KR19990087350A - Coating composition comprising a bicyclo- or spiro-orthoester-functional compound - Google Patents

Abstract

The present invention relates to a coating composition comprising a first component composed of at least one bicyclo-orthoester group or a spiro-orthoester group, and a second component composed of at least two hydroxyl-reactive groups and a method for curing the coating composition. As for

If the coating composition according to the invention is cured, the latent hydroxyl group of the bicyclo-orthoester group or the spiro-orthoester group is unblocked and reacted with the hydroxyl-reactive group of the second compound,

The invention also relates to a process for preparing a bicyclo-orthoester composition from a corresponding oxetane compound,

The polymer is characterized by consisting of at least one bicyclo-orthoester group or spiro-orthoester group.

Description

Coating composition consisting of bicyclo- or spiro-orthoester functional compounds

The present invention relates to a coating composition composed of a first compound consisting of at least one bicyclo- or spiro-orthoester group.

The use of compounds consisting of bicyclo-orthoester groups in coating compositions is known from US Pat. No. 4,338,240. In this patent publication, the preparation and use of bicyclo-orthoester-functional compounds (hereinafter bicyclo-orthoesters are abbreviated as BOE) is described. A BOE-functional compound is described which is an adduct of two compounds consisting of one hydroxyl group and one BOE group and one compound consisting of two isocyanate groups. The compound is crosslinked by cationic ring opening homopolymerization of the BOE group. In this case, however, the presence of moisture should be excluded. Moreover, energy or heat in the form of ultraviolet, infrared or microwave irradiation must be supplied during the polymerization process.

The present invention is to provide a coating composition of the above form without the above drawbacks. For this reason the coating compositions described above are characterized in that they consist of a second compound consisting of at least two hydroxyl-reactive groups.

A coating composition consisting of a compound consisting of at least one bicyclo- or spiro-orthoester group (hereinafter spiro-orthoester is abbreviated as SOE) is a composition having a latent hydroxyl group. The presence of water or moisture in the air will hydrolyze the BOE or SOE groups to form hydroxyl groups. This reaction is also known as deblocking. When a little block is released, especially volatile components are released. When the BOE- or SOE- group is unblocked in this manner, it is not possible to obtain a homopolymer of BOE- or SOE groups by cation polymerization. However, it was found that when a second compound consisting of at least two hydroxyl-reactive groups is present in the composition, the unblocked hydroxyl group reacts with the hydroxyl-reactive group to provide a crosslinked polymer.

BOE- and SOE-functional compounds can be used as the main binder or reactive diluent in the coating compositions of the present invention.

The use of compounds consisting of BOE or SOE groups in the coating composition is for example compounds having free hydroxyl groups such as hydroxyl-functional reactive diluents, hydroxyl-functional main binders, for example polyester polyols and acrylate polyols and BOE or SOE There are several advantages to using compounds in which the groups have already been hydrolyzed.

First, the viscosity of the compound consisting of BOE or SOE groups is lower than that of the corresponding hydrolyzed compound. As a result, a solvent is required in the coating composition that has been evaporated into the air to reduce the viscosity.

Secondly, because of the stability of the BOE- and SOE-functional compounds, the ratio of pot life: drying time of the composition according to the invention is particularly beneficial for hydrolysis which may occur in the presence of water or moisture.

Third, in the coating compositions of the present invention, the BOE- and SOE-functional compounds have the advantage that the hydrolysis of the BOE or SOE groups is substantially increased in the viscosity of the composition. High viscosity provides reduced sagging of the coating composition of the substrate.

Finally, the coating compositions of the present invention provide high build behavior.

BOE group means a linking group which has a structure of following formula (1).

(In Formula 1, X and Z are each independently selected from a linear or branched alkylene (alkenylene) group optionally containing oxygen or nitrogen atoms and having 1-4 carbon atoms; Y is absent or oxygen or Independently selected from X and Z which are linear or branched alkylene (alkenylene) groups optionally containing nitrogen atoms and having 1 to 4 carbon atoms; R ₁ and R ₂ are the same or different and are hydrogen, hydroxyl, Alkyl (alkenyl) groups, which may be linear or branched, optionally containing one or more heteroatoms, consisting of a group selected from oxygen, nitrogen, sulfur, phosphorus, sulfone, sulfoxy and esters; , Optionally epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro, phosphorus, sulfoxy, amido, ether, ester, urea, urethane, thioester, thioamide, amide, carbox It may be linear or branched with monovalent radicals substituted with carboxyl, carbonyl, aryl and acrylic groups, selected from oxygen, nitrogen, sulfur, phosphorus, sulfone, sulfoxy and esters, optionally epoxy, cyano, amino, thiol , Hydroxyl, halogen, nitro, phosphorus, sulfoxy, amido, ether, ester, urea, urethane, thioester, thioamide, amide, carboxyl, carbonyl, aryl and acrylic group, ester group; ether group; amide Alkylene having 1 to 10 carbon atoms selected from the group substituted with a thioester group, thioamide group, urethane group, urea group, and a single bond, and optionally containing one or more heteroatoms Niylene) group is selected from the group of divalent radicals.)

Preferably X, Y and Z are methylene. In this case R ₁ and R ₂ are linked to a divalent 2,6,7-trioxabicyclo [2.2.2] octane radical.

In the case of R ₁ and R ₂ both are monovalent radicals and the BOE group defined by formula (1) is the same as the BOE-functional compound. Monovalent radicals R ₁ and R ₂ are each linear, branched alkyl (alkenyl) groups having 1-20 carbon atoms, optionally substituted with hydrogen, hydroxyl and optionally one or more hydroxyl groups, optionally with ester groups It is preferably selected from the group of respectively. Examples of such groups are: methyl, methylol, ethyl, ethylol, propyl, propylol, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, -CH ₂ -CH ₂ -O-CO-C _1-20 alkyl (alkenyl) groups and mixtures thereof.

Preferably, R ₁ is a linear or branched alkyl (alkenyl) group having 1-20 carbon atoms, optionally substituted with hydroxyl, while R ₂ is methyl or ethyl. Optionally, R ₁ is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and mixtures thereof, while R ₂ is methylol, ethyl, ethylol or -CH ₂ -CH ₂ -O-CO-C _1-20 alkyl (alkenyl) group.

When a divalent radical is selected with an R ₁ or R ₂ group or together, a high molecular weight BOE-functional compound can be formed. It may be a polymer or adduct consisting of several BOE groups. As such two BOE groups can form adducts by selecting monovalent radicals for one of the R ₁ and R ₂ groups and _divalent radicals for one another. In addition, the BOE group may be bonded together through a divalent radical. The BOE group can also be linked to the monomer or oligomeric compound via a divalent radical. Such BOE-functional compounds are described, for example, in US Pat. No. 4,338,240, described above. For example, two BOE groups can be linked to dimeric fatty acids, such as Pripol 1009 from Unichema. Optionally, in the above-described configuration, the BOE groups can function as side or end groups in the polymer chain. The polymer can be, for example, polyester, polyether, polyacrylate, polyamide or polyurethane. When the divalent radical is a single bond, the BOE group can be directly bonded to the polymer. When both the R ₁ and R ₂ groups are bivalent, the BOE group can be integrated into the main chain of the polymer or can be provided to link two polymer chains together. Preferably one or both of the R ₁ and R ₂ groups may be ester, ether, urethane, single bond and linear or branched and have 1-10 carbon atoms which may contain one or more ester, ether or urethane groups It is selected from the group of alkylene (alkenylene) group.

In this case, the term SOE group refers to a group having a structure represented by the following formula (2) or (3).

(In Formula 2 and Formula 3, R ₃ and R ₅ is linear or branched alkyl (alkenyl) optionally containing one or more oxygen, nitrogen, sulfur or phosphorus atoms, and optionally substituted with halogen atoms, Each independently selected from the group of aryl or acrylic; and R ₄ and R ₆ are optionally selected from linear or branched alkyl (alkenyl), aryl or acrylic groups containing one or more oxygen, nitrogen, sulfur and Divalent radicals such as monovalent radicals and alkylene groups and single bonds having 1 to 10 carbon atoms with or without groups selected from oxygen, nitrogen, sulfur and phosphorus, one or more atoms and ethers, esters and urethane groups Each independently selected from alkylene groups having 1-3 carbon atoms optionally substituted with one or more groups selected from

Preferably R ₃ and R ₅ are 1-4 carbon atoms and are independently selected from linear or branched alkyl (alkenyl) groups having methyl or ethyl groups.

In this case neither of R ₄ and R ₆ is substituted with a divalent radical, and the SOE group defined by the above formulas (2) and (3) is the same as the SOE-functional compound.

When the divalent radical is selected as a substituent for the R ₄ or R ₆ group or both, high molecular weight SOE-functional compounds can be prepared in the same manner as described above for high molecular weight BOE compounds. When R ₄ or R ₆ has one divalent radical substituent, the adduct or polymer may be prepared to have an SOE group as a terminal or side chain group. In formula (3), when both R ₄ and R ₆ have a divalent radical as a substituent, in this case, the SOE group may be included in the main chain. The polymer can be for example polyacrylate, polyester, polyether, polyamide or polyurethane.

Optionally R ₄ has a compound capable of forming point symmetry with respect to C ^s It may be, to provide an SOE compound according to the formula (4).

R ₄ provides a SOE compound according to Formula 4 below.

Preferably Formula 4 is represented by the following Formula 5.

Preferably R ₄ is ethylene, optionally substituted with a linear or branched alkyl group having 1-5 carbon atoms, and optionally comprises one or more oxygen and nitrogen atoms. For example, R ₄ is as follows.

Preferably R ₆ is propylene.

The coating composition according to the invention as well as the BOE- or SOE-functional compound consists of a second compound consisting of at least two hydroxyl-reactive groups. The hydroxyl-reactive group is selected from isocyanate, epoxy, acetal, carboxyl, anhydride and alkoxy silane groups. Also included are mixtures of these groups in one compound. Optionally the second compound may be an amino resin.

Examples of compounds consisting of at least two isocyanate groups can be aliphatic, cycloaliphatic and aromatic polyisocyanates, for example trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 2,3-butylene diisocyanate, Hexamethylene diisocyanate, octamethylene diisocyanate, 2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, dodecamethylene diisocyanate, α, α'-dipropyl ether diisocyanate, 1 , 3-cyclopentylene diisocyanate, 1,2-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4-methyl-1,3-cyclohexylene diisocyanate, 4,4'-dicyclo Hexylene diisocyanate methane, 3,3'-dimethyl-4,4'-dicyclohexylene diisocyanate methane, m- and p- Phenylene diisocyanate, 1,3- and 1,4-bis (isocyanate methyl) benzene, 1,5-dimethyl-2,4-bis (isocyanate methyl) benzene, 1,3,5-triisocyanate benzene, 2, 4- and 2,6-toluene diisocyanate, 2,4,6-toluene triisocyanate, α, α, α ', α'-tetramethyl o-, m- and p-xylylene diisocyanate, 4,4 '-Diphenylene diisocyanate methane, 4,4'-diphenylene diisocyanate, 3,3'-dichloro-4,4'-diphenylene diisocyanate, naphthalene-1,5-diisocyanate, isophorone di Isocyanate and transvinylidene diisocyanate and mixtures of these polyisocyanates.

