ₃ independently of one another are hydrogen, C ₁ -C ₆ alkyl, phenyl, C ₁ -C ₁₆ alkoxy, OSiR ₆ R ₇ R ₈ or —O (CH ₂ CH ₂ O) _q -C ₁ -C ₁₆ Alkyl, where q is 1 to 20, or R ₂ and R ₃ together with the carbon atom to which they are attached form a cyclohexyl ring,

R ₄ is hydroxy, C ₁ -C ₁₆ alkoxy or —O (CH ₂ CH ₂ O) _q -C ₁ -C ₁₆ alkyl,

Provided that R ₂ , R ₃ and R ₄ are not all C ₁ -C ₁₆ alkoxy or —O (CH ₂ CH ₂ O) _q- C ₁ -C ₁₆ alkyl at the same time,

R ₅ is hydrogen, C ₁ -C ₈ alkyl, , or ,

R ₆ , R ₇ and R ₈ are each, independently of one another, C ₁ -C ₄ alkyl or phenyl.

In Formula Ia above,

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently of each other hydrogen, methyl, phenyl, methoxy, -COOH, unsubstituted or C ₁ -C ₄ alkyl substituted phenyl, or a group -OCH ₂ CH ₂ OR ₅ Or —SCH ₂ CH ₂ OR ₅ , wherein R ₅ is as defined in formula (I).

In Formula Ib above,

R ₁₃ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, halogen or group N (R ₁₇ ) ₂ ,

R ₁₄ is one of those defined for R ₁₃ , or a group And (where a radical R ₁₃ is a direct bond together, other radicals are as defined under which the radical R ₁₃ from the group of the art from the formula Ib),

R ₁₅ is C ₁ -C ₈ alkyl,

R ₁₆ is hydrogen, —CH═CHR ₂₀ , or phenyl unsubstituted or trisubstituted with C ₁ -C ₁₂ alkyl, C ₁ -C ₄ alkoxy or halogen,

R ₁₅ and R ₁₆ together with the carbon atoms to which they are attached form a cyclohexyl ring,

R ₁₇ and R ₁₈ are each independently of the other C ₁ -C ₄ alkyl, or

R ₁₇ and R ₁₈ together with the nitrogen atom to which they are attached form a 5 or 6 membered saturated or unsaturated ring which may be blocked with -O-, -NH- or -N (CH ₃ )-,

R ₁₉ is hydrogen or C ₁ -C ₁₂ alkyl,

R ₂₀ is hydrogen or C ₁ -C ₄ alkyl.

In Formula II above,

R ₂₁ is a 5 or 6 membered heterocyclic ring or group containing naphthyl, anthracyl, O or S ego,

R ₂₂ is C ₁ -C ₁₂ alkyl, cyclohexyl, cyclopentyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl; Phenyl, biphenyl or naphthyl, monosubstituted or tetrasubstituted, each unsubstituted or substituted with C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy; C ₂ -C ₁₈ alkyl blocked one or more times with —O—; Or Si (R ₂₈ ) (R ₂₉ ) (R ₃₀ ),

R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ are each independently hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, phenyloxy, phenylthio, substituted Phenyl unsubstituted or tetrasubstituted with C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy, phenyl-C ₁ -C ₄ alkyl, halogen or NO ₂ ,

R ₂₈ , R ₂₉ and R ₃₀ are each independently of each other C ₁ -C ₈ alkyl, cyclohexyl, cyclopentyl, phenyl or C ₁ -C ₈ alkoxy.

In Formula III above,

Z is S or O,

R ₃₁ and R ₃₂ are each independently of each other C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkyl blocked one or more times with -O-, phenyl substituted C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl ; Phenyl, naphthyl or biphenyl, unsubstituted or mono-substituted or substituted with halogen, hydroxy, C ₁ -C ₈ alkyl and / or C ₁ -C ₈ alkoxy, respectively; A 5 or 6 membered heterocyclic ring containing C ₅ -C ₁₂ cycloalkyl, O, S or N, or a group COR _33, or

R ₃₁ is a radical , , OH, OR _34, O ^- NH ₄ ⁺ or _{^{O - [Mn +] 1 /}} n ( where a, n is an integer from 1 to 3, M n is the valence of metal ion), or

R ₃₁ and R ₃₂ together are C ₄ -C ₇ alkylene and together with the P atom to which they are attached form a ring,

R ₃₃ is C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₈ alkenyl; Phenyl, naphthyl or biphenyl, monosubstituted or tetrasubstituted, each unsubstituted or substituted with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio and / or halogen; 5 or 6 membered heterocyclic ring containing O, S or N, or a group ego;

R ₃₄ is C ₁ -C ₈ alkyl, phenyl, naphthyl, C ₁ -C ₈ alkylphenyl or C ₁ -C ₄ alkylnaphthyl,

Y is phenylene, C ₁ -C ₁₂ alkylene or C ₅ -C ₆ cycloalkylene,

X is C ₁ -C _{18 alkylene, -O-, -S-, -NR 35 -} , P (O) R 36 - or -SO ₂ - 1 times or more the block C ₂ -C ₁₈ alkylene, or a Cl, F, C ₁ -C ₄ alkoxy, COOR ₃₇ , phenyl, phenyl-C ₁ -C ₄ alkyl, naphthyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C ₁ -C ₄ alkylnaph C ₁ -C ₆ alkylene substituted by butyl, phenyl-C ₁ -C ₄ alkoxy, naphthyl-C ₁ -C ₄ alkoxy and / or CN;

X is C ₁ -C ₈ alkylene substituted with one or two radicals of formula A, or

X is a group of formula A1 to A9, or

In the above formulas A1 to A9,

a and b are each independently 0 or 1,

The sum of d and f is an integer of 3 to 8, provided that neither d nor f is zero.

X is a group -CH ₂ -CH = CH-CH ₂ -or -CH ₂ -C≡C-CH _2- , or

X is phenylene, xylene, mono- or trisubstituted, each unsubstituted or substituted with Cl, F, C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy, or Or

X is phenylene which is mono- or trisubstituted by one or two groups (A) and further substituted with Cl, F, C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy, or

X is a group of formulas A10 to A13.

