DE3508399C2 - 2-component paints and their use - Google Patents

Description

It is known to use unsaturated compounds, such as cinnamic acid esters, with H-active compounds, e.g. B. malonic acid esters or acetoacetic ester, by Michael addition to form of substituted compounds, e.g. B. substituted malonic acid esters, implement (Krauch-Kunz "name reactions der organic chemistry "5th edition 1976, page 42).

Furthermore, it is known to be an acrylate resin containing OH groups or an acrylate resin modified with ε-caprolactone in a mixture with polyisocyanates as two-component paints to use (DE-PS 30 05 945, 30 27 776 and 31 48 022). Another publication describes the implementation of Acrylate copolymers containing epoxy groups with a partially blocked isocyanate and the use of the reaction product as a paint binder (DE-OS 31 30 545).

Some of the well-known products have proven their worth. However, attempts have been made to create more environmentally friendly products by making use of systems with no free Isocyanate runs out.

Another publication contains an oxazolidine Acrylic resin describes the water or humidity used as hardener (EP-OS 34 720). This System has the disadvantage that the hardened surface a deeper penetration of water into the lower layers counteracts the coating and so a complete Prevents hardening through the entire layer thickness.

It is also a two-component reaction without isocyanate System known. This consists of an epoxy group  containing acrylic resin that with another Acrylic resin containing tertiary amino groups is curable. The product produced by this process leads the insufficient degree of cross-linking to an insufficient chemical resistance, so that with this system produced coatings only for a limited area of application are suitable.

Acrylic polymers are described in US Pat. No. 4,408,018, into which acetoacetate groups have been introduced and the Michael addition in the presence of strong bases are crosslinked with α, β-olefinically unsaturated esters can. The acetoacetate group is introduced about the acetoacetic esters of hydroxymethylacrylates or methacrylates and subsequent copolymerization with other copolymerizable monomers or by reaction OH group-containing polymers with the precursor of the acetoacetic ester component, the diketene. As an organic component, crosslinked the polymers contained with the acetoacetate groups are polyacrylates with more than two Acrylate groups, reaction products of polyisocyanates with Hydroxyl group-containing acrylic acid esters and reaction products of epoxy resins with acrylic acid called. These However, compounds have the disadvantage that they act as catalysts strong bases such as alkali hydroxides or alcoholates to a strong yellowing and clouding of the Lead paint.

The invention is based on the object, the offer of the paint binders on the market to expand a system that does not have free isocyanates for curing needed, so it is environmentally friendly. Here are Catalysts are used that do not shorten the pot life and also cause no yellowing of the paint films and the  when using small amounts of catalyst, coatings result that are high Requirements regarding hardening properties and chemical resistance correspond.

The present invention therefore relates to a two-component paint consisting of

• A) Compounds with at least two groups of the formula (I)
• B) Connections that
  • B1) at least two active H atoms, or
  • B2) at least two groups with active H atoms of the type AH (II), or
  • B3) contain or form at least one active H atom and at least one group of the formula (II),
• in what mean
  X -CO- which is bonded to another R 1 R 2 C = CR 3 group either directly or via a residue of a polyhydric alcohol or an amine formed by removing two hydrogen atoms,
  R¹ is hydrogen or the monovalent radical of a hydrocarbon having 1 to 10 carbon atoms
  R² is hydrogen, the monovalent radical of a hydrocarbon having 1 to 10 C atoms, an ester group -CO-OR¹⁴ with the radical R¹⁴ of a monohydric alcohol having up to 12 C atoms, -CN≡N, -NO₂, -CO- NHR¹- or CO-R¹,
  R³ is the same as R² and hereby the same or different, and
  AH in formula (II) one of the groups <CH-, <NH or -SH, and
• C) a catalyst from the group consisting of halides of quaternary ammonium compounds, alone or in a mixture with silicic acid esters or organic phosphonium salts with 1 to 20 carbon atoms in the alkyl radical and / or aryl radical, and also phosphanes, alone or in combination with customary additives.
  In the reaction product, component A is a Michael acceptor, component B) is a Michael donor.

The product according to the invention has the advantage that it consists of Components are manufactured that are not toxic included and therefore without special precautions can be applied.

Although in the implementation of compounds A) with each two groups (I) with compounds B) with two active H- Atoms or two groups (II), even if only one Contain hydrogen atoms due to the mutual bifunctionality it is to be expected that only this a chain extension occurs, surprisingly the crosslinked reaction products cured according to the invention. The effective groups of compounds A) and B) can also be contained in a single molecule be so that there are systems that are intermolecular Networking is curable and self-crosslinking.

If higher reactivity and therefore stronger networking of the product is aimed at, one can take advantage proceed in such a way that in at least one of the connections A) and B) three or more groups of type (I) or active H atoms and / or groupings of type (II) present are.