The compound may also be an adduct of polyisocyanates such as, for example, biuret, isocyanurate, alloponate uretdione and mixtures thereof. Examples of such adducts include adducts of two molecules of diols such as hexamethylene diisocyanate or isophorone diisocyanate and ethylene glycol, three molecules of hexamethylene diisocyanate and one molecule of water, one molecule of trimethylol propane An adduct of 3 molecules of isophorone diisocyanate, an adduct of 1 molecule of pentaerythritol and 4 molecules of toluene diisocyanate, available from Bayer under the trade name Desmodur N3390. Isocyanurate of hexamethylene diisocyanate, uretdione of hexamethylene diisocyanate available under the trade name Desmodeu N3400, allophore of hexamethylene diisocyanate available under the trade name Desmodeu LS2101 under the trade name Vestanate T1890 Isocyanurate of isophorone diisocyanate available from Huels under the trade name). Also suitable for use are (co) polymers of isocyanate-functional monomers such as α, α'-dimethyl-m-isopropenyl benzyl isocyanate. Finally, the isocyanates described above and their adducts may be present in the form of masked isocyanates known to those of ordinary skill in the art.

Examples of compounds consisting of at least two epoxy groups are, for example, aliphatic, cycloaliphatic or aromatic hydroxyl compounds such as ethylene glycol, glycerol, cyclohexane diol, mononuclear di- or polyhydric phenols, bisphenols such as bisphenol-A and bisphenol-F and polynuclears. Soluble di- or polyhydric phenols; Polyglycidyl ethers of phenol formaldehyde novolac; Epoxidized divinyl benzene; Epoxy compounds composed of isocyanurate groups; Epoxidized polyalkandienes such as epoxidized polybutadiene; Hydantoin epoxy resins; Epoxy resins obtained by epoxidized aliphatic and / or cycloaliphatic alkenes include, for example, dipentene dioxide, dicyclopentadiene dioxide and vinylcyclohexene dioxide; And glycidyl groups such as polyesters or polyurethanes having from 2 to more glycidyl groups per molecule; Solid and liquid epoxy compounds such as di- or polyglycidyl ethers of mixtures of these epoxy compounds.

Ethylene-based, optionally consisting of compounds such as glycidyl (meth) acrylate, N-glycidyl (meth) acrylamide and / or allyl glycidyl ether and, if desired, one or more copolymerizable, ethylenically unsaturated monomers (Co) polymers of unsaturated epoxy groups are used.

Examples of compounds consisting of at least two acetal groups are described in US Pat. Nos. 4,788,288, 4,864,055, 5,155,170 and 5,336,807. Other suitable acetal-functional compounds are, for example, polyesters such as aminobutyralaldehyde di (methyl) ethyl acetal (ABDA) and carboxyl ester-, isocyanate- or cyclocarbonate-functional (co) oligomers or (co) polymers , Polyacrylates, and compounds obtained by reacting with polyurethanes. Examples of such polymers include copolymers of glycerol cyclocarbonate methacrylate and styrene. Also mixtures of compounds consisting of at least two acetal groups can be used.

Examples of compounds consisting of at least two carboxyl groups include saturated or unsaturated aliphatic, cycloaliphatic and aromatic polycarboxylic acids, such as malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, decane dicar Acids, dimer fatty acids, maleic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroendomethylene tetrahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid And mixtures thereof.

Examples of anhydride-functional compounds include radical polymers of unsaturated cyclic anhydride monomers such as maleic anhydride, itaconic anhydride or citraconic anhydride. It is also possible to use copolymers of these anhydride monomers and one or more ethylenically unsaturated monomers. The copolymer will comprise 10-50 wt.% Anhydride groups. Examples of ethylenically unsaturated monomers are styrene, substituted styrene, vinyl chloride, vinyl acetate and esters of acrylic or methacrylic acid, for example methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylic Elate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) Acrylate, 2,2,5-trimethylcyclohexyl (meth) acrylate and isobornyl (meth) acrylate. The anhydride-functional (co) polymers comprise, for example, (meth) acrylic acid in small amounts, for example from 1 to 10 wt.% Of ethylenically unsaturated carboxylic acid groups. The molecular weight of the anhydride-functional (co) polymer is preferably 1000-50000.

When the coating composition according to the invention is used as a top coat, the ethylenically unsaturated monomer is preferably used in a molar ratio of 1: 1 with an anhydride monomer as described in US Pat. No. 4,798,745.

Optionally, the anhydride-functional compound can be an adduct of a polymer consisting of anhydride monomers and functional groups. Examples of such adducts include those of polybutadiene or butadiene / styrene copolymers and maleic anhydride; Adducts of styrene / allyl alcohol copolymers and maleic anhydride esterified with unsaturated fatty acids, terpene resins and maleic anhydride; Of polymers and anhydride monomers consisting of tricarboxylic compounds capable of forming anhydride groups and copolymers of styrene / allyl alcohol or hydroxyl such as hydroxylethyl (meth) acrylate as described in EP-A-0 025 917 Adducts; Adducts of trimellitic anhydride and polyols as described in EP-A-0 134 691; And adducts of unsaturated ring anhydrides and polymers containing thiol groups such as maleic anhydride, itaconic anhydride or citraconic anhydride. Mixtures of anhydride-functional compounds can also be used.

Examples of the alkoxysilane-functional compound are alkoxysilanes having the following structure.

Wherein T is -OCH ₃ , -OC ₂ H ₅ or -OC ₂ H ₄ OCH ₃ , R ₇ and R ₈ is a reactive group selected independently of each other. Examples of such reactive groups include vinyl, aminoalkyl, epoxyalkyl and methacryloxyalkyl groups. It is also possible to use reaction products of alkoxysilane-functional compounds and mixtures of alkoxysilane-functional compounds and / or the above reaction products.

Examples of vinyl-functional alkoxysilanes include vinyl triethoxysilane and vinyl trimethoxysilane. As an example of the reaction product of the vinyl-functional alkoxysilane, mention may be made of silicone resins formed by the reaction of (CH ₂ = CHSiO _3/2 ) _x (R ₂ SiO) _y and styrene.

Reaction products of amino-functional alkoxysilanes can be prepared by reacting the silane with an inorganic acid (HA):

NH ₂ (CH ₂ ) ₃ Si (T) ₃ + HA → A-NH (CH ₂ ) ₃ Si (T) ₃

Wherein A has an acid residue ion or an ester of organic acid R ₉ (COOR ₁₀ ) _n , where n is an integer of at least 1, R ₉ is a linear or branched, optionally unsaturated alkane radical, and R ₁₀ is lower Alkyl groups are, for example, C _1-4 alkyl groups. For example,

NH ₂ (CH ₂ ) ₃ Si (T) ₃ + R ₉ COOR ₁₀ → R ₉ CO-NH (CH ₂ ) ₃ Si (T) ₃

2NH ₂ (CH ₂ ) ₃ Si (T) ₃ + 1R ₁₀ OOCR ₉ COOR ₁₀ →

(T) ₃ Si (CH ₂ ) ₃ NH-OCR ₉ CO-NH (CH ₂ ) ₃ Si (T) ₃

For example, an adduct of 1 mole of diethyl malonate and 2 mole of 3-amino propyl trimethoxy silane is a suitable alkoxy silane containing compound. It is also suitable to use reaction products of amino-functional alkoxy silanes and isocyanate-functional compounds.

One example of a reaction product of an epoxy-functional silane compound is β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane and the reaction product of amines, acids and alcohols.

Examples of reaction products of methacryloxyalkyl trialkoxysilanes include γ-methacryloxypropyl trimethoxysilane and γ-methacryloxypropyl tri (β-methoxyethoxy) silane and vinyl-functional monomers such as styrene and methyl Reaction product of methacrylate.

Examples of suitable amino resins are urea resins, guanamine resins and melamine resins and mixtures thereof. Examples of urea resins are etherified methylol urea, butyl urea and isobutyl urea. One example of guanamine resins is tetra (methoxymethyl) benzoguanamine. Examples of melamine resins are hexa (methoxymethyl) melamine (HMMM) and isobutylate melamine.

The BOE- and SOE-functional compounds and the hydroxyl-reactive compounds described as well as other compounds may be present in the coating compositions according to the invention. The compound may be a reactive diluent and / or main binder consisting of a reactive group capable of crosslinking with a hydroxyl-functional compound and / or a hydroxyl-reactive compound. For example, H. Polyester polyols, polyether polyols, polyacrylate polyols, polyurethane polyols, cellulose acetobutyrates, hydroxyl- as described in Lackkunstharze, 5th edition, 1971 (Carl Hanser Verlag, Munich), by H. Wagner et al. Functional epoxy resins, alkyds and hydroxyl-functional binders such as dendritic polyols such as those described in WO 93/17060. There will also be hydroxyl-functional oligomers and monomers such as castor oil and trimethylolpropane. Finally, as ketone resins, asparagiic acid esters and latent or non-latent amino-functional compounds, for example oxazolidine, ketamine, aldimine, diimine, secondary amines and polyamines can be present. These and other compounds are known to those of ordinary skill in the art and are specifically mentioned in US Pat. No. 5,214,086.

The ratio of hydroxyl-reactive groups to hydroxyl groups is in the range of 50 to 300 eq.%, Preferably 70 to 250 eq.%.

The present invention also includes a method of curing the present coating composition. In particular, the latent hydroxyl group of the BOE or SOE-functional compound may be unblocked and react with the hydroxyl-reactive group of the second compound to provide a cured coating composition.

Unblocking of the latent hydroxyl groups of the BOE and SOE compounds occurs under added water or under the influence of water, such as moisture, in the air. The deblocking is preferably carried out with Lewis acids such as AlCl ₃ , SbCl ₅ , BF ₃ , BCl ₃ , BeCl ₂ , FeCl ₃ , FeBr ₃ , SnCl ₄ , TiCl ₄ , ZnCl ₂ and ZrCl ₄ and BF ₃ Et ₂ O, BF _{3 -2CH 3 COOH, BF 3 -2H 2} O, BF 3 -H 3 PO 4, BF 3 - (CH 3) 2 O, BF 3 -THF, BF 3 -2CH 3 OH, BF 3 -2C 2 H 5 OH And an organic catalyst such as BF ₃ -C ₆ H ₅ CH ₂ and a first catalyst selected from the group of Bronsted acid. Preferably mono- or dialkyl phosphates optionally substituted with naphthalene sulfonic acid, dodecyl benzene sulfonic acid, dibutyl phosphate, trichloroacetic acid, phosphoric acid and mixtures thereof, carboxyl with at least one chlorine and / or fluorine atom Acid, alkyl or aryl sulfonic acids or (alkyl) phosphoric acids, especially Bronsted acids with pKa <3, such as methane sulfonic acid, paratoluene sulfonic acid can be used.