In the above formulas A10 to A13,

Q is a single bond, CR ₃₉ R ₄₀ , -O-, -S-, -NR _35- , -SO ₂ -,-(CH ₂ ) _p -or -CH = CH-,

p is an integer from 2 to 12,

Z is O or S,

R ₃₅ is hydrogen, C ₁ -C ₁₂ alkyl or phenyl,

R ₃₆ is C ₁ -C ₄ alkyl or phenyl,

R ₃₇ is C ₁ -C ₁₂ alkyl, C ₂ -C ₁₈ alkyl blocked at least once with -O-, benzyl, phenyl, cyclophenyl or cyclohexyl,

R ₃₈ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen,

R ₃₉ is hydrogen, methyl or ethyl,

R ₄₀ is hydrogen or C ₁ -C ₄ alkyl.

C ₁ -C ₂₀ alkyl is straight or branched, for example C ₁ -C ₁₈ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₈ alkyl, C ₁ -C ₆ alkyl or C ₁ -C ₄ alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, Decyl, undecyl, dodecyl, tetradecyl, heptadecyl, octadecyl and isoyl. C ₁ -C ₁₈ alkyl, C ₁ -C ₁₂ alkyl, C ₁ -C ₈ alkyl and C ₁ -C ₄ alkyl are as defined above with suitable carbon numbers or less.

C ₂ -C ₁₈ alkyl blocked one or more times with —O— or —S— is blocked 1 to 5 times (eg, 1 to 3 times or 1 or 2 times), eg, with —O—, eg For example, -S (CH ₂ ) ₂ OH-, -O (CH ₂ ) ₂ OH, -O (CH ₂ ) ₂ OCH ₃ , -O (CH ₂ CH ₂ O) ₂ CH ₂ CH ₃ , -CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ ,-[CH ₂ CH ₂ O] _y -CH ₃ (where y is 1 to 5),-(CH ₂ CH ₂ O) To form structural units such as ₅ CH ₂ CH ₃ , -CH ₂ -CH (CH ₃ ) -O-CH ₂ -CH ₂ CH _3, and -CH ₂ -CH (CH ₃ ) -O-CH ₂ -CH ₃ . .

C ₃ -C ₁₂ cycloalkyl is, for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl. C ₅ -C ₁₂ cycloalkyl is, for example, cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl. Cyclopentyl and cyclohexyl are preferred, and cyclohexyl is particularly preferred.

C ₁ -C ₁₈ alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secondary butoxy, t-butoxy, pentyloxy, hexyloxy , Heptyloxy, decyloxy or dodecyloxy, for example C ₁ -C ₁₂ alkoxy, C ₁ -C ₈ alkoxy, preferably C ₁ -C ₄ alkoxy, in particular methoxy. C ₁ -C ₈ alkoxy is as defined above with no more than suitable carbon atoms.

C ₁ -C ₁₂ alkylthio is straight or branched chain, for example methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, isobutyl thido, secondary butylthio, t-butyl Thio, pentylthio, hexylthio, heptylthio, decylthio or dodecylthio, for example C ₁ -C ₈ alkylthio, preferably C ₁ -C ₄ alkylthio, in particular methylthio.

5 or 6 membered heterocyclic rings containing O or S are, for example, furyl, thienyl, oxynyl or dioxyyl.

5 or 6 membered heterocyclic rings containing O, S or N are, for example, furyl, thienyl, pyrrolyl, pyridyl, oxynyl or dioxyyl.

C ₁ -C ₁₂ alkenyl is for example allyl, metallyl, 1,1-dimethylallyl, butenyl, hexenyl, octenyl or dodecenyl, for example C ₂ -C ₈ alkenyl or C ₂ -C ₄ alkenyl, especially allyl. C ₂ -C ₄ alkenyl is, for example, allyl, metallyl, 1,1-dimethylallyl or butenyl.

The radical —O (CH ₂ CH ₂ O) _q —C ₁ -C ₁₆ alkyl represents 1 to 20 consecutive ethylene oxide units, the chain of which terminates with C ₁ -C ₁₆ alkyl. q is preferably 1 to 10, for example 1 to 8, in particular 1 to 6. The chain of ethylene oxide units is preferably terminated with C ₁ -C ₁₀ alkyl, for example terminated with C ₁ -C ₈ alkyl, in particular C ₁ -C ₄ alkyl.

Phenyl-C ₁ -C ₄ alkyl is, for example, benzyl, phenylethyl, α-methylbenzyl or α, α-dimethylbenzyl, in particular benzyl.

Substituted phenyl, naphthyl or biphenyl are mono- to 5-substituted, for example mono- to tetra-substituted, for example mono-, di- or tri-substituted, especially di- or tri-substituted.

R ₃₁ , R ₃₂ and R ₃₃ as substituted phenyl, naphthyl or biphenyl are, for example, straight or branched C ₁ -C ₈ alkyl (eg methyl, ethyl, n-propyl, isopropyl, n-butyl , Isobutyl, secondary butyl, t-butyl, pentyl, hexyl, heptyl or octyl), or straight or branched C ₁ -C ₈ alkoxy (e.g. methoxy, ethoxy, n-propoxy, isopropoxy, substituted or substituted with n-butoxy, isobutoxy, secondary butoxy, t-butoxy, hexyloxy or octyloxy, straight or branched C ₁ -C ₈ alkylthio (e.g. methylthio, ethylthio, n-propyl Thio, isopropylthio, n-butylthio, isobutylthio, secondary butylthio, t-butylthio, pentylthio or hexylthio) or halogen (eg fluorine, chlorine, bromine or iodine). Preferred substituents of the phenyl, naphthyl, and biphenyl as R _31, R ₃₂ and R ₃₃ is a C ₁ -C ₄ alkyl, especially methyl, C ₁ -C ₄ alkoxy, teuksi methoxy and chlorine. In particular, R ₃₁ , R ₃₂ and R ₃₃ are, for example, 2,4,6-trimethylphenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl or 2,6-dimethoxyphenyl.

Examples of n valent metals (n is 1 to 30) are Na, Li, K, Mg, Ca, Ba, Fe, Co and Al.

When R ₃₁ and R ₃₂ are C ₄ -C ₇ alkylene and form a ring together with the P atom to which they are bonded, the ring (including P atom) is preferably 5-6 membered.

C ₁ -C ₈ alkylphenyl is, for example, C ₁ -C ₄ alkylphenyl, for example tolyl, xylyl, mesityl, ethylphenyl or diethylphenyl, preferably tolyl or mesityl. C ₁ -C ₄ alkylnaphthyl is naphthyl substituted with methyl, ethyl and / or propyl or butyl.