According to one embodiment of the invention, the rest R¹R²C = CR³-X (I) from a mono- or polyunsaturated at most dibasic carboxylic acid, e.g. B. mono- and / or Dicarboxylic acid, having 2 to 10, preferably 3 to 6, carbon atoms, such as cinnamic acid, crotonic acid, citraconic acid or their anhydride, Mesaconic acid, fumaric acid, dehydrolevulinic acid, Sorbic acid, but preferably acrylic acid, methacrylic acid and / or maleic acid or its anhydride, also of unsaturated ketones, such as divinyl ketone, Dibenzalacetone; also of unsaturated nitriles, such as Maleic mononitrile monoesters of polyhydric alcohols,  of cyanoacrylic acid esters of the formula H₂C = C (CN) -COOR, of Nitrites of the formula ROOC-R³C = CH-NO₂, from alkylidene malonic esters of the formula ROOC-C (COOR⁴) = CR¹R², alkylidene acetoacetic esters of the formula ROOC-C (CO-CH₃) = CR¹R² or the corresponding nitriles, where R the rest of a polyhydric alcohol, R¹ and R² are hydrogen or is alkyl. These Residues are usually in the form of an ester or amide bound before. You can add to the rest of a multi-valued one Alcohol, a compound with NH groups such as a polyamine, Polyamides or polyiminoamides of a polyvalent Phenol, preferably an oligomer and / or polymer be bound. For example, the compound A) deriving from saturated and / or unsaturated, OH Group-containing polyethers or polyesters, e.g. B. those based on maleic acid, phthalic acid and Diols; Acrylic groups containing OH groups; aliphatic or preferably aromatic, optionally OH groups containing epoxy resins, e.g. B. those based on Diphenylolpropane and / or methane, hydantoin and / or amine resins. The ester-bonded radical (I) z. B. by adding acrylic or methacrylic acid to the Epoxy group may have arisen. As starting substances for A) suitable polyhydric alcohols are, for example, alkanediols and triols, such as ethanediol, the various propane, Butane, hexane, octanediols or their homologues, the corresponding oligomeric ether, also glycerol, trimethylolethane or propane, hexanetriol, pentaerythritol, dipentaerythritol, Sorbitol, polyvinyl alcohol or the like.

Starting compounds containing NH groups for the Compounds A are e.g. B. called alkylenediamines and their oligomers, such as ethylenediamine, propylenediamine, Butylene diamine, diethylene triamine, tetramine and higher Homologs of these amines, also amino alcohols, such as diethanolamine.  As amines come e.g. B. also aminocarboxylic acid esters polyhydric alcohols in question. As connections come with NH groups z. B. in question acrylic or Methacrylic acid polyamides, also polyurethanes, e.g. B. polyisocyanates, which capped in the form of polyurethane groups are like those made by reacting hydroxyethyl acrylate of polyisocyanates, amine resins such as methylolmalamines, preferably hexamethylolmelamine, urea resins, the rest (I) with the grouping -CO- to the amine groups of these compounds is bound as an amide. If these amine compounds via OH groups or alkylol groups have, it is also possible that the rest (I) immediately via an ester group (formula III see formula sheet) or indirectly via an ether group (formula IV see formula sheet) these resins is bound. For the ether binding of the rest (I) can be obtained from a hydroxyalkyl ester or Hydroxyalkylamide of an unsaturated acid, such as acrylic acid, going out. The same applies to a corresponding bond to Polyhydroxy compounds.

The grouping -AH- (II) is derived in connection B)

• aa) for the meaning from a compound with the grouping -CO-CHR¹-CO-, NC-CHR¹-CO-, NC-CH₂-CN, = PO-CHR¹-CO-, = PO-CHR¹-CN, = PO-CHR¹-PO =, -CO-CHR¹-NO₂, wherein R¹ is preferably hydrogen,
• bb) for the meaning -NH-, which also includes NH₂, from one primary and / or secondary amine and
• cc) for the meaning -SH of a thioalcoholic acid ester, amide and / or a mercaptan.

β-dioxo compounds are preferred.

Suitable compounds B) of type aa) are, for example Ketones, such as acetylacetone, benzoylacetone, acetyldibenzoylmethane, further esters of optionally alkyl-substituted Acetoacetic acid such as α- and / or γ-methylacetoacetic acid, or acetone dicarboxylic acid, bound in ester-like fashion  Malonic acid units of malonic acid and its monoalkyl derivatives, straight-chain or branched, with 1 to 6 carbon atoms in the Alkyl radical, e.g. B. methyl, ethyl and n-butyl or phenyl, or cyanoacetic acid with monohydric to hexahydric alcohols with 1 to 10 carbon atoms. The alkyl substituted esters, e.g. B. α-methyl or α, γ-dimethylacetoacetic ester have only one active H atom and are therefore preferably in the form of Di- or polyesters of polyhydric alcohols used to a sufficient number of reactive groups to have. Suitable alcohols for the esterification of the above Acids are e.g. B. methanol, ethanol, butanol, octanol and / or, which is preferred, polyhydric alcohols or polyhydroxy compounds like those as starting substances for A) mentioned. Other compounds B) are, for. B. acetoacetic ester, Ethanodiol bisacetoacetic ester, glycerol tris malonic acid ester, Trimethylolpropane tris-acetoacetic ester, partial ester of this Acids with polyhydric alcohols, also the corresponding ones Esters of OH-containing acrylic resins, Polyesters, polyethers, polyester amides and imides, Polyhydroxylamines, also nitriles of these acids, if these exist, e.g. B. malonic acid mono- or dinitrile, Alkoxycarbonyl-methanephosphonic acid esters and the corresponding Bis-methanephosphonic acid ester (formula VII see Formula sheet). The acids mentioned above can also bound in the form of amides to amines, preferably polyamines be, e.g. B. the connection-related A) mentioned, which also include oligomers and / or polymers Amine resins include, aliphatic amines are preferred.