If desired, the first catalyst may be blocked, releasing Bronsted acid or Lewis acid under influence such as, for example, electromagnetic radiation (light or UV), heat or moisture. Acid-generating photoinitiators are particularly sensitive. G. Li Bassi et al., "Photoinitiators for the Simultaneous Generation of Free Radicals and Acid Hardening Catalysts", Radcure '86 Proceedings, for example 2-methyl-1 of Fratelli Lamberti Spa, Varese, Italy. -[4- (methylthio) phenyl] -2- [4-methylphenylsulfonyl] propan-1-one (MDTA). Alternatively, Lewis acid producing compounds such as Ciba Geigy's Irgacure 261 (trade name) and trimethyl silyl benzene sulfonic acid ester can be used.

The first catalyst can be used alone or as an effective amount of the catalyst mixture. The term effective amount here depends on the use of a BOE- or SOE-functional compound. When the BOE- or SOE-functional compound is used as the main binder, sufficient catalyst should be present to hydrolyze substantially all of the BOE- or SOE-functional compound. However, if the BOE- or SOE-functional compound is used first as the reaction diluent and other compounds are present as the main binder, then hydrolysis of at least some of the BOE- or SOE-functional compounds will be sufficient.

A quantitation of 0 to 10 wt.% Relative to the BOE- or SOE-functional compound of the first catalyst is sufficient. Preferably 0.3 to 8 wt.%, In particular 0.5 to 6 wt.%, Is present.

The reaction of the unblocked hydroxyl group of the BOE- or SOE compound, the hydroxyl-reactive group of the second compound, and optionally the third compound, present in the composition consisting of a hydroxyl group or a hydroxyl-reactive group is influenced by the second catalyst. It is preferable to take place under. Such catalysts are known to those of ordinary skill in the art. The second catalyst is 0-10 wt.%, Preferably 0.001-5 wt, calculated on a solid material (e.g., a quantification of a BOE- or SOE, a hydroxyl group-reactive compound, and optionally a third compound described above). .%, Especially 0.01 to 1 wt.%.

As examples for the various hydroxyl-reactive groups, the following catalysts will be mentioned: polyisocyanates; Dimethyl dilaurate tin, dibutyl dilaurate tin, dibutyl diacetic acid tin, octosan tin, zinc octoate, aluminum chelate and dimethyl dichloride tin; Polyepoxy compounds; Tertiary amines and Lewis acids such as BF ₃ or an organic complex thereof; Polyacetal compounds; Paratoluene sulfonic acid and dodecyl benzene sulfonic acid; Polycarboxylic compound; Dodecyl benzene sulfonic acid, polyanhydride compound; Organotin compounds; Alkoxysilane compounds; Organotin compounds, phosphoric acid, paratoluene sulfonic acid, dodecyl benzene sulfonic acid and tertiary amines; And amino resins; Dodecyl benzene sulfonic acid.

As described above, the first and second catalysts may be the same in some coating compositions. In this case, the quantification of the catalyst is higher than that indicated by the first or second catalyst alone.

The coating composition according to the invention may be part of a component system, for example a two-component system. For example, one component consists of a BOE- or SOE-functional compound and a hydroxyl-reactive compound. The second component consists of a catalyst for the hydrolysis of the BOE- or SOE-functional compound.

Optionally a three-component system can be used. For example, one component consists of a BOE- or SOE-functional compound. The second component consists of a hydroxyl-reactive component. The third component consists of a catalyst for a BOE- or SOE-functional compound.

In addition, coating compositions such as those described above may contain water traps such as solvents, pigments, fillers, leveling agents, emulsifiers, antifoams and flow regulators, reducing agents, oxidizing agents, HALS-stabilizers, UV-stabilizers, molecular sieves traps), and common additives such as anti-precipitants.

The substrate may be applied by methods known to those skilled in the art, for example by rolling, spraying, brushing, flow coating, dipping and roller coating. Preferably a coating composition as described above is applied by spraying.

The coating composition of the present invention can be applied to a particular substrate. The substrate can be, for example, iron, steel and aluminum, plastic, wood, glass, composites, paper, leather or other coating layers. The other coating layer may be made of the coating composition of the present invention or may be another coating composition. The coating compositions of the present invention show particular uses such as clearcoats (basecoats, water phases and solvent phases), basecoats, pigmented topcoats, primers and fillers. The composition is particularly suitable for reworked motor vehicles and transport vehicles, and the processed large transport vehicles are trains, trucks, buses and aircraft.

The applied coating composition can be cured very effectively at a temperature of 0-50 ° C. If desired, the coating composition may be baked at a temperature in the range of 50-120 ° C.

The present BOE-functional compounds can be prepared in several ways.

One method is to transesterify the polyol in a suitable solvent. Examples of such polyols include glycerol, trimethylol propane and pentaerythritol. The transesterifying agent is a trialkyl orthoester selected from the group of triethyl orthoformate, triethyl orthoacetate and triethyl orthopropionate. Preferably, solvents such as diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether may be used as the solvent inert to the transesterification reaction. The catalyst for the reaction can be paratoluene sulfonic acid or a strong acid such as BF ₃ Et ₂ O. The method is tee. Polymer Journal 13 (1981), p. 715 to T. Endo et al.

When the selected polyol is pentaerythritol, a BOE group consisting of hydroxyl groups is formed. The BOE group can be converted to a BOE-functional compound by transesterification or by reaction with an acid chloride. In this way hydroxyl-functional BOE groups can be bonded via transesterification to saturated or unsaturated carboxylic acids, preferably having up to 20 carbon atoms. The resulting BOE-functional compounds have the advantage of being nonvolatile or slightly volatile because of their high molecular weight, and surprisingly low in viscosity. For this reason, BOE-functional compounds can be used very suitably as reactive diluents. When the carboxylic acid group is unsaturated, the present coating composition of the BOE-functional compound can be cured in two ways, for example, through hydrolyzed BOE groups and unsaturated compounds as described above.

The hydroxyl-functional BOE group also provides a vinyl group through transesterification with (meth) acrylate. By polymerization under the influence of radicals using vinyl-containing BOE, BOE-functional polyacrylates can be prepared.

BOE-functional polyacrylates can also be prepared by transesterification of polyacrylates with hydroxyl-functional BOE groups. In this case, it is preferable to use polyacrylates having esters having 1-4 carbon atoms, preferably as short chain esters. The advantage of the polyacrylate is that the alcohol groups produced after the transesterification reaction are generally separated by distillation, and all polymers having ester groups in the side chain can be provided to the BOE group via the transesterification. Examples of the polymer may be mentioned polyesters, polyethers, polyamides and polyurethanes.

Optionally, the hydroxyl-functional BOE group can be provided with a group that is reactive or not, for example using an isocyanate-functional compound. Moreover, two or more BOE-functional groups can be internally bonded using di- or polyisocyanate-functional compounds. As such, the hydroxyl-functional BOE groups can be bonded to hydroxyl-functional polymers such as, for example, polyester polyols, polyether polyols, and polyacrylate polyols.

In addition, BOE-functional compounds are E.J. It can be prepared by converting the corresponding ester-functional oxetane compound into BF ₃ Et ₂ O, as described in Tetrahedron letters, 24 (1983), pp 5571-5574 to EJ Corey et al.

The oxetane compound has the following structure.

In the above, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are each independently selected from the group of linear and branched alkyl groups having hydrogen and 1-10 carbon atoms; And R ₁₆ is a nucleophilic group selected from the group of hydroxyl, mercaptan, and primary or secondary amines and / or electrophilic group selected from derivatives of halogen and methane sulfonate, p-toluene sulfonate and trifluoromethane sulfonate It is a linear or branched alkyl group having 1-4 carbon atoms substituted with.

Preferably, R ₁₆ is hydroxylmethyl, hydroxylethyl, chloromethyl or chloroethyl. The preparation of the oxetane compound consisting of hydroxyl groups is described in J. B. Chem. J. Am. Of JB Pattison. Chem. Soc., 79 (1957), pp. 3455-3456.

The hydroxyl-functional oxetane compound can be converted to the ester-containing oxetane via transesterification with the appropriate ester R ₁₇ (COOR ₁₈ ) _n , where n is an integer of at least 1 and R ₁₇ is 1- Saturated or unsaturated alkyl, aryl or acyl radicals having 40 carbon atoms and optionally substituted with reactive groups such as vinyl, carbonyl, carboxyl ester or hydroxyl groups, R ₁₈ is an alkyl group having 1-4 carbon atoms . R ₁₈ is preferably methyl, ethyl or propyl. The alcohol (R ₁₈ OH) released in transesterification can be separated from the reaction mixture, for example by distillation. Such suitable esters can be, for example, methyl esters of fatty acids, mixtures of fatty acids such as Henkel's Edeno ME C610 (tradename) and dimethyl esters of dimer fatty acids such as Unipole's Freepol 1009. have.

The ester group-containing oxetane compound may also be a polymer, wherein the oxetane compound is a terminal group or a side chain group. In this case, R ₁₇ may be a polymerizable group such as polyester, polyether, polyacrylate, polyamide or polyurethane. Suitable polyesters can be obtained by nucleophilic addition of carbanions to α, β-unsaturated carbonyl compounds. Likewise suitable are ester group terminated polyesters derived from polycarboxylic acids, polyols or their ester-forming equivalents. Preferably R ₁₈ may be used.

Other examples include hydroxyl-functional oxetane and adducts in which diethyl fumarate and diethyl malonate are converted to tetraethyl esters of 1,1,2,3-propane tetracarboxylic acid. In the presence of diols or polyols, terminal oxetane-functional polyesters are formed.

The hydroxyl-functional oxetane compound can also be converted using acid chloride (R ₁₇ (COCl) _n ).

Preferably, R ₁₇ is a group having a high molecular weight, such as pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or the above polymers. The resulting BOE compounds are non-volatile or slightly volatile because of their high molecular weight, and surprisingly low in viscosity, making them suitable as reactive diluents.

Halogen-functional oxetane can be converted to ester-functional oxetane by reacting with a carboxylate salt such as silver or an ammonium compound such as substituted or unsubstituted ammonium salt.