C ₁ -C ₁₈ alkylene and C ₁ -C ₁₂ alkylene are linear or branched alkylenes, for example methylene, ethylene, propylene, isopropylene, n-butylene, secondary butylene, isobutylene, t- Butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tetradecylene, heptadecylene or octadecylene. X and Y are each in particular C ₁ -C ₁₂ alkylene, for example ethylene, decylene, —CH (C ₁₁ H ₂₃ ) —, —CH (CH ₃ ) —CH ₂ —, —CH (CH ₃ ) -(CH ₂ ) _2- , -CH (CH ₃ )-(CH ₂ ) ₃ -,-(CH ₃ ) ₂ -CH ₂ -or to be.

When X is C ₂ -C ₈ alkylene blocked with —O—, —S—, —NR ₃₅ —, —P (O) R ₃₆ — or —SO ₂ —, for example, —CH ₂ —O -CH _2- , -CH ₂ CH ₂ -O-CH ₂ CH ₂ -,-[CH ₂ CH ₂ O] y- (where y is 1 to 9),-(CH ₂ CH ₂ O) ₇ CH ₂ CH _2- , -CH ₂ -CH (CH ₃ ) -O-CH ₂ -CH (CH ₃ )-, -CH ₂ -S-CH _2- , -CH ₂ CH ₂ -S-CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ -S-CH ₂ CH ₂ CH ₂ -,-(CH ₂ ) ₃ -S- (CH ₂ ) ₃ -S- (CH ₂ ) _3- , -CH _2- (NR ₃₅ ) -CH _2- , -CH ₂ CH _2- (NR ₃₅ ) -CH ₂ CH _2- , -CH _2- (P (O) R ₃₆ ) -CH _2- , -CH ₂ CH _2- (P (O ) R ₃₆ ) -CH ₂ CH _2- , , , -CH ₂ -SO ₂ -CH _2-, and -CH ₂ CH ₂ -SO ₂ -CH ₂ CH ₂ -and the like are obtained.

C ₁ -C ₄ alkoxy substituents are, for example, methoxy, ethoxy, propoxy and butoxy, in particular methoxy. A C ₁ -C ₆ alkylene substituted by C ₁ -C ₄ alkoxy, or -COOR ₃₇ is, for example, -CH (OCH ₃₎ - or -CH (COOCH ₃₎ -CH ₂ - a.

C ₁ -C ₄ alkylphenyl is, for example, tolyl, xylyl, mesityl, ethylphenyl or diethylphenyl, preferably tolyl or mesityl.

C ₁ -C ₄ alkylnaphthyl is naphthyl substituted with methyl, ethyl and / or propyl or butyl.

Phenyl-C ₁ -C ₄ alkyl is, for example, benzyl, phenylethyl, α-methylbenzyl or α, α-dimethylbenzyl, in particular benzyl.

Naphthyl-C ₁ -C ₄ alkyl is, for example, naphthylmethyl, naphthylethyl, naphthyl- (1-methyl) -eth-1-yl or naphthyl- (1,1-dimethyl) eth- 1-yl, in particular naphthylmethyl.

Phenyl-C ₁ -C ₄ alkoxy can be understood as, for example, benzyloxy, phenylethyloxy, α-methylbenzyloxy or α, α-dimethylbenzyloxy, in particular benzyloxy.

Naphthyl-C ₁ -C ₄ alkoxy is, for example, naphthylmethyloxy or naphthylethyloxy.

Examples of the group A1 are as follows:

d + f = 3 , , d + f = 4 , And d + f = 6 (Where the sum of d and f is 3 to 8). , And Is preferred.

Examples of the groups A2, A3, A4, A5, A6, A7, A8 and A9 , , And to be. Examples of the group A10 , , And to be.

Examples of unsubstituted phenylene and xylylene and substituted phenylene and xylylene are , , , , , And to be.

Processes for the preparation of compounds of formula (I) and formula (I ') are generally known and some of these compounds are commercially available. Methods for preparing oligomeric compounds of formula (I) are described, for example, in EP 161 463. Processes for the preparation of compounds of formula (Ia) can be found, for example, in EP-209-831.

Processes for the preparation of compounds of formula (Ib) are described, for example, in EP 284 561. Compounds of formula III are prepared, for example, by the method described in EP 184 095.

Some compounds of formulas Ib, II and III are also commercially available.

R ₁ is hydrogen, C ₁ -C ₁₂ alkyl or —OCH ₂ CH ₂ —OR ₅ , and R ₂ and R ₃ are each independently of each other C ₁ -C ₆ alkyl, phenyl or C ₁ -C ₁₆ alkoxy, or R ₂ and R ₃ together with the carbon atom to which they are attached form a cyclohexyl ring, R ₄ is hydroxy or C ₁ -C ₁₆ alkoxy and R ₅ is hydrogen or A compound of formula (I) wherein R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are hydrogen,

R ₁₃ is hydrogen, R ₁₄ is C ₁ -C ₄ alkylthio or N (R ₁₇ R ₁₈ ), R ₁₅ is C ₁ -C ₈ alkyl, R ₁₆ is phenyl, and R ₁₇ and R ₁₈ are each A compound of formula (Ib) wherein, independently of _one another, C ₁ -C ₄ alkyl, or R ₁₇ and R ₁₈ together with the nitrogen atom to which they are attached, form a saturated six-membered ring which may be blocked with -O-, R ₂₁ is phenyl Is a compound of Formula II wherein R ₂₂ is C ₁ -C ₁₂ alkyl, Z is O, and R ₃₁ and R ₃₂ are each independently of each other C ₁ -C ₁₈ alkyl, unsubstituted or C ₁ -C ₈ alkyl, and / Or phenyl mono- or substituted-substituted with C ₁ -C ₈ alkoxy, or a group COR ₃₃ and R ₃₃ is unsubstituted or mono- or tetra-substituted phenyl with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy Preferred are the compounds of III.

Preferably, in formula (I), R ₂ and R ₃ are each independently of each other C ₁ -C ₆ alkyl or together with the carbon atom to which they are attached form a cyclohexyl ring, and R ₄ is hydroxy.

More particularly, in formula (I) R ₂ and R ₃ are the same and each is methyl and R ₄ is hydroxy or isopropoxy.

In formula (Ia), R ₉ to R ₁₂ are preferably hydrogen.