Reactive nitro compounds are also suitable as compounds (aa), e.g. B. nitroacetic acid derivatives such as tris (nitroacetic acid) - glycerol ester or trimethylolpropane nitroacetic acid ester.  

As compounds bb) are, for. B. primary and / or secondary polyamines, especially aliphatic di-, tri- and higher amines, e.g. B. their homologs, oligomers and / or Polymers including amine resins, as follows are described above, urea and its derivatives, also cyclic, e.g. B. aromatic polyamines, such as Phenylenediamine or mixtures of aliphatic and aromatic amines, also in this Case preferably aliphatic amines are used.

Suitable compounds B) with a group -SH from Type cc) are e.g. B. thioglycolic acid, β-mercaptopropionic acid or thiosalicylic acid esters of polyhydric alcohols and thio alcohol ethers and esters, mercaptans, for example Ethyl, propyl mercaptan and their homologues or their ether, e.g. B. thioglycerin, substitution products cyclic amines with thioalkanols.

Among compounds B) which form groups of type (II), are z. B. diketene and its mono-α-alkyl substitution products, also to mention tetrahydrodioxin, which with suitable Components to form acetoacetic ester or amide groups can react.

The reaction component B) can at least one polyvalent Compound of the group of mono- or polyhydric alcohols, Polymers containing OH groups, e.g. B. the further above, polyamines and polymercaptans bound and is multi-valued in relation to the CH function. So it can, for example, by esterification of a polyepoxide with one forming the grouping -AH- (II) Carboxylic acid, e.g. B. cyanoacetic acid (equation V see formula sheet) have been produced. You get a component like this B) with two active H atoms per epoxy group. Aromatic or araliphatic polyepoxides can be used here insert, e.g. B. the above.  

If one starts from polyamines, connections can be made B) both of type aa) in the form of amides as well as such of type bb). If the groupings -AH- the Meaning -CH- has z. B. from 1 mole of an alkylenediamine go out, implemented with 2 moles of acetoacetic ester is to form compound VI (see formula sheet), which also has four H atoms activated by amide groups having. As compounds B) in which group (II) -NH- means that the polyamines as such are sufficient. In this way, z. B. 1 mole of trimethylolpropane tris react with 3 moles of ethylenediamine, the free amine groups of the product with other active ones Double acrylate bonds can react with crosslinking.

The 2-component paints are made from
A) compounds with at least two R¹R²C = CR³-X groups (I) and B) compounds that

• a) at least two active H atoms or
• b) at least two groups with active H atoms type -AH- (II) or
• c) at least one active H atom and at least one Type (II) group

contain, or form the corresponding number of this group (II), wherein in formula (I)
X -CO- which is bonded to another R 1 R 2 C = CR 3 group either directly or via the remainder of a polyhydric alcohol or an amine,
R¹ is hydrogen or a hydrocarbon radical having 1 to 10 carbon atoms,
R² is hydrogen, a hydrocarbon radical with 1 to 10 C atoms, an ester group with the radical R⁴ of a monohydric alcohol with up to 12 C atoms, -CN, -NO₂, a CO-NHR¹ or a CO-R¹ group,
R³ has the same meaning as R²,
in formula (II) -AH- one of the groupings

mean where the connections A) and B) under Formation of an oligomeric and / or polymeric reaction product be implemented, in the event that -AH- a of the groups

represents the implementation in the present at least one catalyst is from the group Diazoabicyclo-octane (DABCO), halides of quaternary Ammonium compounds, alone or in a mixture with silicic acid alkyl esters, Amidines, organic phosphonium salts with 1 to 20 carbon atoms in the alkyl radical and / or aryl radical, tertiary Phosphines of the general formula P (CH₂-Y) ₃, in which Y is the same or different, the radical -OH, -CH₂CN or -N (Z) ₂ means, where Z is an alkyl radical having 1 to 5 carbon atoms is tertiary phosphines of the general formula P (R⁴, R⁵, R⁶), in which the radicals R⁴, R⁵ and R⁶ are an alkyl radical with 1 to 12 carbon atoms or a phenyl radical, unsubstituted or substituted with at least one alkyl, alkoxy or Dialkylamino group, each with 1 to 4 carbon atoms in the alkyl radical mean R⁴, R⁵ and R⁶ are the same or different, however, at least one of the residues is a phenyl residue represents and aminophosphoranes of the general formula (R⁷, R⁸, R⁹) P = N-C (R¹⁰, R¹¹, R¹²), in which R⁷, R⁸, R⁹ are the same or are different and an alkyl radical with 1 to 12 carbon atoms or a phenyl radical, unsubstituted or substituted with at least one alkyl, alkoxy or dialkylamino group each with 1 to 4 carbon atoms in the alkyl radical and R¹⁰, R¹¹, R¹² are the same or different and are an alkyl radical with 1-5 carbon atoms or a phenyl radical.