It is known that the conversion of ester-functional oxetane compounds in the BOE-functional compounds takes place in the presence of strong Bronsted or Lewis acids or organic complexes thereof. Lewis acids are preferred. Examples of the Lewis acid include AlCl ₃ , SbCl ₅ , BF ₃ , BCl ₃ , BeCl ₂ , FeCl ₃ , FeBr ₃ , SnCl ₄ , TiCl ₄ , ZnCl ₂ and ZrCl ₄ and their organic complexes, for example BF ₃ Et _{2 O, BF 3 -2CH 3 COOH} , BF 3 -2H 2 O, BF 3 -H 3 PO 4, BF 3 - (CH 3) 2 O, BF 3 -THF, BF 3 -2CH 3 OH, BF 3 - 2C ₂ H ₅ OH and BF ₃ -C ₆ H ₅ CH ₂ . In particular _{BF 3 Et 2 O, BF 3} -2CH 3 COOH , and SnCl ₄ are preferred. Preference is given to 0.001-0.1 moles of catalyst per mole of oxetane compound, in particular 0.004-0.08 mole / mole. It is also known that such conversion can take place in the presence of a small amount of solvent and, if desired, without solvent. In the above, the term solvent refers to a solvent conventionally used in organic chemistry and has been described for the conversion of an oxetane compound. The conversion takes place in the range of -100 to 200 ° C, preferably in the range of 0 to 80 ° C. The conversion time is 30 minutes to 2 days, yielding at least 90% yield.

Various methods can be used to prepare SOE-functional compounds. One method is to react an epoxy-functional compound such as butyl glycidyl ether with a lactone such as caprolactone or butyrolactone. Optionally, the SOE-functional polymer may be prepared in an epoxy-functional polymer such as polyacrylate of glycidyl (meth) acrylate using lactone or in polylactone using monoepoxide. Again a catalyst such as Lewis acid or Bronsted acid can be used, preferably paratoluene sulfonic acid or BF ₃ Et ₂ O.

SOE-functional compounds can also be prepared by reacting pentaerythritol and triethyl orthopropionate with certain trimethyl benzenes that can be used as solvents in the presence of paratoluene sulfonic acid. Surprisingly, a compound having two SOE groups is synthesized in such a manner that the structure of Formula 5 is very selective.

(Formula 5)

The invention will be further described with reference to the following examples.

In this example, the following abbreviations are used:

Paratoluene sulfonic acid: PTSA

Dibutyl Tin Dilaurate: DBTL

Methyl Amyl Ketone: MAK

Ethyl Amyl Ketone: EAK

Boron trifluoride etherate: BF ₃ Et ₂ O

Dibutyl phosphate: DBP

Dodecyl Benzene Sulphonic Acid: DDBSA

In the present examples, the following compounds are used.

Henkel's Edenor® ME C6-10, a mixture of fatty acid methyl esters with the following chain length distribution: C6: 1-8%, C8: 40-60%, C10: 30-50%, C12: 0-5%

Byk 333 is a silicone surface additive, manufactured by Byk Chemie.

Byk 300 is a flow additive, manufactured by Byk Chemie.

Byk 322 is a flow additive and is a Byk Chemie product.

Byk 355 is a flow additive and is a Byk Chemie product.

DisperByk 110 is a dispersant and is manufactured by Byk Chemie.

DisperByk 166 is a dispersant and is a product of Byk Chemie.

Nacure 5076 is 70% DDBSA in isopropanol and is from King Industries.

Fascat 4202 is a 10% DBTL solution in xylene, manufactured by Air Products.

Desmodur ™ N3400 is a uretdion based aliphatic polyisocyanate of hexamethylene diisocyanate, manufactured by Bayer.

Desmodure® VL50 is a diphenylmethane diisocyanate-based aromatic polyisocyanate product from Bayer.

Desmodure® N3390 is an isocyanurate aliphatic polyisocyanate of hexamethylene diisocyanate and is a Bayer product.

Desmodure® L75 is a toluene diisocyanate-based aromatic polyisocyanate product from Bayer.

Desmodure® LS2025 is a low hexamethylene diisocyanate-based aliphatic polyisocyanate product from Bayer.

Vestanat® T1890E is an isocyanurate aliphatic ring polyisocyanate of isophorone diisocyanate, manufactured by Huels.

Sikkens' Hardener MS is made up of Desmodure® N3390 (S.C. = 36%).

Polyester polyol A is a high quality solid polyester having a hydroxyl number of 148, an acid number of 8.8 and a Mn of 1888 (GPC, Polystyrene Standard). This polyester has a viscosity of 7 Pa · s in 81% -solution in butyl acetate.

Polyester polyol B is a 1,4-dimethanol cyclohexane, hexahydrophthalic anhydride, 3,5,5-trimethyl hexanoic acid, trimethylol propane and 1,1-disubstituted branched decane monocarboxylic acid glycidyl ester system . This polyester polyol has a solids content of 70%, a viscosity of 580 mPa.s at 20 ° C, a Tg of -3 ° C, an acid value of 0.2, a hydroxyl number of 160, a Mn of 1090, and a Mw of 3140. (Measured by gel permeation chromatography using polystyrene as a standard).

Polyester polyol C is phthalic anhydride, hexahydrophthalic anhydride, 3,5,5-trimethyl hexanoic acid and trimethylol propane system. This polyester polyol has a solids content of 80.5%, a viscosity of 7.5 Pa.s at 20 ° C, a Tg of -2 ° C, an acid value of 9.3, a hydroxyl number of 145, Mn of 1900, and Mw of 4500 (Measured by gel permeation chromatography using polystyrene as standard).

Sikkens' Autoclear MS 2000 consists of a polyacrylate polyol resin and 0.02% DBTL (solid). S.C. is 46%.

Resimene RF 4518 is a melamine resin from Monsanto.

Irgazin DPP Red BO is a bright red pigment and is a Ciba-Geigy product.

Zinc phosphate ZP 10 is a preservative and is manufactured by Heubach.

Tioxide TR 92 is a titanium dioxide pigment, manufactured by Tioxide.

Aerosil R972 is a silica compound, manufactured by Degussa.

Clay grade C made in China is an extender, and ECC International Ltd. Product.

Blank fix is an extender and is from Sachtleben Chemie GmbH.

Tinuvin 1130 is a UV stabilizer and is a Ciba-Geigy product.

Tinuvin 123 is a HALS stabilizer and is a Ciba-Geigy product.

Solvesso 100 is an aromatic solvent mixture, manufactured by Exxon.

Sikkens products 1.2.3. Thinner slow is a solvent mixture.

Unless otherwise stated, the properties of the coating composition and the film obtained are measured as follows.

Viscosity was measured at DIN flow cup number 4 according to DIN 53211-1987. Viscosity is expressed in seconds.

Portlife is defined as the time period in which the viscosity of the coating composition is doubled after initiating the mixing of all compounds.

Drying time is measured as follows. Tension bars are added to the coating composition or sprayed and applied to the steel sheet. The time until the end of the third phase in the layer is dried is measured using a BK drying recorder. The term third phase means a dry phase while the needle of the BK drying recorder (trade name) becomes small and the intra-membrane tight scratch is no longer filled.

The coating is "touch dry" when the mark resulting from the squeeze with the thumb disappears after 1 or 2 minutes.

Solids content (S.C.) is measured after 1 day drying at room temperature and 1 hour drying at 150 ℃. Theoretical maximum S.C. is S.C. when all BOE or SOE are hydrolyzed and bound in a dry membrane. Theoretical minimum S.C. is S.C. when all BOE or SOE are assumed to evaporate in the dry membrane.

Gloss is measured according to ISO 2813: 1994. Gloss is expressed in gloss units.

Solvent resistance is measured by exposing the coated steel panel to MEK. The time required to soften the paint film to a pencil hardness of 2b provides resistance.

Example 1

Preparation of 4-methylol-1-methyl-2,6,7-trioxabicyclo [2.2.2] octane (BOE 1)

The flask with a stirrer, distillation column, nitrogen inlet, heating jacket and thermometer was charged with 486 g of triethyl orthoacetate, 408 g of pentaerythritol, 300 g of diethylene glycol dimethyl ether and 0.9 g of PTSA. The mixture was gradually heated to 170 ° C. for at least 5 hours. 490 g of distillate were obtained during this time. The distillate mostly contained ethanol and small amounts of diethylene glycol dimethyl ether. The temperature was lowered to 100 ° C. and the remaining diethylene glycol dimethyl ether was distilled off under reduced pressure (30 mbar). The residue was used for vacuum distillation. A fraction with a boiling temperature of 126-130 ° C. at a pressure of 4 mbar yielded 426 g of oil. This oil solidified into a clean solid having a melting point of 99 ° C. and had the following structure.

Example 2

Preparation of 1,4-diethyl-2,6,7-trioxabicyclo [2.2.2] octane (BOE 2)

The flask as described in Example 1 was filled with 529 g of triethyl orthopropionate, 402 g of trimethylol propane, 330 g of diethylene glycol dimethyl ether and 0.9 g of PTSA. The mixture was heated with 402 g of distilled ethanol at 140 ° C. for 0.5 h. The temperature was lowered to 100 ° C. and the remaining diethylene glycol dimethyl ether was distilled off under reduced pressure. The residue was added to vacuum distillation. The fraction having a boiling temperature of 54 ° C. at a pressure of 0.5 mbar has the following structure and yields 370 g of a clean, low viscosity liquid having a boiling point of 223 ° C. at atmospheric pressure.

Example 3

Preparation of Spiro-orthoesters (SOE 1)

The flask as described in Example 1 was charged with 125 g of trimethyl benzene, 89 g of triethyl orthopropionate, 68 g of pentaerythritol and 0.125 g of PTSA. The mixture was heated at 140 ° C. for 4 hours. After 2 hours ethanol distillation was stopped. Overall, only 36 g of ethanol were distilled off. Only a portion of pentaerythritol was dissolved in the reaction mixture. After cooling, the mixture was neutralized with potassium carbonate and all solids were filtered off. A portion of triethyl orthopropionate that did not react with trimethyl benzene was distilled off under reduced pressure and the residue was distilled under vacuum. A fraction with a boiling temperature of 140-145 ° C. at a pressure of 1 mbar yielded 37 g of oil. After analysis via H ¹ and ¹³ C-NMR spectroscopy, it was found that a spiro-orthoester compound of the following structure was formed.

Example 4

Preparation of Spiro-orthoesters (SOE 2)

The flask with stirrer, reflux cooler, dropping funnel, heating jacket and thermometer was charged with 43 g of γ-butyrolactone, 65 g of diethyl ether and 1.4 g of a 35% -BF ₃ Et ₂ O solution in diethyl ether. To the mixture was added 93 g of butyl glycidyl ether for 1 hour. The reaction was slightly exothermic. The temperature was maintained in the range of 23-28 ° C. by cooling to the outside. After addition of butyl glycidyl ether, the mixture was kept at this temperature while stirring continued for 3 hours. The reaction mixture was then heated to reflux for 1 hour. After cooling to room temperature, 2 g of sodium carbonate were added and stirring continued at room temperature overnight. The solid was filtered off and 1 g more sodium carbonate was added. Diethyl ether was distilled off under reduced pressure at room temperature. The residue was vacuum distilled. A fraction with a boiling point in the range 45-65 ° C. under a pressure of 0.1 mbar gave 31 g of a clear liquid. After analysis (H ¹ and ¹³ C-NMR spectroscopy), it was found that spiro-orthoesters of the following structure were formed.