Preferably, in formula (Ib) R ₁₆ is phenyl or -CH = CHR ₂₀ , R ₁₄ is C ₁ -C ₄ alkylthio or N (R ₁₇ ) ₂ , and R ₁₅ , R ₁₇ and R ₁₈ are C _1- C ₄ alkyl.

In formula (II), R ₂₁ is preferably phenyl and R ₂₂ is C ₁ -C ₄ alkyl.

Preferably, in formula (III), R ₃₁ is COR ₃₃ wherein R ₃₃ is mono- or tetrasubstituted phenyl with C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and / or halogen, and R ₃₂ is Mono- or missubstituted C ₁ -C ₁₂ alkyl, unsubstituted phenyl, or C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy.

Furthermore, preferably in formula III R ₃₁ and R ₃₂ are phenyl and R ₃₃ is phenyl mono- to trisubstituted with C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy.

Z is preferably O.

Examples of component (C) include 1-hydroxycyclohexyl-phenyl ketone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one or 2 -Hydroxy-2-methyl-1-phenyl-propane, (4-morpholino-benzoyl) -1-benzyl-1-dimethylamino-propane or (4-methylthiobenzoyl) -1-methyl-1- Morpholino-ethane, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl ) -2,4,4-trimethylpentyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl)-(2-methylprop-1-yl) -phosphine oxide, bis (2,4,6 -Trimethylbenzoyl) -phenyl-phosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide with 1-hydroxycyclohexyl-phenyl ketone, hydroxy- Mixture with 2-methyl-1-phenyl-propaneone or 2-methoxy-1-phenyl-ethane-1,2-dione, or bis (2,4,6-trimethylbenzoyl) -phenyl-fo A mixture of fin oxide with 1-hydroxy-cyclohexyl-phenyl ketone, hydroxy-2-methyl-1-phenyl-propanone or 2-methoxy-1-phenyl-ethane-1,2-dione, or 2 , 4,6-trimethylbenzoyl-diphenyl-phosphine oxide with 1-hydroxycyclohexyl-phenyl ketone, hydroxy-2-methyl-1-phenyl-propanone or 2-methoxy-1-phenyl-ethane Particular preference is given to mixtures with -1,2-dione.

The photopolymerizable composition advantageously contains a photoinitiator (C) in an amount of 0.05 to 20% by weight, preferably 2 to 10% by weight, based on 100 parts of component (A).

When the photoinitiator (C) is a compound of formula I, a compound of formula Ia, a compound of formula Ib or a compound of formula II with a compound of formula III, the compound of formula I, the compound of formula Ia, the compound of formula Ib or The proportion of the compound is, for example, 25 to 90% (eg 25 to 75%), preferably 50 to 75%.

Polyester polyols, acrylate polyols or hexamethoxymethylmelamine (A), isocyanurate or OH-functionalized acrylates (B) and 1-hydroxy-cyclohexyl-phenyl ketone, or 25% bis (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide with 75% 1-hydroxycyclohexyl-phenyl ketone or 4-[(2-hydroxyethoxy) -benzoyl] -1 Preferred is a composition comprising -hydroxy-1-methyl-ethane (C).

OH-, NH _2- , COOH-, epoxy- or NCO-functionalized component (B) and photoinitiator further containing free double bonds separated from functional groups by space groups of four or more linear linking atoms ( Including C) is a feature of the composition. According to the method according to the invention, by further crosslinking the surface coating irradiated with light after thermal curing by adding these components, the surface coating improves surface properties, in particular hardness and resistance to scratching.

Surface coatings according to the invention may comprise organic solvents or solvent mixtures in which the binder and / or crosslinker are water soluble or dispersible. However, the composition may be an aqueous solution or a dispersion. Also, for example, one of the two components may act as a dispersion medium or dissolution medium for the other components. The excipient may be a mixture of an organic solvent and water. The coating may be a high solid surface coating or may be a solvent free surface coating (eg a powder coating composition).

The composition according to the invention is prepared by mixing all the components. For example, through this functional group, only OH-, NH _2- , COOH-, epoxy- or NCO-functionalized component (B) is combined with component (A) or components thereof, and then all other components. It can also be mixed with

The composition according to the invention can be coated on a desired substrate, for example a metal, wood, plastic or ceramic material. They are preferably used as finishing lacquers for surface coating of automobiles. If the finishing lacquer consists of two layers, a colored bottom layer and an uncolored top layer, the coating according to the invention can be used for the top layer or the bottom layer or both, but it is preferred to use it as the top layer.

The composition according to the invention can be coated on a substrate according to conventional procedures (eg painting, spraying, pouring, impregnation or electrophoresis). Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pp. 491-500].

The present invention therefore relates to a method of coating a substrate, wherein the composition according to the invention is coated on the surface of the substrate, cured by heat and then irradiated with UV light.

In addition to the photoinitiator, the composition may comprise further commercially available additives, or in the process according to the invention further additives may be added to the formulation. For example, the composition may comprise additional components in addition to components (A), (B) and (C) and further additives to components (B) and (C) in the process according to the invention. For example, light stabilizers, solvents, dyes, pigments, plasticizers, stabilizers, thixotropes, drying catalysts and / or flow improvers can be added. Possible components are described, for example, in Ullmann's Encylcopedia of Industrial Chemistry, 5th Ed., Vol. A18, pp. 429-471, VCH, Weinheim 1991].

UV absorbers such as hydroxyphenyl-benzotriazole, hydroxyphenyl-benzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type UV absorbers can be added as light stabilizers. With or without sterically hindered amines (HALS), for example, individual compounds or mixtures of these compounds can be used.

Possible drying catalysts or curing catalysts are, for example, organometallic compounds, amines, amino group containing resins and / or phosphines. The organometallic compounds are for example metal carboxylates, in particular carboxylates of metals Pb, Mn, Co, Zn, Zr and Cu, and metal chelates, in particular chelates of metals Al, Ti and Zr and organometallic compounds, for example For example, it is an organic tin compound.

Examples of metal carboxylates are stearates of Pb, Mn and Zn, octanoates of Co, Zn and Cu, naphthenates of Mn and Co, and corresponding linoleates, resinates and thalates.

Examples of metal chelates are aluminum, titanium and zirconium chelates of acetylacetone, ethyl acetoacetate, salicyaldehyde, salicylicoxime, o-hydroxyacetophenone and ethyltrifluoroacetoacetate and alcoholates of these metals.

Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate and dibutyltin dioctanoate.

Examples of amines are, in particular, t-amines, for example tributylamine, triethanolamine, N-methyl-diethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine, diazabicyclo Octane (triethylenediamine) and salts thereof. Further examples are quaternary ammonium salts such as trimethylbenzylammonium chloride. The amino group containing resin acts simultaneously as a binder and a curing catalyst. Amino group containing acrylate copolymers are examples thereof. As the curing catalyst, phosphine such as triphenyl-phosphine may be used. The pigment may be an inorganic pigment, an organic pigment or a metal pigment. Preferably, the coating according to the invention is used as a clear lacquer without containing pigments.

The composition according to the invention is preferably used as a coating, in particular as a finishing lacquer for the furniture industry and the automotive industry, and more particularly as a colored or uncolored top layer of surface coatings. However, it is also possible to use them for the foundation layer. When the composition according to the invention is used in the base layer simultaneously with the UV curable finishing lacquer, the double bonds present in each of these layers react, resulting in improved adhesion of the UV curable finishing lacquer to the base layer.

Preference is given to curing processes which do not add uncolored compositions and pigments.

Curing of the composition according to the invention is first limited by heat treatment. The surface is postcured by subsequent irradiation of UV light. Thus, in the curing process according to the invention, the coatings to be crosslinked are first all hardened by the action of heat, and the surface hardness is improved by the subsequent irradiation of UV light.

Thermosetting is usually carried out in an oven (eg circulating air oven) or by irradiation using an IR lamp. Curing without assistive devices at room temperature is possible depending on the binder system used. The curing temperature is generally from room temperature to 150 ° C, for example 25 to 150 ° C or 50 to 150 ° C. In the case of a powder coating composition, the curing temperature may be 250 ° C. or less, for example.

The photochemical curing step is generally carried out using light rays having a wavelength of about 200 to about 600 nm, in particular 200 to 450 nm. As the light source, most modified forms are used a lot. Both local light sources and flat floodlights (lamp carpets) are suitable. Examples include carbon arc lamps, xenon arc lamps, medium pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, metals (halogenated metal lamps) that are optionally doped with metal halides, microwave excited metal-vapor lamps, excimer lamps, polar fluorescent tubes, X-rays generated by fluorescent lamps, argon filament lamps, electric flash lamps, photographic flood rays, electron beams and synchroton or laser plasmas. According to the invention, the distance between the lamp to be irradiated and the substrate can vary, for example from 2 to 150 cm, depending on the intended use and the shape and intensity of the lamp. Laser light sources (eg excimer lasers) are particularly suitable. Selecting the type of lamp depends in particular on the type of photoinitiator (C) used. For example, bisacylphosphine oxide photoinitiators are also excited by lamps having a relatively long emission spectrum.

The following examples further illustrate the invention. Unless stated otherwise, in the remainder of the detailed description of the invention and in the claims, parts or percentages are parts by weight or percentages by weight.

Examples 1-4

Two-component polyurethane clear lacquers are prepared by mixing the following ingredients:

50.10 parts Desmophen ^R 680; Polyester polyols; 70% in butyl acetate [Bayer AG],

0.48 parts Baysilone ^R OL 17; Flow improvers; 10% in xylenes (Bayer AG),

1.45 parts diazabicyclooctane (DABCO); accelerant; 10% in butyl acetate,

14.64 parts xylene / butyl acetate / Solvesso ^R 100 (2/2/1); {Solvesso ^R = aromatic hydrocarbon [Esso]},

Desmodur ^R N 3390 parts 14.76; Isocyanurate; 90% (by Bayer AG),

18.57 parts Xylene / Butyl Acetate / Solvesso ^R 100 (2/2/1)

100 parts of resin solid

To the sample of lacquer thus prepared was added 10% ebecryl ^R 600 [OH functional acrylate resin (UCB)] (based on the resin solid), and further 15% ebecryl ^R 600 [OH functional acrylic Latex resin (UCB)], then 5% photoinitiator (PI-1 or PI-2), and the mixture is coated on a white coil coated sheet, followed by air drying for 15 minutes and 30 minutes at 80 ° C. Warm up. Anhydrous films of about 40 μm in thickness are obtained.

Ten minutes after thermal curing, pendulum hardness is measured according to König (DIN 53157). The irradiation is then carried out using a UV treatment device (2 x 120 W / cm) at a band speed of 10 m / min and the pendulum hardness is measured again. The larger the pendulum hardness measurement, the more durable and harder the hardened surface.

The results of measuring the initiator and pendulum hardness used can be seen in Table 1 below.

Example OH functional resin Photoinitiator Pendulum Hardness [sec] Before the investigation After investigation increase One 10% PI-1 29 41 12 2 10% PI-2 34 47 13 3 15% PI-1 31 46 15 4 15% PI-2 34 53 19

PI-1: 1-hydroxy-cyclohexyl-phenyl ketone [Irgacure ^R 184; Ciba Spezialitatenchemie]

PI-2: 25% bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide + 75% 1-hydroxy-cyclohexyl-phenyl ketone (Irgakur ^R 1800; Ciba Super Chi Alite Tenhemy)

Example 5:

High Solid Clear Lacquer is made by mixing the following ingredients:

56.16 g Joncryl ^R 510; OH functional acrylates; 80% in xylene [SC Johnson Polymer BV / Netherlands],

19.18 g of Cymel ^R 303; Hexamethoxymethylmelamine [Cytec Industries / USA],

14.16 g butanol,

9.89 g methylamyl ketone (MAK),

0.61 g DC-57; Flow improver, 10% in MAK [Dow Corning / Belgium]

100.00 g

0.5% p-toluenesulfonic acid (10% in butanol) is added to the above mixture.

15% 8-hydroxyoctyl acrylate (HOAc) was added to the lacquer sample thus prepared, and another sample 15% Tegomer ^R V-Si 2150 [α, ω-acryloxyorgano functional poly Dimethylsiloxane, Goldschmidt AG / Germany], followed by two additional samples, respectively, and 6% 4-[(2-hydroxyethoxy)-previously dissolved in methyl ethyl ketone. Benzoyl] -1-hydroxy-1-methyl-ethane (Irgacure ^R 2959, Ciba Speccialiteteneheme / Switzerland) is further added. The samples are each coated on a white coil covering sheet, air dried for 15 minutes and then warmed at 120 ° C. for 30 minutes. Anhydrous films of about 45 μm in thickness are obtained.