Another manufacturing process of the 2-component paints mentioned in claim 1, wherein in In case -AH- one of the groups

represents, takes place the reaction in the presence of at least one quaternary ammonium compound or an alkali alcoholate as a catalyst.  

These processes are very smooth. Because preferably of oligomeric and / or polymeric compounds A) and B) it is assumed that oligomers and / or polymers are also obtained Reaction products. The reaction generally takes place at -10 to 180, preferably 0 to 100, in particular 20 up to 80 ° C. For example, at room temperature you get after 2 up to 24 hours or at 60 ° C after 10 to 40 minutes of products with good hardness.

Implementation of compounds B) in which the grouping (II) -NH- or -NH₂ can be carried out without a catalyst become. On the other hand, you usually work with one or more catalysts, provided the grouping -AH- one

(preferred form) or -SH group represents. Suitable catalysts for Michael addition are, for example, those from the group the halides of quaternary ammonium compounds, such as Alkyl, aryl and / or benzylammonium bromides, chlorides, and in particular fluorides, the halides optionally in combination with silicic acid alkyl esters be used to the activity of the catalyst yet to improve. In particular, for. B. Alkylbenzyldimethylammonium halides (Alkyl = C₁₆-C₂₂), benzyltrimethylammonium halides, Tetrabutylammonium halides, in particular each fluoride and polymerized triphenylvinylphosphonium fluoride called. Are also suitable as Catalysts corresponding to the above ammonium halides organic phosphonium salts with 1 to 20 carbon atoms in the alkyl radical and / or aryl radical, e.g. B. trimethylbenzyl phosphonium halides, tributylhexadecylphosphonium bromide, Amides such as tetramethylguanidine, diaza-bicyclo-undecene, Diaza-bicyclo-nonen.

Other suitable catalysts for the manufacturing process of Michael adducts are the phosphines (formerly  referred to as phosphines) z. B.

• a) tertiary phosphines of the general formula P (CH₂-Y) ₃, in which Y is the same or different and represents the radical -OH, -CH₂CN or -N (Z) ₂, where Z is an alkyl radical having 1 to 5 carbon atoms,
• b) tertiary phosphines general formula P (R⁴, R⁵, R⁶), in which the radicals R⁴, R⁵ and R⁶ have an alkyl radical 1 to 12 carbon atoms or a phenyl radical, unsubstituted or substituted with at least one alkyl, alkoxy or dialkylamino group each having 1 to 4 carbon atoms in the alkyl radical, R⁴, R⁵ and R⁶ are the same or different, wherein however, at least one of the radicals is a phenyl radical and
• c) aminophosphoranes of the general formula (R⁷, R⁸, R⁹) P = N-C (R¹⁰, R¹¹, R¹²), in the R⁷, R⁸, R⁹ are the same or different and an alkyl radical with 1 to 12 carbon atoms or a phenyl radical, substituted or unsubstituted with at least an alkyl, alkoxy or dialkylamino group each having 1 to 4 carbon atoms in the Mean alkyl radical and R¹⁰, R¹¹, R¹² are the same or different and one Alkyl radical having 1 to 5 carbon atoms or a phenyl radical.

Trishydroxymethylphosphane, trisdimethylaminomethylphosphine, tris-o- anisylphosphine, methyl-diphenylphosphine, methyl-di-p-anisylphosphine and α, α- Dimethylbenzyliminotributylphosphorane.

For the production of certain implementation products as catalysts for Michael addition, for example those of the group alkali alcoholates, such as lithium butylate, Sodium, potassium methylate, quaternary ammonium compounds, such as alkyl, aryl and / or benzylammonium hydroxides, carbonates are used. In particular e.g. B. alkyl-benzyldimethylammonium hydroxide (alkyl = C₁₆-C₂₂), Benzyltrimethylammonium hydroxide and tetrabutylammonium hydroxide called. The catalysts or catalyst mixtures mentioned can in the presence of itself at room temperature inactive tertiary aliphatic amines, such as triethylamine, N-methyldiethanolamine, N- Methyl di-isopropanolamine or N-butyldiethanolamine used become. These adjuvants can be 0.1-5, preferably 0.1-1% by weight.  

The amount of the catalyst is generally 0.01 to 5, preferably 0.02 to 2 wt .-%, based on the total solids content of the starting product. Depending on the Reactivity of compounds A) and B) and the intended Procedures can be varied. The addition of catalyst can also in portions, d. H. in several stages.