Example 5

Preparation of A: 3-ethyl-3-hydroxymethyl oxetane

This oxetane is described in J. Am. Chem. Soc., 79 (1957), p. 3455 by J. B. Pattison and by JMS-Pure Appl. Prepared as described in Chem., A30 (1993), p. 189.

Trimethylol propane (1023.6 g, 7.63 moles), diethyl carbonate (901.3 g, 7.63 moles) and potassium hydroxide (0.77 g) were charged to a 5-L three necked flask. The reaction mixture was heated to reflux (123 ° C.). After lowering the reaction temperature to 105 ℃, ethanol distillation was started. The reaction temperature was raised to 150 ° C. At the end of the distillation, vacuum (15 mbar) was used to remove the remaining ethanol and diethyl carbonate from the reaction mixture. The reaction mixture was then heated to 220 ° C. A gas was observed to form and a clean oil was obtained which was identified as 3-ethyl-3-hydroxymethyl oxetane at 130 ° C. under reduced pressure (40 mbar). Yield was 698.0 g (79%); ¹ H NMR (CDCl ₃ ) d (ppm): 0.9 (t, ³ H); 1.7 (q, ² H); 3.1 (t, ¹ H); 3.7 (d, ² H); 4.4 (dd, ⁴ H).

B: Preparation of 3-ethyloxetan-3-yl methyl laurate

Ethyl laurate (228.4 g, 1.0 moles), 3-ethyl-3-hydroxymethyl oxetane (116.0 g, 1.0 moles), dibutyl in a three necked flask (1 L) with a Vigreux distillation column Tin oxide (0.34 g) and xylene (25.0 g) were charged. The reaction mixture was heated to reflux. At 170 ° C., ethanol began to distill. The reaction mixture was heated so that ethanol distillation proceeded smoothly. All ethanol was distilled off at a reaction temperature of 250 ° C. Xylene was removed under reduced pressure. ^{According to 1} H NMR analysis, the residue (298.7 g) was pure 3-ethyloxetan-3-yl methyl laurate. This product was solidified at room temperature.

_{^{1 H NMR (CDCl 3) d}} (ppm): 0.9 (2 × t, 6 H); ^{1.3 (brs, 16 H),} 1.65 (m, 2 H); 1.8 (q, ² H); 2.4 (t, ² H); 4.2 (s, ² H); 4.45 (dd, ⁴ H).

C: Preparation of 4-ethyl-1-undecyl-2,6,7-trioxabicyclo [2.2.2] octane

This reaction was carried out under nitrogen atmosphere. 3-ethyloxetan-3-yl methyl laurate (270.0 g, 904 mmoles) and BF ₃ Et ₂ O (1.0 g) prepared as described in Example 5B were mixed in a Erlenmeyer flask. The reaction mixture was cloudy but cleared after a few minutes. After standing up overnight, ¹ H NMR analysis showed that virtually all oxetane esters were converted to the corresponding BOE compounds. The reaction mixture was vacuum distilled. At 155 ° C./1 mbar, 4-ethyl-1-undecyl-2,6,7-trioxabicyclo [2.2.2] octane was obtained. Yield was 205 g (76%).

¹ H NMR (CDCl ₃ ) d (ppm): 0.75 (t, ³ H); 0.8 (t, ³ H); 1.2 (brs, ¹⁶ H); 1.35 (brm, ² H); 1.50 (t, ² H); 3.80 (s, ⁶ H).

Example 6

A: Preparation of 3-ethyl-3-hydroxymethyl oxetane

Trimethylol propane (1489 g, 11.1 moles), dimethyl carbonate (1201 g, 13.3 moles) and potassium hydroxide (5.38 g) were charged into a 5 L three-necked flask equipped with a stirrer, reflux cooler, nitrogen inlet, heating jacket and thermometer. The reaction mixture was heated to reflux (86 ° C.) and refluxed for 2 hours. This temperature was lowered to 80 ° C. Then, the temperature of this reaction mixture was raised to 155 degreeC within 6 hours. At the end of distillation, 890 g of distillate containing methanol and dimethyl carbonate in a ratio of 60 to 40 were obtained. The temperature was lowered to 120 ° C. and ethanol and dimethyl carbonate remaining under vacuum (200-40 mbar) were removed from the reaction mixture (about 14 g). The reaction mixture was then heated stepwise to 180 ° C. Under a CO ₂ stream and reduced pressure (60-40 mbar), a clear oil identified as 3-ethyl-3-hydroxymethyl oxetane was obtained. Yield was 860 g.

B: Preparation of Fatty Acid 3-ethyloxetan-3-yl Methyl Ester

In a flask (5 L) as in Example 6A, Edenor® ME C6-10 (1268 g, 7.4 moles), 3-ethyl-3-hydroxymethyl oxetane (858.4 g, 7.4 moles) and di of Example 6A Butyl tin oxide (2.13 g) was charged. The reaction mixture was heated to reflux. At 150 ° C. methanol began to distill. The reaction mixture was heated to 240 ° C. in 5 hours. 197 g of distillate consisting mainly of methanol (83% of theory) was obtained. The temperature was lowered to 150 ° C. and 40 g of distillate remaining under vacuum (40 mbar) were removed. This residue (1834 g) was found to have the following structure, where R is a mixture of pentyl, heptyl, nonyl and undecyl groups;

C: Preparation of crude 4-ethyl-1- (C5-11 alkyl) 2,6,7-trioxabicyclo [2.2.2] octane (BOE 3A)

This reaction was carried out under nitrogen atmosphere. The fatty acid 3-ethyloxetan-3-yl methyl ester (1834 g) prepared as in Example 6B was cooled to 50 ° C. and BF ₃ -CH ₂ COOH (4.59 g) was carefully added thereto. The reaction mixture was heated to 70 ° C. and maintained at this temperature for 6 hours. The reaction mixture was then cooled to 50 ° C. and 2.45 g of triethyl amine was added to neutralize the catalyst. 1% filter additive was added to the obtained residue and filtered. This filtrate was 1730 g and contained about 78% BOE and 22% polymer.

D: Preparation of pure 4-ethyl-1- (C5-11 alkyl) -2,6,7-trioxabicyclo [2.2.2] octane (BOE 3B)

Into a flask (5 L) as in Example 6A was charged 1730 g of crude BOE 3A prepared in Example 6C. The reaction mixture was heated to 140 ° C. and reduced to 40 mbar. The temperature was gradually raised to 240 ° C. to obtain a clear liquid. 1235 g of what was collected was found to be pure BOE 3B with the following structural formula, where R is a mixture of C5, C7, C9 and C11 alkyl groups;

Example 7

A: Preparation of Dimer Fatty Acid Dimethyl Ester

Prepol 1009 dimer fatty acid (742g, 1.31moles, 2.62eq.acid) from Unichema, methanol (2000g) and Amberlyst 15 acidic ion exchange resin (40g) from Rohm & Haas were mixed with agitator, reflux cooler, The flask was filled with a nitrogen inlet, thermocouple and heating jacket. The reaction mixture was heated to reflux (65 ° C.). The samples were regularly analyzed by infrared spectroscopy. Heating was continued until the carbonyl signal of carboxylic acid at 1710 cm ⁻¹ disappeared in the infrared spectrum (about 18 hours). The reaction mixture was cooled to room temperature and the liquid was decanted from the ion exchange resin. This liquid was rotary evaporated to evaporate all the methanol. The evaporated residue was diluted with diethyl ether (300 g). The ether solution was washed with aqueous 10% sodium carbonate solution (500 g) followed by water (500 g) in three portions. Magnesium sulfate (30 g) was added to the organic layer and stirred for 12 hours. This liquid was filtered and diethyl ether distilled by rotary evaporation. The evaporation residue was colorless oil, Freepol 1009 dimethyl ester (752 g, 96% theoretical).

B: Preparation of Dimer Fatty Acid Di-3-ethyloxetan-3-yl Methyl Ester

Prepol 1009 dimethyl ester of Example 7A (713.5 g, 2.4eq.), 3-ethyl in Example 6A, in a flask equipped with a stirrer, distillation head, nitrogen inlet, thermocouple, vacuum line and heating jacket 3-hydroxymethyl oxetane (278.4 g, 2.4 moles) and dibutyl tin oxide (1.0 g) were charged. The reaction mixture was heated stepwise to 240 ° C. within 4 hours. 47 g of methanol was distilled off during this time. The temperature was lowered to 160 ° C. and vacuum was applied. The pressure was gradually reduced to 20 mbar over 3 hours. Residual methanol was distilled off during this time. When distillation stopped, the reaction mixture was cooled to room temperature. The light yellow oil product was analyzed by infrared spectroscopy. There was no hydroxyl group at 3400 cm ^-1 as seen in the infrared spectrum. Yield was 914 g.

C: Preparation of BOE Derivatives (BOE 4) of Dimer Fatty Acid Di-2-ethyloxetan-3-yl Methyl Ester

Into the flask as in Example 7A was filled the dimer fatty acid di-2-ethyloxetan-3-yl methyl ester (914 g) and butyl acetate (1400 g) prepared in Example 7B. At room temperature, BF ₃ -Et ₂ O (9.15 g) was added above for 15 minutes. The reaction mixture was heated to 50 ° C. and maintained at that temperature for 10 hours. Next, the reaction mixture was cooled to room temperature and 6.5 g of triethyl amine was added. A precipitate formed, which was filtered off. The product analyzed by infrared spectroscopy showed a small signal at 3400 cm ⁻¹ indicating hydroxyl functionality. Phenyl isocyanate (9 g) was added to the product. After 1 hour, infrared spectroscopy at room temperature showed no hydroxy functionality (no signal at 3400 cm ⁻¹ ) and no isocyanate functionality (no signal at 2270 cm ⁻¹ ). Some of the butyl acetate was evaporated. The final product has a solids content of 82.7% and is a yellow oil.

Example 8

A: Preparation of Oxetane-functional Polyester

Diethyl malonate (686.0 g, 4.3 moles), neopentylene glycol (358.1 g, 3.45 moles), 3-ethyl-3-hydroxymethyl oxetane (196.2 g 1.7) in a 2-liter three-neck flask with distillation apparatus moles), dibutyl tin oxide (1.2 g) and xylene (100 g). The reaction mixture was heated to reflux. At 189 ° C., ethanol distillation was started. The distillation rate was controlled by slowly increasing the reaction temperature. At a temperature of 210 ° C., all ethanol was distilled off. Xylene was removed from the reaction mixture under reduced pressure. The oxetane-functional polyester obtained had a molecular weight of Mn = 1021 and Mw = 1875 (GPC, Polystyrene Standard).