After thermal curing, the sample sheet is cooled to 50 ° C. and irradiated using a UV treatment apparatus (2 × 81 W / cm) at a band speed of 5 m / min. According to Konnich (DIN 53157), the electron hardness before and after irradiation is measured. The result of measuring pendulum hardness is shown in Table 2 below.

Photoinitiator resin Pendulum Hardness [sec] increase Before the investigation After investigation Without photoinitiator HOAc 57 64 7 No photoinitiator tegomer 59 57 -2 Use photoinitiator HOAc 53 95 42 Use photoinitiator Tegomer 95 113 18

A clear increase in pendulum hardness is observed in the case of samples added with photoinitiator.

Example 6

High Solid Clear Lacquer is made by mixing the following ingredients:

53.4 g of John Cryl ^R 510; OH functional acrylates; 80% in xylene (Sc Johnson Polymer Beppa / Netherlands),

19.18 g of Simel ^R 303; Hexamethoxymethylmelamine (Cytech Industries / USA),

14.16 g butanol,

12.65 g of methylamyl ketone (MAK),

0.61 g DC-57; Flow improver, 10% in MAK (Dow Corning / Belgium)

100.00 g

0.5% p-toluenesulfonic acid (10% in butanol) is added to the above mixture. 15% 8-hydroxyoctyl acrylate (HOAc) was added to the lacquer sample thus prepared, and another sample 15% tegomer ^R V-Si 2150 (α, ω-acryloxyorgano functional polydimethylsiloxane, Goltschmidt AG / Germany), followed by two additional samples, respectively, and 6% 4-[(2-hydroxyethoxy) -benzoyl] -1-hydroxy previously dissolved in methyl ethyl ketone 1-Methyl-ethane (Irgacure ^R 2959, Ciba Spechaliitetenheme / Switzerland) is further added. The samples are each coated on a white coil covering sheet, air dried for 15 minutes and then warmed at 120 ° C. for 30 minutes. Anhydrous films of about 45 μm in thickness are obtained.

After thermal curing, the sample sheet is cooled to 50 ° C. and irradiated using a UV treatment apparatus (2 × 81 W / cm) at a band speed of 5 m / min. Pendulum hardness is measured before and after irradiation in accordance with Zonnich (DIN 53157). The result of measuring pendulum hardness is shown in Table 3 below.

Photoinitiator resin Pendulum Hardness [sec] increase Before the investigation After investigation Without photoinitiator HOAc 53 57 4 No photoinitiator tegomer 69 80 11 Use photoinitiator HOAc 69 102 43 Use photoinitiator Tegomer 63 95 32

Example 7

As described in Example 1, 15% 8-hydroxyoctyl acrylate (HOAc) was added to a sample of a two-component polyurethane lacquer mixture, and another sample 15% 4-hydroxybutyl acrylate (HBAc) was added. Next, two additional samples were each added and 6% 4-[(2-hydroxyethoxy) -benzoyl] -1-hydroxy-1-methyl-ethane (yr) pre-dissolved in methyl ethyl ketone Add cure ^R 2959, Ciba Speccialiteteneheme / Switzerland). The samples are each coated on a white coil covering sheet, air dried for 15 minutes and then warmed at 80 ° C. for 30 minutes. Anhydrous films of about 45 μm in thickness are obtained.

After thermal curing, the sample sheet is cooled to 50 ° C. and irradiated using a UV treatment apparatus (2 × 81 W / cm) at a band speed of 5 m / min. MEK resistance before and after irradiation is measured. For this purpose, a piece of felt impregnated with methyl ethone ketone is placed on the lacquer surface, covered with watch glass, and the time until foaming is formed is measured. The longer it takes for the foam to form, the greater the resistance to the surface coating formulation. The results are shown in Table 4.

Photoinitiator resin MEK resistance [min] increase Before the investigation After investigation Without photoinitiator HOAc 2 2 0 Without photoinitiator HBAc 2 2 0 Use photoinitiator HOAc 2 25 23 Use photoinitiator HBAc 2 15 13

When the photoinitiator is added for subsequent irradiation, the increase in resistance to the solvent is clearly recognized.

Example 8

Two-component polyurethane lacquers are prepared by mixing the following components:

53.80 g of Macrynal ^R SM 510N; Acrylate polyols (Wöst / Germany),

0.15 g of Bike ^R 300; Flow improvers [Byk-Chemie / Germany],

0.07 g Nuodex; Zinc octanoate; accelerant,

11.50 g butyl glycol acetate,

4.70 g Solvesso 100; Aromatic hydrocarbons (esso),

5.68 g methyl isobutyl ketone (MIBK),

23.10 g Desmodur N57; Isocyanates (Bayer AG / Germany)

100.00 g

15% 8-hydroxyoctyl acrylate (HOAc) was added to the lacquer sample thus prepared, and 6% 4-[(2-hydroxyethoxy) -benzoyl] -1- previously dissolved in methyl ethyl ketone. Hydroxy-1-methyl-ethane (Irgacure ^R 2959, Ciba Specilitetethehememi / Switzerland) is further added. The samples are each coated on a white coil covering sheet, air dried for 15 minutes and then warmed at 130 ° C. for 30 minutes. Anhydrous films of about 45 μm in thickness are obtained.

After thermal curing, the sample sheet is cooled to 50 ° C. and irradiated using a UV treatment apparatus (2 × 81 W / cm) at a band speed of 5 m / min. Pendulum hardness is measured before and after irradiation in accordance with Zonnich (DIN 53157). The result of measuring pendulum hardness is shown in Table 5 below.