According to one embodiment of the invention, the compounds A) in a mixture with a minor part of those compounds A) which are only one group of the formula I contain, or the compounds B) in a mixture with one subordinate proportion of compounds B), which is only a contain active H atom or only one group of the formula (II), implemented. You only get this possibility then make use of it if you reduce the crosslink density wants and the associated properties of Product would like to vary accordingly. Most of all, this is then the case when at least one of components A) and B) by a relatively high proportion of reactive Groups, e.g. B. when using a monomolecular hexaacrylic acid ester, creates a particularly strong network, so that if necessary with an undesirable tension of the reaction product and therefore the risk of any Embrittlement is to be expected. In this embodiment the proportion of compounds with only one group (I) or (II) at most 20, preferably at most 10, in particular up to 5% by weight, based on the respective analogous compound A) or B). With such an addition you can Hardness and elasticity of the reaction product in a certain Control extent. The ones to be used for this variant Compounds A) with only one reactive group (I) e.g. B. the esters or amines of the unsaturated listed for A) Carboxylic acids, however, only with monohydric alcohols or esterified or reacted with amide formation have been.  

Suitable compounds B) for this embodiment are e.g. B. those with the groups mentioned under aa) above, in which R¹ has a meaning other than hydrogen, for example the alkyl substitution products of acetoacetic acid and malonic acid, which is only with a monohydric alcohol have been esterified or reacted with a monoamine. Compounds B) of type bb) are amines with only one active one H atom on the amino group, such as secondary monoamines, e.g. B. Diethylamine, and those of type cc) are alkanol mercaptans, which contain only one mercaptan group, e.g. B. ethyl mercaptan.

The process can be done in one or carry out several stages. As a rule, however prefer the one-step procedure for economic reasons, for example with equivalent proportions of the components with two active groups or H- Atoms works (equation XII see formula sheet see underlined H atoms). The choice of process stages, the pot life and properties of the product therefore depend on the Process conditions, d. H. on the type and amount of raw materials, the metering of the catalyst and the temperature control from. This is how the elasticity of the networked Product within a tolerance range z. B. by the chain length of the oligomers used for A) or B) and / or control polymers.

Although the process according to the invention is generally discontinuous is operated, it is also within the scope of the invention the mixing of the components and the course of the reaction to be carried out continuously, for example by means of an automatic painting device.

In the multi-stage procedure, one can add several of the components in portions. For example can in the first stage 1 mol of butanediol bis-acrylate  are reacted using 2 mol of malonic acid diamide (equation XI s. Formula sheet) to form a product containing two Groups (II) each with an active (underlined) H atom contains. This product can be used in at least one other Step implemented with further molecules of a compound A) become chain extension and networking. On analog Way z. B. a mole of trimethylolpropane tris-acrylate or methacrylate in the first stage with three moles of acetylacetone implement.

The networking in the second and possibly also the following Steps can be carried out, for example, by adding a catalyst. One can proceed in such a way that one is in the first stage only with a relatively small amount of catalyst, e.g. B. less than 2%, or with a relatively little active catalyst works. If the second or following Stages relatively shortly after the production of the preliminary product be carried out, it is not necessary to do so remove catalyst used in the first stage. Man can now either take a higher dose of it in the second stage Use a catalyst and / or another catalyst. There is also the option of entering in the first stage To manufacture intermediate product over a longer period of time is stable in storage and can even be shipped to the processor can. In this case, the catalyst becomes advantageous, e.g. B. by neutralization or distillation or use a catalytic converter, either from the outset to a polymer, such as polymerized triphenylvinylphosphonium fluoride, is bound or during the reaction is bound to a polymer. Before the final Application is the crosslinking reaction by renewed Add a sufficient amount of catalyst in progress set.  

The procedure can be in the presence or absence be carried out by organic solvents, which may also have an impact on activity of the catalysts. Suitable solvents are e.g. B. aromatic and aliphatic hydrocarbons such as toluene, the various xylenes, mixtures of aliphatic and / or aromatic hydrocarbons, mineral oil fractions, esters, Ether or alcohol.

All reaction components can be used individually or in a mixture, if they are compatible with each other.

Although the procedure is usually under Normal pressure expires, it may be desirable in individual cases be to work even under increased pressure to increase the curing speed to increase.

The mutual quantitative ratio of the reaction components A) and B) depends on the number of unsaturated groups (I) of compound A) and the sum of the active H atoms in Compound B) thus including those in the groups (II) (hereinafter briefly with "active double bonds: active H atoms ")) in the multi-stage procedure it can be used to manufacture intermediate products can be varied within a wide range. For Production of the cross-linked end product is, however the ratio of active double bonds: active H atoms generally about 2.4: 0.8 to 0.8: 2.4, preferably about 2: 1 to 1: 2, especially about (0.8 to 1.2): 1 to 1: (0.8 to 1.2). For one mole of ethanediol bisacrylate are therefore because of the two active H atoms in the acetoacetic ester e.g. B. applied only about 0.8 to 1.2 moles of acetoacetic ester. On the other hand, you only want an H atom from acetoacetic ester implement, so you can also 2 × (0.8 to 1.2) mol  Use acetoacetic ester (formula XII see formula sheet). As can be seen from this formula, the reaction product contains another reactive group (see underlined H atom), so it's either with other molecules or can continue to network with itself. The relationship active double bonds: then there is active hydrogen atoms 1: 1. On the other hand, it is also possible to mix the Components A on the one hand and / or B on the other hand each with different functionality to use to control the degree of crosslinking of the end products.