B: Preparation of BOE-functional Polyester

This reaction was carried out under nitrogen atmosphere. In a round bottom flask was charged oxetane-functional polyester (800.0 g, 1.6 equivalents of oxetane) and BF ₃ Et ₂ O (about 1 g) prepared in 8A in Example. An exothermic reaction occurred. The temperature of the reaction mixture was raised to 62 ° C. Next, it cooled by water bath. After one night it was found that virtually all oxetane groups were converted to the corresponding BOE group (BOE signal at d (ppm) 4.0 in ¹ H NMR). The obtained BOE-functional polyester had a molecular weight of Mn = 1648 and Mw = 7449 (GPC, polystyrene standard).

Example 9

A: Preparation of 3-ethyloxetan-3-yl methyl acrylate

Synthesis is performed by Chem. Gas such as P.G.Gassman. (1989), p. 837.

This reaction was carried out under nitrogen atmosphere. To a mixture of 3-ethyl-3-hydroxymethyl oxetane (170.6 g, 1.50 moles) and triethyl amine (153.8 g, 1.52 moles) in tetrahydrofuran (500 g) cooled in an ice bath, acryloyl chloride ( 137.5 g, 1.52 moles) was added dropwise. The reaction mixture was stirred at room temperature for 1 hour. 500 g of water was added to the reaction mixture. The organic layer was separated from the aqueous layer. The aqueous layer was extracted with diethyl ether (2 x 500 mL). The combined organic layer was dried over saturated NaCl solution and magnesium sulfate. After filtering the ether layer, a volatile organic compound was removed under vacuum using a rotary vacuum evaporator. The residue was distilled under vacuum. 3-ethyloxetan-3-yl methyl acrylate was separated as clear oil at 122 ° C./19 mbar. Yield was 200.4 g (80%).

_{^{1 H NMR (CDCl 3) d}} (ppm): 0.92 (t, 3 H); 1.80 (q, ² H); 4.30 (s, ² H); 4.48 (dd, ⁴ H); 5.88 (d, ¹ H); 6.18 (dd, ¹ H); 6.45 (d, ² H).

B: Preparation of Polyacrylate Having BOE-functional Side Group

Butyl acrylate (38.0 g), trimethyl cyclohexyl methacrylate (Nourycryl MC 109, 45.0 g), 3-ethyloxetan-3-yl methyl acrylate (17.0 g), t-butylperoxy-3 A mixture of 5,5-trimethyl hexanoate (Trigonox ™ 42S, 3.0 g) and dodecyl mercaptan (2.0 g) was added over a 2 hour cycle to reflux the MAK (42.7 g). The temperature was raised from 155 ° C. to 169 ° C. during the feed. After feeding, a Trigonox® 42S (0.25 g) solution in MAK (1.0 g) was added twice more for 30 minutes. The reaction mixture was cooled to room temperature. Next, BF ₃ Et ₂ O (0.75 g) was added. The resulting resin had the following physical characteristics: Mn = 1736, Mw = 4567, Viscosity = 1.28 Pa.s and SC = 74.7% (30 min after heating at 150 ° C.).

Example 10 and Comparative Example A

BOE as main binder reacting with polyisocyanate-containing compounds

Desmodure ™ N3390 was mixed with (2,2-dimethylol-n-butyl) propionate (DBP) and BOE2, respectively (130 eq.% NCO calculated on (latent) hydroxyl). 0.15 wt.% DBTL calculated on solids and 0.33 wt.% Of PTSA calculated on DBP were added to the DBP mixture, while DB5 0.15 wt.% Calculated on solids and 0.83 wt. On PTSA calculated on BOE2. % Was added to the BOE2 mixture. The two mixtures were diluted to a spray viscosity (± DINC4 18 ″) with a 50:50 mixture of MAK / EAK. For desirable viscosity it was necessary to add 270 g of MAK / EAK to the DBP mixture. In contrast, only 200 g of BOE 2 mixture was needed. That is, using BOE 2 reduces the amount of diluent required to obtain a sprayable composition by 70 g. Port life and drying time data are shown below. Fort life means the time during which the viscosity of the coating composition is increased to 30 ″ DINC4. After drying, the coating composition was sprayed onto the steel sheet to obtain a 50μ layer. It is evident that the coating composition according to the invention has a longer potlife and shorter drying time, ie a particularly preferred potlife: dry time ratio.

Example Port Life Drying time (minutes) A DBP 10 minutes 140 9 BOE 2 ＞ 1 day 100

Example 11 and Comparative Example B

SOE as main binder reacting with polyisocyanate-containing compounds

Two samples of SOE2 were added to both mixtures of Desmodure N3390 (NCO 130eq.% Calculated on latent hydroxyl) and DBTL 0.3wt.% Calculated on solids, while the PTSA calculated on SOE2 was calculated. 1.1 wt.% Was added to one of the mixtures. The coating composition was added to the steel sheet with a 100μ tensile rod. S.C. results are shown below. These show that PTSA affects unblocking hydroxyl groups in the SOE composition.

Example PTSA S.C. Theoretical maximum Measure 11 1.1wt.% 83.6% 80.4% B - 83.6% 59.1%

Example 11-28

BOE as main binder reacting with polyisocyanate-containing compounds

4.3 parts by weight of BOE 2 were mixed with 10.8 parts by weight of Desmodure N3390 (100 eq.% NCO calculated on latent hydroxyl). 0.3 wt.% Of DBTL calculated on solids was added. Several acids were added as catalyst for the hydrolysis of the BOE compound. The coating composition was applied to the steel plate with a 100μ tensile rod. The data is shown below. The percentage of catalysts mentioned in the table below is based on the amount of BOE2. PTSA has a pKa of 0.5-1, pKa of benzoic acid (BZ) is 4.2, and pKa of DBF is 2-3. S.C. is measured after 1 day drying at room temperature and 1 hour drying at 120 ° C.

Example catalyst(%) S.C.Film Theoretical maximum S.C. Theoretical minimum S.C. Gel time Dry contact time 12 - 72.2 93.2 62.6 ＞ 1 week 3 hours 13 1.63 ZnCl ₂ 64.3 92.4 60.6 ＞ 1 week 1 hours 14 1.63 BZ 70.2 89.2 56.6 ＞ 1 week 2 hours 15 0.47 PTSA 71.4 92.4 62.0 ＞ 1 week 4 hours 16 1.63 PTSA 89.4 92.4 60.6 ＞ 1 week 3 hours 17 1.63 BF ₃ Et ₂ O 87.5 92.4 60.6 ＞ 1 week ＞ 4 hours 18 1.63 DBP 88.0 92.4 60.6 ＞ 1 week ＞ 5 hours

In all cases, portlife is excellent. By using strong acids or large amounts of acid, S.C. is improved. Example 16 provides the best results with high S.C. and moderate drying time.

Comparative Example C and Comparative Example D

Example 12 was repeated. 2-ethyl-1,3-hexanediol was added instead of 4.3 parts by weight of BOE 2. Two mixtures were prepared, each consisting of 0.005 parts by weight and 0.05 parts by weight of DBTL calculated on solids. For the first mixture, 0.5 hour potlife was measured and for the second mixture, once every minute. When using 0.05 parts by weight of DBTL, the contact drying time of the coating composition was at least 4 hours at room temperature.

Example 19 and Comparative Example E

BOE as a reactive diluent in a composition consisting of polyester polyols and polyisocyanate-functional compounds

The dilution ability of BOE 2 was compared with ethylbutyl propane diol (EBP), a hydroxy-functional compound in higher solid urethane coating formulations. 130eq.% Of NCO (Desmodure N3390) was used on the (latent) hydroxyl. Polyester polyol A was used as binder. The catalyst used for BOE hydrolysis was PTSA and the catalyst for the isocyanate-hydroxyl reaction was DBTL. From the table below it can be seen that when BOE 2 is used, the solvent present per kilogram of paint is less than 65 g (about 65 g per liter). Due to the lower equivalent of BOE 2 compared to EBP, relatively little isocyanate is required for crosslinking. All amounts are parts by weight.

Example E Example 19 Polyester A 40 40 BOE 2 - 8.1 EBP 8.1 - Desmodure® N3390 54.4 61.9 DBTL 0.12 0.06 PTSA - 0.4 (4.9 wt.% Calculated on BOE 2) MAK 30.8 26.3 EAK 16 9.5 Shellsol D 7.34 8.4 Viscosity (DINC4) 18.2 ″ 17.6 ″

Example 20 and Comparative Example F

BOE as main binder with polyisocyanate-functional compounds

The result of BOE 2 is a commercially available reactive diluent from Angus Chemical Company, oxazolidine zolidine (trade name) RD 20 (1-Aza-3,7-dioxo-bicyclo-2,8-diisopropyl-5- Ethyl- [3,3,0] -octane).

Desmodure N3390 was crosslinked with two compounds (130 eq.% NCO calculated on (latent) hydroxyl). The coating composition was diluted with MAK: EAK (50:50) to a viscosity of 19 ″ DINC4. 0.1 wt.% DBTL calculated on solids and 0.57 wt.% PTSA calculated on BOE 2 were added. The two compositions were sprayed onto bare steel. The temperature during drying was 20 ° C. and the relative humidity was 70%. It can be seen from the following that when BOE 2 is used, the port life is longer, while the drying process is faster.

Example Viscosity after 6 hours (DINC4) Drying (minutes) 20 BOE 2 23 ″ 175 F Zolidine® 29 ″ 400

Example 21 and Example 22 and Comparative Example G

BOE as main binder with polyisocyanate-functional compound and acid generator

5.3 parts by weight of BOE 3B, 10.8 parts by weight of Desmodure N3390, 1.5 parts by weight of 10% DBTL in butyl acetate, 20% 2-methyl-1- [4- (methylthio) from Vartelli Lamberti Spa, Varese, Italy in butyl acetate A coating composition containing 1.06 parts by weight of phenyl] -2- [4-methylphenylsulfonyl] propan-1-one (MDTA) was prepared.

The coating composition was applied on two steel plates with a tension rod to give a 50 μm film thickness after drying. Five minutes after the addition, one steel plate was exposed to UV-A for 1 minute (Example 21). After 1 hour at room temperature, the coating was contact dried to clean. The uncoated coating (Comparative Example G) was contact dried after 5 hours, but was very problematic due to unhydrolyzed BOE. The coating composition was stored at 50 ° C. for 1 week. Then it was used as above (Example 22). The coating was again contact dried for 1 hour. The storage stability of MDTA containing the coating composition is very good.

Example 23 and Comparative Example H

Polyacetal-functional resins and BOE as main binder

Two coating compositions were prepared as shown below (all amounts by weight). The polyacetal-functional resin is a copolymer of glycerol cyclocarbonate methacrylate and styrene, on which amino butyraldehyde dimethyl acetal was added (S.C. = 62% in butyl acetate (wt.eq. acetal group = 951)). BOE 4 has 83% S.C. in butyl acetate (wt.eq. BOE = 476). The cure was diluted with a 10% solution in butyl acetate.