Photoinitiator resin Pendulum Hardness [sec] increase Before the investigation After investigation Without photoinitiator HOAc 118 120 2 Use photoinitiator HOAc 120 140 20

Claims (13)

Polyacrylate polyols and / or polyester polyols (I) with melamine, polyacrylate polyols and / or polyester polyols (II) with blocked or unblocked polyisocyanates, epoxy-functional polyesters or polyacrylates Coatings based on carboxyl-, anhydride- or amino-functional polyesters and / or polyacrylates (III) or mixtures of (I), (II) (III) and / or (IV) System (A), OH-, NH _2- , COOH-, epoxy- or NCO-functional resins further containing at least one ethylenically unsaturated double bond (B) {A spacer group of four or more linear linking atoms is a double bond and a functional group Need to be present between them, wherein component (A) and component (B) do not contain halogen] and A method of curing the polymerizable composition by thermally treating the polymerizable composition comprising at least one photoinitiator (C), followed by photochemical treatment with light rays having a wavelength of 200 to 600 nm for the purpose of improving surface properties. The compound of claim 1 wherein the photoinitiator (C) in the composition is a compound of formula I, a compound of formula Ia, a compound of formula Ib, a compound of formula II or a compound of formula III, or a compound of formula I, a compound of formula Ia, A compound of formula Ib or a mixture of compounds of formula II and compounds of formula III. Formula I In Formula I above, R ₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, —OCH ₂ CH ₂ —OR ₅ , group Or group Where I is an integer from 2 to 10 and A is a radical ) R ₂ and R ₃ independently of one another are hydrogen, C ₁ -C ₆ alkyl, phenyl, C ₁ -C ₁₆ alkoxy, OSiR ₆ R ₇ R ₈ or —O (CH ₂ CH ₂ O) _q -C ₁ -C ₁₆ Alkyl, where q is 1 to 20, or R ₂ and R ₃ together with the carbon atom to which they are attached form a cyclohexyl ring, R ₄ is hydroxy, C ₁ -C ₁₆ alkoxy or —O (CH ₂ CH ₂ O) _q -C ₁ -C ₁₆ alkyl, Provided that R ₂ , R ₃ and R ₄ are not all C ₁ -C ₁₆ alkoxy or —O (CH ₂ CH ₂ O) _q- C ₁ -C ₁₆ alkyl at the same time, R ₅ is hydrogen, C ₁ -C ₈ alkyl, , or , R ₆ , R ₇ and R ₈ are each, independently of one another, C ₁ -C ₄ alkyl or phenyl. Formula Ia In Formula Ia above, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently of each other hydrogen, methyl, phenyl, methoxy, -COOH, phenyl unsubstituted or substituted with C ₁ -C ₄ alkyl, or a group -OCH ₂ CH ₂ OR ₅ or —SCH ₂ CH ₂ OR ₅ , wherein R ₅ is as defined in formula (I). Formula Ib In Formula Ib above, R ₁₃ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, halogen or group N (R ₁₇ ) ₂ , R ₁₄ is one of those defined for R ₁₃ , or a group And (where a radical R ₁₃ is a direct bond together, other radicals are as defined in the following from the radicals R ₁₃ and the group of the art from the formula Ib), R ₁₅ is C ₁ -C ₈ alkyl, R ₁₆ is hydrogen, —CH═CHR ₂₀ , or phenyl unsubstituted or trisubstituted with C ₁ -C ₁₂ alkyl, C ₁ -C ₄ alkoxy or halogen, R ₁₅ and R ₁₆ together with the carbon atoms to which they are attached form a cyclohexyl ring, R ₁₇ and R ₁₈ are each independently of the other C ₁ -C ₁₄ alkyl, or R ₁₇ and R ₁₈ together with the nitrogen atom to which they are attached form a 5 or 6 membered saturated or unsaturated ring which may be blocked with -O-, -NH- or -N (CH ₃ )-, R ₁₉ is hydrogen or C ₁ -C ₁₂ alkyl, R ₂₀ is hydrogen or C ₁ -C ₄ alkyl. Formula II In Formula II above, R ₂₁ is a naphthyl, anthracyl, 5 or 6 membered heterocyclic ring containing O or S, or a group ego, R ₂₂ is C ₁ -C ₁₂ alkyl, cyclohexyl, cyclopentyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl; Phenyl, biphenyl or naphthyl, monosubstituted or tetrasubstituted, each unsubstituted or substituted with C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy; C ₂ -C ₁₈ alkyl blocked one or more times with —O—; Or Si (R ₂₈ ) (R ₂₉ ) (R ₃₀ ), R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ are each independently hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, phenyloxy, phenylthio, substituted Phenyl unsubstituted or tetrasubstituted with C ₁ -C ₄ alkoxy and / or C ₁ -C ₄ alkoxy, phenyl-C ₁ -C ₄ alkyl, halogen or NO ₂ , R ₂₈ , R ₂₉ and R ₃₀ are each independently of each other C ₁ -C ₈ alkyl, cyclohexyl, cyclopentyl, phenyl or C ₁ -C ₈ alkoxy. Formula III In Formula III above, Z is S or O, R ₃₁ and R ₃₂ are each independently of each other C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkyl blocked one or more times with -O-, phenyl substituted C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl ; Phenyl, naphthyl or biphenyl, unsubstituted or mono-substituted or substituted with halogen, hydroxy, C ₁ -C ₈ alkyl and / or C ₁ -C ₈ alkoxy, respectively; A 5 or 6 membered heterocyclic ring containing C ₅ -C ₁₂ cycloalkyl, O, S or N, or a group COR _33, or R ₃₁ is a radical , , OH, OR _34, O ^- NH ₄ ⁺ or _{^{O - [Mn +] 1 /}} n ( where a, n is an integer from 1 to 3, M n is the valence of metal ion), or R ₃₁ and R ₃₂ together are C ₄ -C ₇ alkylene and together with the P atom to which they are attached form a ring, R ₃₃ is C ₁ -C ₁₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₈ alkenyl; Phenyl, naphthyl or biphenyl, monosubstituted or tetrasubstituted, each unsubstituted or substituted with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio and / or halogen; 5 or 6 membered heterocyclic ring containing O, S or N, or a group ego, R ₃₄ is C ₁ -C ₈ alkyl, phenyl, naphthyl, C ₁ -C ₈ alkylphenyl or C ₁ -C ₄ alkylnaphthyl, Y is phenylene, C ₁ -C ₁₂ alkylene or C ₅ -C ₆ cycloalkylene, X is C ₁ -C _{18 alkylene, -O-, -S-, -NR 35 -} , P (O) R 36 or -SO ₂ - the blocked one or more times with C ₂ -C ₁₈ alkylene, or Cl , F, C ₁ -C ₄ alkoxy, COOR ₃₇ , phenyl, phenyl-C ₁ -C ₄ alkyl, naphthyl-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylphenyl, C ₁ -C ₄ alkylnaphthyl Or C ₁ -C ₆ alkylene substituted with phenyl-C ₁ -C ₄ alkoxy, naphthyl-C ₁ -C ₄ alkoxy and / or CN, X is C ₁ -C ₈ alkylene substituted with one or two radicals of formula A, or Formula A X is a group of formula A1 to A9, or Formula A1 Formula A2 Formula A3 Formula A4 Formula A5 Formula A6 Formula A7 Formula A8 Formula A9 In the above formulas A1 to A9, a and b are each independently 0 or 1, The sum of d and f is an integer of 3 to 8, provided that neither d nor f is zero. X is a group -CH ₂ -CH = CH-CH ₂ -or -CH ₂ -C≡C-CH _2- , or X is phenylene, xylylene, mono- or tri-substituted, each unsubstituted or substituted with Cl, F, C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy, or Or X is phenylene which is mono- or trisubstituted by one or two groups (A) and further substituted with Cl, F, C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy, or X is a group of formulas A10 to A13. Formula A10 Formula A11 Formula A12 Formula A13 In the above formulas A10 to A13, Q is a single bond, CR ₃₉ R ₄₀ , -O-, -S-, -NR _35- , -SO ₂ -,-(CH ₂ ) _p -or -CH = CH-, p is an integer from 2 to 12, Z is O or S, R ₃₅ is hydrogen, C ₁ -C ₁₂ alkyl or phenyl, R ₃₆ is C ₁ -C ₄ alkyl or phenyl, R ₃₇ is C ₁ -C ₁₂ alkyl, C ₂ -C ₁₈ alkyl blocked at least once with -O-, benzyl, phenyl, cyclopentyl or cyclohexyl, R ₃₈ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen, R ₃₉ is hydrogen, methyl or ethyl, R ₄₀ is hydrogen or C ₁ -C ₄ alkyl. The composition of claim 1 wherein the composition In formula (I), R ₁ is hydrogen, C ₁ -C ₁₂ alkyl or —OCH ₂ CH ₂ -OR ₅ , and R ₂ and R ₃ are each independently of each other C ₁ -C ₆ alkyl, phenyl or C ₁ -C ₁₆ alkoxy Or R ₂ and R ₃ together with the carbon atom to which they are attached form a cyclohexyl ring, R ₄ is hydroxy or C ₁ -C ₁₆ alkoxy and R ₅ is hydrogen or ego, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ in formula (Ia) are hydrogen, In formula (Ib) R ₁₃ is hydrogen, R ₁₄ is C ₁ -C ₄ alkylthio or N (R ₁₇ R ₁₈ ), R ₁₅ is C ₁ -C ₈ alkyl, R ₁₆ is phenyl, R ₁₇ and R ₁₈ are each independently of each other C ₁ -C ₄ alkyl, or R ₁₇ and R ₁₈ together with the nitrogen atom to which they are attached form a saturated six-membered ring which may be blocked with -O-, In formula (II), R ₂₁ is phenyl, R ₂₂ is C ₁ -C ₁₂ alkyl, Z is O in formula (III), and R ₃₁ and R ₃₂ are each independently of the others phenyl substituted or substituted with C ₁ -C ₁₈ alkyl, unsubstituted or substituted with C ₁ -C ₈ alkyl and / or C ₁ -C ₈ alkoxy Or group COR ₃₃ and R ₃₃ is unsubstituted or mono- or tetrasubstituted phenyl with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy. The method of claim 1 wherein the initiator (C) in the composition is 1-hydroxy-cyclohexyl-phenyl ketone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1 -Propane-1-one or 2-hydroxy-2-methyl-1-phenyl-propanone, (4-morpholino-benzoyl) -1-benzyl-1-dimethylamino-propane or (4-methylthiobenzoyl ) -1-methyl-1-morpholino-ethane, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl)-(2-methylprop-1-yl) -phosphine oxide , Bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide, or bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide and 1-hydroxy-cyclo Hexyl-phenyl ketone, hydroxy-2-methyl-1-phenyl-propanone or a mixture with 2-methoxy-1-phenyl-ethane-1,2-dione, or bis (2,4 , 6-trimethylbenzoyl) -phenyl-phosphine oxide with 1-hydroxy-cyclohexyl-phenyl ketone, hydroxy-2-methyl-1-phenyl-propanone or 2-methoxy-1-phenyl-ethane-1 Or mixtures with 2-dione or 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide with 1-hydroxy-cyclohexyl-phenyl ketone, hydroxy-2-methyl-1-phenyl-propane A mixture with 2-methoxy-1-phenyl-ethane-1,2-dione. The process according to claim 1, wherein the polyester polyol, acrylate polyol or hexamethoxymethylmelamine (A), isocyanurate or OH-functionalized acrylate (B) and 1-hydroxy-cyclohexyl-phenyl ketone or 25% bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide with 75% 1-hydroxycyclohexyl-phenyl ketone or 4-[(2-hydroxyethoxy) -Benzoyl] -1-hydroxy-1-methyl-ethane (C) wherein a composition is used. The process according to claim 1, wherein the composition comprises 0.05 to 20% by weight, in particular 2 to 10% by weight, based on 100 parts of component (A). The method according to claim 1, wherein the composition comprises 1 to 50% by weight, in particular 5 to 30% by weight of component (B), based on 100 parts of component (A). The method of claim 1 wherein the composition is a composition based on acrylate / melamine, bicomponent polyurethane, monocomponent polyurethane, bicomponent epoxy or monocomponent epoxy / carboxy. The method of claim 1 wherein the spacer group in component (B) is Group, where y is 2 or more. Polyester polyols (I) with melamine, polyacrylate polyols with blocked or unblocked polyisocyanates and / or polyester polyols (II), carboxyl-, anhydride- with epoxy-functional polyesters or polyacrylates Or coating systems (A) based on amino-functional polyesters and / or polyacrylates (III) or mixtures (I), (II), (III) and / or (IV), OH-, NH _2- , COOH-, epoxy- or NCO-functional resins containing one or more ethylenically unsaturated double bonds (B) {A spacer group of four or more linear linking atoms is formed between a double bond and a functional group. Need to be present}, wherein component (A) and component (B) contain no halogen] and A composition comprising at least one photoinitiator (C). Use of the composition according to claim 10 as a coating. Use according to claim 11 as a finishing lacquer in the furniture industry and the automotive industry. A method of coating a substrate, wherein the composition according to claim 10 is coated on the surface of the substrate, heat cured and then irradiated with UV light.