The implementation mixture is a 2-component System that shows pot lives depending on the selection of the compounds A) and B) and the type and amount of Catalyst or the catalyst combination between Vary 5 minutes and about 12 hours. This is one high processing security guaranteed. Based on these beneficial property related to the product with its quick and flawless hardening Room temperature or elevated temperature and its chemical Resistance it is excellent as a binder suitable for covers.

The 2-component systems can be applied as coatings, preferably in a thin layer bring up various documents, e.g. B. on such organic or of an inorganic nature, such as wood, wood fiber materials, e.g. B. as a wood sealer, textiles more natural or of synthetic origin, plastics, glass, ceramics, Building materials, such as concrete, fiberboard, artificial stones, in particular however on metal. The covers can also be used for Objects and devices used in the household and business be, e.g. B. refrigerators, washing machines, electrical appliances, Windows, doors or furniture. However, is preferred the use for motor vehicles. That can apply by brushing, spraying, dipping or electrostatically  be performed. Of course, the 2- Component systems still contain the usual additives such as dyes, pigments, fillers, plasticizers, Stabilizers, leveling agents, neutralizing substances such as tertiary amines and catalysts used in the usual Amounts can be used. These substances can Individual components and / or the total mixture added become.

As dyes or pigments, the more inorganic or organic For example, the following are mentioned: Titanium dioxide, graphite, carbon black, zinc chromate, strontium chromate, Barium chromate, lead chromate, lead cyanamide, lead silicochromate, Calcium molybdate, manganese phosphate, zinc oxide, cadmium sulfide, Chromium oxide, zinc sulfide, nickel titanium yellow, chrome titanium yellow, Iron oxide red, iron oxide black, ultramarine blue, phthalocyanine complexes or napthol red.

Suitable fillers are e.g. B. talc, mica, kaolin, Chalk, quartz flour, asbestos flour, slate flour, barium sulfate, various silicas or silicates.

The usual solvents are used for the fillers, for example aliphatic and aromatic hydrocarbons, Ethers, esters, glycol ethers and their esters, Ketones, chlorinated hydrocarbons, terpene derivatives, such as toluene, Xylene, ethyl and butyl acetate, ethylene glycol monoethyl or -butyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Cyclohexanone, methyl ethyl ketone, acetone, Isophorone or mixtures thereof.

The scope of the invention therefore also includes 2-component Systems suitable for the production of coatings, preferably Automotive paints and especially automotive refinish paints own. Here is the xylene resistance and  thus also good resistance to premium petrol especially of interest. Therefore, the invention Use of the reaction products is particularly advantageous. Because the 2-component system in proportion can cure itself at room temperature for a short time without that polluting substances are released is his Use as a car refinish paint of considerable practical Meaning.

In the rules and examples below mean % each wt.% and T each part by weight. Under vacuum is understood that the water jet pump.

Examples I) Production of component A (Michael acceptor)

A1) 400 parts of a solvent-free hydroxyl-containing acrylate resin (OH number 150) with 400 T acrylic acid, 200 T toluene, 3 T hydroquinone monomethyl ether and 3 parts of p-toluenesulfonic acid were added. Under Passing air was until the end of the H₂O development heated at the water separator. After cooling down Room temperature and washing with water became the excess Acrylic acid removed. The organic phase was freed from solvent by distillation under vacuum and diluted to a solids content of 60%. C = C- Equivalent weight 864.

A2) 510 T of the acrylic resin mentioned under A1 with 500 T methyl acrylate, 3 T hydroquinone monomethyl ether and 6 T dibutyltin oxide were added. Within 30 hours over a Vigreux column 26 T methanol at 80 to 90 ° C. Distilled internal temperature. The excess was removed under vacuum Acrylic acid distilled off. The residue was adjusted to a solids content of 60% with xylene diluted. C = C equivalent weight 1083.  

A3) 1000 parts of an acrylate resin containing glycidyl groups made from styrene, glycidyl methacrylate and dimethyl maleinate (Epoxy equivalent weight 510) were in 660 T. Xylene dissolved at 70 ° C. At 70 ° C 127 T acrylic acid and 1 T tetraethylammonium bromide were added. Passing through air was stirred at 80 ° C. until the acid number 1. The light yellow solution was diluted with 17T xylene. Solids content 62.5%, C = C equivalent weight 1022.