As can be seen from the following results, the composition of the present invention is excellent in port life. The coating composition was applied with a tensile rod on the steel sheet to provide a 50 μm film thickness after drying. The contact drying time of the coating composition of the present invention is the same as that of the comparative coating composition as well as solvent resistance to MEK.

Example 23 Comparative Example H Polyacetal-functional resin 9.5 9.5 BOE 4 4.8 --- Hydrolyzed BOE 4 --- 4.8 10% Secure 5076 1.0 1.0 Gelation time in the pot ＞ 2 weeks 5 hours Contact drying time 10 minutes 10 minutes MEK resistance after 1 week 2 2

Example 24 and Comparative Example I

Polyalkoxysilane-functional Resin and BOE as Main Binder

Two compositions were prepared as described below (all amounts are in parts by weight). The polyalkoxysilane-functional resin is an adduct of 1 mole of diethyl malonate and 2 moles of 3-amino propyl trimethoxy silane (AMEO-T from Wacker) (SC = 95.6% (wt.eq.Si (EtO) in xylene) ) ₃ groups = 255)). BOE 4 has 83% SC in butyl acetate (wt. Eq. BOE = 476). The cure 5076 was diluted with 10% solution in butyl acetate.

As can be seen from the following results, the composition of the present invention is excellent in port life. The coating composition was applied with a tensile rod on the steel sheet to provide a 50 μm film thickness after drying. The contact drying time of the coating composition of the present invention is the same as that of the comparative coating composition as well as solvent resistance to MEK.

Example 24 Comparative Example I Polyalkoxysilane-functional Resin 5.1 5.1 BOE 4 4.8 --- Hydrolyzed BOE 4 --- 4.8 10% Secure 5076 0.9 0.9 Gelation time in the pot ＞ 2 weeks 1 hours Contact drying time 20 minutes 20 minutes MEK resistance after 1 week 2 2

Example 25

Melamine resin and BOE as main binder

The following coating compositions were prepared (all amounts by weight).

Example 25 Resimen RF 4518 8 BOE 3B 2 Cure 5076 0.6 Gelation time in the pot <1 hour Contact drying time 1.5 hours MEK resistance after 1 week 2

The results show that the composition consisting of melamine resin and catalyst is devoid of water to obtain very fast ring opening of the BOE compound. Therefore, the pot life is very short, and the coating composition requires a 2K component system or a block catalyst. The coating composition is added with a tensile rod on the steel sheet to obtain a 50 μm film thickness after drying.

Example 26 and Example 27

A solvent glass clearcoat component was prepared as follows. Coatings were prepared according to the 3-pack system. The first component is contained in the BOE compound, the second component is contained in the polyisocyanate, and the third component is contained in the acid catalyst. Solvent-glass is defined as VOC <100 g / l.

ingredient compound Example 26 Example 27 One BOE 3B 34.2 g 30.2 g Caster oil --- 6.0 g DBTL 0.51 g 0.54 g Byk 333 0.41 g 0.44 g 2 Desmodure® N3400 63.5 g 46.5 g Desmodure (trade name) VL50 - 1.48g 3 Cure 5076 1.37 g 1.45 g

Both compositions have a viscosity of 23 ″ (DINC4). The clearcoat was sprayed with a high volume low pressure sprayer (HVLP) on a steel panel coated with Sikkens' Autobase MM basecoat. The coating was cured at room temperature and 60 ° C. The appearance was excellent, the gloss was good, and the flow / level was good. It was also excellent in stone chip resistance, solvent resistance and adhesion.

Example 28 and Example 29

Solid Color Topcoat Compositions

Two solid color topcoat compositions were prepared based on BOE. In the first composition, the pigment was dispersed in BOE, while the polyester-based pigment paste was used in the second composition. Component 1 was milled on the bead mill until the particle size was less than 10 microns.

ingredient compound Example 28 Example 29 One BOE 3B 37.5 g --- Polyester polyol B --- 45.0 g Irgin DPP Red BO 33.6 g 24.7 g Disperbyk 166 16.8 g 17.0 g Butyl acetate 6.1g 6.6 g Solvesso 100 6.1g 6.6 g 2 BOE 3B 34.8 g 28 g Desmodour N3390 141.4 g 80 g DBTL 1.08g 0.96 g 3 Cure 5076 1.44 g 0.56 g Solvesso 100 17.0 g 4.0g Ethoxyethyl propionate 17.0 g 4.0g

Both coating compositions were sprayed onto steel panels made from conventional primers as automotive resurfacing topcoats. The appearance and use behavior were excellent. VOC levels were very low, about 250 g / l.

Example 30 and Example 31

Clear Coat Coating Composition

Two clearcoat coating compositions were prepared as follows. Both coating compositions have a viscosity of 16 ″ DINC4. The potlife of the coating composition of Example 30 is shorter than the potlife of the coating composition of Example 31 due to the presence of the hydroxy-functional polymer in BOE 3A. Both clearcoat compositions were sprayed onto a steel panel made of an Autobase MM basecoat from Sikkens using a HVLP sprayer. Room temperature curing of the coating composition of Example 30 is faster than curing of the coating composition of Example 31. The appearance and gloss of both coatings were excellent.

ingredient compound Example 30 Example 31 One BOE 3A 40 g - BOE 3B - 40 g DBTL (10% in butyl acetate / xylene (1/1)) 4 g 4 g Byk 322, Byk 355, Butyl Acetate (20/15/65) 2 g 2 g Solvesso 100 / ethoxyethyl propionate (1/1) 14 g 24 g 2 Des Modu (trade name) N3390 67.6 g 78.5 g 3 Cure 5076 1.14 g 1.14 g

Example 32 and Example 33

Clear Coat Coating Composition

Two clearcoat coating compositions were prepared as follows. Both clearcoat compositions were sprayed onto a steel panel made of an Autobase MM basecoat from Sikkens using a HVLP sprayer. Both clearcoats have excellent paint properties. The application characteristics were very good. The appearance and gloss were excellent.

ingredient compound Example 32 Example 33 One BOE 3B 34 g 34 g Polyester polyol B 7.5g --- Polyester Polyol C --- 7.5g DBTL (10% in butyl acetate / xylene (1/1)) 4.0g 4.0g Byk 322, Byk 355, Butyl Acetate (20/15/65) 8.56 g 8.56 g Solvesso 100 5.6 g 5.6 g Ethoxyethyl propionate 5.6 g 5.6 g Tinuvin 1130 0.1g 0.1g Tinuvin 123 0.05g 0.05g 2 Desmodour N3390 71.0 g 71.0 g 3 Cure 5076 0.98g 0.98g

Example 34 and Example 35

Primer composition

An ultra-high solid primer composition was prepared as follows. Component 1 was stirred at high speed for 15 minutes and then passed through a closed mill twice to give a powder level of less than 25 μm. Then, component 1 was mixed with components 2 and 3 mixed in advance.

ingredient compound Example 34 Example 35 One BOE 3B 17.0 g 17.0 g Disperbyk 110 1.4 g 1.4 g Toxide TR92 21.0 21.0 Zinc Phosphate ZP10 13.6 13.6 Blank Fix N 11.0 11.0 Chinese clay grade C 23.5 23.5 Aerosil R972 0.8 0.8 Solvesso 100 6.0 6.0 Ethoxyethyl propionate 5.9 5.9 2 Fascat 4202 0.25 0.25 Cure 5076 0.35 0.35 Byk 300 0.8 0.8 3 Desmodur L75 --- 23.4 Vestanath T1890E 25.1 --- Desmodure LS2025 25.1 25.1 Butyl acetate 4.0 4.3 Solvesso 100 7.0 7.5

Two primer coating compositions were applied on a steel panel with conventional spraying equipment and had a spray viscosity of 2.0 poise (measured with Sheen Rotothinner) at VOCs near 290 g / l. Coating compositions and / or regular care finish tops of the invention, such as those exemplified in Examples 26-29 by drying at room temperature (overnight) or 60 ° C. (30 minutes) (as well as colored topcoats as well as base / clear systems) A hard, good sandable coating can be obtained that can be top coat with a regular carrefinish topcoat.

The advantages over conventional Medium Solid 2k primer / filler materials when used in today's care finish market are very low VOCs, long port life and high assembly behavior. Advantages compared to conventional high-grade solid primer compositions composed of imine crosslinkers are long pot life, fast drying at 60 ° C. and no volatile block components are released (from crosslinkers such as ketamine, aldimine and oxazolidine) Similar to ketones and aldehydes).

Example 36, Example 37 and Example 38 and Comparative Example J

BOE 3B as a Reactive Diluent in Clearcoat Coating Compositions

Commercially available clearcoat component Sikkens Autoclear MS 2000 was diluted with different amounts of BOE 3B. The composition is described below. Component 1 was mixed with components 2 and 3 and sprayed onto a steel panel made of an Autobase MM basecoat from Sikkens using a HVLP sprayer.

ingredient compound Comparative Example J Example 36 Example 37 Example 38 One MS 2000 100 100 100 100 BOE 3B 4.4 11.1 17.8 DBTL 0.2 0.9 1.6 Acetyl acetone 0.3 1.1 1.9 Cure 5076 0.1 0.3 0.5 2 Hardener MS Standard 50 Desmodour N3390 32.6 43.1 53.6 3 1.2.3 Thinner Slow 9.4 33 35 35

Characteristic Comparative Example J Example 36 Example 37 Example 38 VOC 560 529 498 468 Viscosity (DINC4, Seconds) 18 18 19 19 Ratio NCO / OH 78 100 100 100 Dry contact (60 ℃, min) 30 10 10 10 Dry contact (RT, min) 120 120 77 60 Port Life (minutes) ＞ 180 60 60 60 Polish 74 86 82 83

Adding BOE 3B as a reactive diluent reduces VOCs, shortens drying time and increases gloss.