A4) 570 T of the resin solution from Example A3) were mixed with 0.1 T dibutyltin dilaurate and 50 T n-butyl isocyanate were added. The mixture was stirred at 60 ° C for 4 h (NCO value 0.2%). Solids content 65%; C = C equivalent weight 1112.

A5) 296 T trimethylolpropane trisacrylate were mixed in one equipped with stirrer, reflux condenser and a gas inlet 1 l flask submitted and with 200 T isopropanol and 1.5 T trithylamine were added. At room temperature 17 T hydrogen sulfide absorbed. It became another Stirred at 30 ° C for one hour. Then the formed one became heavier Product phase separated as an almost colorless liquid. Solids content 88%; C = C equivalent weight 172.

A6) In a three-necked flask equipped with a stirrer and thermometer as well as a distillation column with a descending condenser, were 657 parts of a melamine resin of the hexamethoxymethylmelamine type (Molecular weight 399), 1053 T 2-hydroxyethyl acrylate, 3.3 T hydroquinone monomethyl ether and 1.65 T sulfuric acid submitted. The mixture was heated to 75 ° C. in vacuo and heated to 95 ° C within 4 h. After cooling to room temperature was with 10 T of a 10% methanolic Potassium hydroxide neutralized and filtered. 141 T were obtained a low viscosity clear resin solution. C = C equivalent weight 175.  

A7) 220 T of isophorone diisocyanate were mixed with 1 T of dibutyltin dilaurate and heated to 50 ° C. At the same temperature, 2 parts of hydroquinone monomethyl ether, dissolved in 232 parts of hydroxyethyl acrylate, were added dropwise within one hour. The mixture was stirred until the N = C = O content was less than 0.5. After addition of 7 parts of a glycidyl ester of a saturated, α-branched C _9-11 fatty acid (epoxy equivalent weight 260) and 0.5 parts of chromium III octoate, the mixture was stirred at 80 ° C. for 5 hours and then with 115 parts of xylene transferred. Solids content 80%; C = C equivalent weight 289.

II) Preparation of component B (Michael donor)

B1) In a 2 liter glass flask equipped with a distillation bridge, Stirrer and contact thermometer, 312 T Neopentylglycol and 706 T methyl acetoacetate under N₂ heated to 130 to 160 ° C as a protective gas. After completion the distillation of the methanol (after about 7 h) was on Chilled 120 ° C. The excess methyl acetoacetate was distilled off in vacuo. There remained 819 T one clear bright liquid as a residue. C-H equivalent weight 70.

B2) 670 parts of trimethylolpropane were in a 4 l apparatus analogous to B1) and within 1972 T methyl acetoacetate Heated from 130 to 180 ° C for 5 h. After distillation has ended there were 465 T methanol in the template. After cooling the low-boiling fraction was reduced to 150 ° C. in vacuo distilled off. 1950 T of a colorless liquid remained as a backlog. C-H equivalent weight 64.

B3) 335 T were in the same apparatus as in B1) Trimethylolpropane and 2400 T malonic acid diethyl under N₂ heated to 150 to 170 ° C as a protective gas. After finished  The excess diethyl malonate was distilled off from the ethanol distilled off in vacuo at 150 to 160 ° C. There remained 1201 T of a colorless liquid as a residue. C-H equivalent weight 79.

B4) In an apparatus as in B1) 92 T glycerol and 426 T 2,2,6-trimethyl-4-oxo-4H-1,3-dioxin. With stirring, 160 parts of acetone were distilled off at 180 ° C. in the course of 5 hours. The residue was then at 120 ° C. freed from low-boiling components in vacuo. There remained 348 T of a yellow, low-viscosity liquid. C-H equivalent weight 58.

B5) While stirring, in a 1 liter three-necked flask, the Equipped with stirrer, reflux condenser and contact thermometer was, 300 T acetoacetic acid ethyl ester, 3 T potassium hydroxide solution and 4 T Submitted hydroquinone monomethyl ether and heated to 130 ° C. 198 T of butanediol diacrylate were metered in within one hour. After a further 2 h, the double bond fraction was less than 0.2%. Then the potash lye was added neutralized methanolic hydrochloric acid. By creating The low-boiling components became high vacuum at 100 ° C away. There remained 464 T of a light yellow viscous Liquid. C-H equivalent weight 232.

B6) 250 parts of a polyethylene glycol diamine (amine number 243), dissolved in 166 T diethylene glycol dimethyl ether -20 ° C to a solution of 190 T diketene in 134 T diethylene glycol dimethyl ether dripped. After stirring for 1½ hours at -28 ° C was heated to + 10 ° C and up to an amine number below 1 stirred. After adding 10 T of ethanol, the mixture was stirred for 40 min heated to 90 ° C. The solvent was then in Vacuum distilled off. The residue was dissolved in 100 parts of dimethoxyethane added. A light yellow clear was obtained Solution. Solids content 81%; C-H equivalent weight 122.  