Claims (39)

A coating composition comprising a first compound composed of at least one bicyclo-orthoester group or a spiro-orthoester group, The coating composition is a coating composition, characterized in that it comprises a second compound consisting of at least two hydroxyl-reactive groups. The method of claim 1, The bicyclo-orthoester group is a coating composition, characterized in that it has a structure of formula (1). (Formula 1) (In Formula 1, X and Z are each independently selected from a linear or branched alkylene (alkenylene) group optionally containing oxygen or nitrogen atoms and having 1-4 carbon atoms; Y is independently selected from X and Z which are absent or linear or branched alkylene (alkenylene) groups optionally containing oxygen or nitrogen atoms and having 1-4 carbon atoms; R ₁ and R ₂ are the same or different, Alkyl (alkenyl) groups having 1-30 carbon atoms, which may be hydrogen, hydroxyl, linear or branched, and optionally contain one or more heteroatoms and oxygen, nitrogen, sulfur, phosphorus, sulfones, sulfoxy and esters Consisting of a group selected from, optionally epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro, phosphorus, sulfoxy, amido, ether, ester, urea, urethane, thioester, thioamide, amide, carbox Monovalent radicals substituted with carboxyl, carbonyl, aryl and acrylic groups; Linear or branched, selected from oxygen, nitrogen, sulfur, phosphorus, sulfone, sulfoxy and ester, optionally epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro, phosphorus, sulfoxy, amido Ether, ester, urea, urethane, thioester, thioamide, amide, carboxyl, carbonyl, aryl and acrylic groups, ester groups; Ether group; Amide group; Thioester group; Thioamide group; Urethane groups; Urea; And an alkylene (alkenylene) group having 1 to 10 carbon atoms, which is selected from a group substituted with a single bond and may optionally contain one or more heteroatoms.) The method of claim 2, X, Y and Z is a coating composition, characterized in that methylene. The method of claim 2 or 3, In the monovalent value, the radicals R ₁ and R ₂ are independently selected from linear or branched alkyl groups (alkenyl groups), hydroxyl, hydrogen having 1-20 carbon atoms, optionally substituted with one or more hydroxy groups, A coating composition, optionally comprising an ester group. The method of claim 4, wherein R ₁ and R ₂ are methyl, methylol, ethyl, ethylol, propyl, propylol, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and -CH ₂ -CH ₂ -O-CO-C Coating composition, characterized in that each independently selected from the group of _1-20 alkyl group (alkenyl group). The method of claim 2, A coating composition, wherein one or both of R ₁ and R ₂ are divalent radicals in which the first compound is a polymer composed of at least one bicyclo-orthoester group. The method of claim 6, One or both of R ₁ and R ₂ are selected from linear or branched alkylene groups (alkenylene groups) having esters, ethers, urethanes, single bonds and 1-10 carbon atoms, optionally one or more esters, ethers or A coating composition comprising a urethane group. The method of claim 1, The spiro-ortho ester group is a coating composition, characterized in that it has a structure of formula (2) or formula (3). (Formula 2) (Formula 3) (In Formula 2 and Formula 3, R ₃ and R ₅ is linear or branched alkyl (alkenyl) optionally containing one or more oxygen, nitrogen, sulfur or phosphorus atoms, and optionally substituted with halogen atoms, Each independently selected from the group of aryl or acrylic; and R ₄ and R ₆ are optionally selected from linear or branched alkyl (alkenyl), aryl or acrylic groups containing one or more oxygen, nitrogen, sulfur and Divalent radicals such as monovalent radicals and alkylene groups and single bonds having 1 to 10 carbon atoms with or without groups selected from oxygen, nitrogen, sulfur and phosphorus, one or more atoms and ethers, esters and urethane groups Each independently selected from alkylene groups having 1-3 carbon atoms optionally substituted with one or more groups selected from The method of claim 8, R ₃ and R ₅ is a coating composition, characterized in that each selected from linear or branched alkyl group (alkenyl group) having 1-4 carbon atoms. The method according to claim 8 or 9, R ₄ is a coating composition, characterized in that ethylene having 1-5 carbon atoms, optionally substituted with a linear or branched alkyl group containing one or more oxygen and nitrogen atoms. The method of claim 10, R ₄ is a coating composition, characterized in that the compound of the formula. The method according to any one of claims 8 to 11, R ₆ is a coating composition, characterized in that propylene. The method according to claim 8 or 9, The first compound is a coating composition, characterized in that the spiro- ortho ester functional compound of the formula (4). (Formula 4) (In Formula 4, R ₃ and R ₅ are selected from linear or branched alkyl (alkenyl) groups having 1-4 carbon atoms.) The method according to claim 8 or 9, A coating composition, wherein one or both of the R ₄ and R ₆ groups are polymers composed of at least one spiro-orthoester group and are substituted with a radical thereof. The method according to any one of claims 1 to 14, The second compound is composed of at least two hydroxyl-reactive groups selected from the group consisting of an isocyanate group, an epoxy group, an acetal group, a carboxyl group, an anhydride group and an alkoxysilane group, and the second compound is an amino resin coating composition. . The method of claim 15, The hydroxyl-reactive compound is a coating composition, characterized in that an aliphatic, aliphatic ring or aromatic compound composed of at least two isocyanate groups or adducts thereof. The method of claim 16, The second compound is selected from the group consisting of biuret, isocyanurate, allophonate, uretdione and mixtures thereof. The method according to claim 1, wherein The coating composition contains additionally at least one compound selected from the group of hydroxyl-functional binders, hydroxyl-functional oligomers and monomers, and ketone resins, asparagiic acid esters and latent or non-latent amino-functional compounds. Coating composition, characterized in that. The method of claim 18, And the hydroxyl-functional binder is selected from polyester polyols, polyether polyols, polyacrylate polyols, polyurethane polyols, cellulose acetobutyrates, hydroxyl-functional epoxy resins, alkyd and dendrimer polyols. The latent hydroxyl group of the bicyclo-orthoester group or the spiro-orthoester group is unblocked in the presence of water, optionally in the presence of the first catalyst, and optionally the hydroxyl- of the second compound in the presence of the second catalyst. 20. A method of curing a coating composition according to any one of claims 1 to 19, characterized in that it is reacted with a reactive group. The method of claim 20, Wherein the first catalyst is selected from the group of Lewis acids and Bronsted acids. The method of claim 21, The Lewis acid is BF ₃ Et ₂ O. The method of claim 22, Said Bronsted acid is pKa &lt; 3. The method of claim 23, Said Bronsted acid is selected from the group of monoalkyl phosphates or dialkyl phosphates, carboxylic acids having at least one chlorine and / or fluorine atom, alkyl or aryl sulfonic acids or (alkyl) phosphoric acids. The method of claim 24, The Bronsted acid is selected from the group of methane sulfonic acid, paratoluene sulfonic acid, optionally substituted naphthalene sulfonic acid, dodecyl benzene sulfonic acid, dibutyl phosphate, trichloroacetic acid, phosphoric acid and mixtures thereof. Way. The method according to any one of claims 20 to 25, A process characterized in that 0 to 10 wt.% Of the first catalyst is used, calculated on BOE- and SOE-functional compounds. The method of claim 26, 0.3 to 8 wt.% Of the first catalyst. The method according to any one of claims 20 to 27, The second catalyst is dimethyl tin dilaurate, dibutyl tin dilaurate, dibutyl tin diacetate, tin octoate, zinc octoate, aluminum chelate, dimethyl tin dichloride, tertiary amine, BF ₃ or an organic complex thereof. Lewis acid, paratoluene sulfonic acid, dodecyl benzene sulfonic acid, phosphoric acid and mixtures thereof. The method of claim 28, Wherein the second catalyst is present in the solid phase in an amount of 0.001 to 5 wt.%. In a binary system, The first component consists of at least one bicyclo-orthoester compound or spiro-orthoester compound and at least one hydroxyl-reactive compound, and the second component is hydrolysis of the bicyclo-orthoester or spiro-orthoester compound Binary system, characterized in that consisting of a first catalyst for. In the three component system, The first component consists of at least one bicyclo-orthoestri or spiro-orthoester compound, the second component consists of at least one hydroxyl-reactive compound, and the third component is bicyclo-orthoester or spiro A three-component system comprising a first catalyst for hydrolysis of an orthoester compound. In the process for preparing a compound composed of at least one bicyclo-orthoester group, Compounds having at least one corresponding oxetane group are converted in the presence of catalytic amounts of strong Bronsted or Lewis acids or organic mixtures thereof The method of claim 32, The Lewis acid is BF ₃ Et ₂ O, BF ₃ -2CH ₃ COOH and SnCl ₄ characterized in that the production method. 34. The method of claim 32 or 33, Wherein the catalyst is used in an amount of 0.001-0.1 mol of catalyst per mol of oxetane group. The method according to any one of claims 32 to 34, wherein Wherein said reaction takes place in the presence of a small amount of solvent, preferably without solvent. In the method for producing a compound of the formula Pentaerythritol is reacted with triethyl orthopropionate in the presence of paratoluene sulfonic acid and with trimethyl benzene used as a solvent. A polymer characterized by consisting of at least one bicyclo-orthoester group of the formula (1). (Formula 1) (In Formula 1, X and Z are each independently selected from a linear or branched alkylene (alkenylene) group optionally containing oxygen or nitrogen atoms and having 1-4 carbon atoms; Y is independently selected from X and Z which are absent or linear or branched alkylene (alkenylene) groups optionally containing oxygen or nitrogen atoms and having 1-4 carbon atoms; One of R ₁ and R ₂ is a radical, the other is a divalent radical or both groups are selected from radical groups, The monovalent radical may be hydrogen, hydroxyl, linear or branched, having an alkyl (alkenyl) group having 1-30 carbon atoms optionally containing one or more heteroatoms and oxygen, nitrogen, sulfur, phosphorus, sulfone , Sulfoxy and esters, optionally epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro, phosphorus, sulfoxy, amido, ether, ester, urea, urethane, thioester, thio Substituted with amide, amide, carboxyl, carbonyl, aryl and acrylic groups, The divalent radical may be linear or branched and is selected from oxygen, nitrogen, sulfur, phosphorus, sulfone, sulfoxy and esters, optionally epoxy, cyano, amino, thiol, hydroxyl, halogen, nitro, phosphorus, Sulfoxy, amido, ether, ester, urea, urethane, thioester, thioamide, amide, carboxyl, carbonyl, aryl and acrylic groups, ester groups; Ether group; Amide group; Thioester group; Thioamide group; Urethane groups; Urea; And an alkylene (alkenylene) group selected from the group substituted with a single bond and having 1 to 10 carbon atoms which may optionally contain one or more heteroatoms.) A polymer comprising at least one spiro-orthoester group of formula (2) or (3). (Formula 2) (Formula 3) (In Formula 2 and Formula 3, R ₃ and R ₅ is linear or branched alkyl (alkenyl) optionally containing one or more oxygen, nitrogen, sulfur or phosphorus atoms, and optionally substituted with halogen atoms, Each independently selected from the group of aryl or acryl; and R ₄ and R ₆ are optionally selected from monovalent radicals such as linear or branched alkyl (alkenyl), aryl or acrylic groups containing one or more oxygen, nitrogen, sulfur and phosphorus and oxygen, nitrogen, sulfur and phosphorus Optionally substituted with one or more groups selected from the selected group, a divalent radical such as an alkylene group having 1-10 carbon atoms with or without one or more atoms and ethers, esters and urethane groups and a single bond Each independently selected from an alkylene group having 3 carbon atoms; 38. The method of claim 36 or 37, The polymer is characterized in that the polyacrylate or polyester.