B7) 134 T trimethylolpropane and 327 T methyl cyanoacetate were with 4 T titanium acetylacetonate from 100 to 180 ° C. heated while distilling off methanol. After 4 h cooled to 140 ° C and the low-boiling fraction in vacuo distilled off. 341 T of a yellow liquid remain; C-H equivalent weight 57.

B8) 750 parts of the acrylic resin mentioned under A1) (OH number 150) and 260 T of ethyl acetoacetate were in one Distillation apparatus heated to 150 ° C. Within 2 hours was heated to 170 ° C. After the distillation of the Ethanol became the low boiling part after investing Vacuum removed. After cooling to 100 ° C 306 T xylene admitted. A clear light yellow liquid was obtained. Solids content 75%; C-H equivalent weight 310.

B9) 510 T one based on trimethylolpropane, terephthalic acid, Adipic acid and neopentyl glycol made polyester (OH number 110) were together with 130 T ethyl acetoacetate heated to 140 ° C. Within 3 h was under continuous distillation of volatile components Heated 170 ° C. After cooling to 140 ° C the low boiling Part distilled off in vacuo. Subsequently was diluted with 198 T xylene. A light yellow was obtained clear solution. Solids content 75%; C-H equivalent weight 402.

B10) 300 T of the OH group-containing acrylate resin mentioned under A1 were dissolved in 200 parts of xylene at 70 ° C. After cooling to room temperature were 0.025 T dimethylaminopyridine added. 60 T diketene were added dropwise within 6 hours. After a further 12 hours, the free diketene content was 0.2%. Solids content 65%; C-H equivalent weight 392.  

B11) 440 T of coconut oil fatty acid methyl ester (saponification number 255) were together with 268 T trimethylolpropane and 1 T Butyl titanate heated to 180 ° C in a distillation apparatus. Within 7 h the temperature became steadily Distillation of methanol slowly increased to 250 ° C. After distilling a total of 59 T of methanol was on Cooled 100 ° C and mixed with 585 T ethyl acetoacetate. After warming to 140 ° C was continued Distillation heated to 175 ° C within 3 h. Overall, were received another 175 T of distillate. After cooling down The low-boiling fraction was removed in vacuo at 150 ° C. 992 parts of a viscous light yellow liquid were obtained. C-H equivalent weight 124.

B12) 200 T acetylacetone and 0.5 trimethylbenzylammonium hydroxide were heated to 40 ° C. 170 T were within 2 h Trimethylolpropane trisacrylate added dropwise. Then was stirred up to a double bond content of less than 0.5%. A light yellow viscous liquid was obtained. C-H Equivalent weight 162.

III) Preparation of a self-crosslinking reaction product according to the invention

C) (Example 17) 924 T of a 70% solution of a radical polymerization of styrene, hydroxyethyl methacrylate and methyl methacrylate made acrylic resin (OH number 130) (carrier substance) in xylene were at 40 ° C with 258 T of a 70% solution of one with hydroxyethyl acrylate half-capped toluene diisocyanate (N = C = O content 9.8%, C = C equivalent weight 290) (component A) in xylene in Presence of 5 T dibutyltin laurate up to an isocyanate Content of less than 0.3% implemented. Subsequently 2 T of dimethylaminopyridine were added and the mixture was added dropwise at room temperature with stirring, 25 parts of diketene (component B).  

After stirring for 24 hours at room temperature, none was found prove free diketen more. Solids content 71%; C = C equivalent weight 2022; C-H equivalent weight 2020. Instead of diketene, the equivalent amount of acetoacetic ester can also be used be implemented, taking a product with receives the same key figures.

IV) Preparation of the coatings - Examples 1 to 51

Examples 1 to 51 according to the invention are in Table 1 and 2 summarized. There are also four comparative tests V1 to 4 with commercially available products executed.

The weight amounts given in Tables 1 and 2 below of components A and B were mixed. When The same substance was used from 31 T glycidyl methacrylate, 15 T dimethyl maleate and 54 T styrene copolymer. Diethylene triamine served as the hardener for this system. In the case of the pigmented coatings, the one desired Degree of pigmentation corresponding amount of titanium dioxide added and the mixture was rubbed on a pearl mill. The coating material obtained was called such or, if necessary, after admixing the specified Catalyst by means of a squeegee in a Wet film thickness of 100 microns applied to glass plates and hardened at room temperature or at 80 ° C (30 min).

The abbreviations used in the table below mean:

ABAH: alkylbenzyldimethylammonium hydroxide (alkyl = C₁₆-C₂₂)
BTAH: benzyltrimethylammonium hydroxide
DETA: diethylene triamine
HH: hot curing = 30 min at 80 ° C
RT: room temperature
TBAF: tetrabutylammonium fluoride
TBAH: tetrabutylammonium hydroxide
TMPSG: Trimethylolpropane trithioglycolic acid ester
TMPTA: trimethylolpropane trisacrylate
TPTP: tris-p-tolylphosphine
MDPP: methane diphenylphosphine
PDOAP: phenyl-di-o-anisylphosphine
DPOAP: Diphenyl-o-anisylphosphine
TPAP: Tri-p-anisylphosphine
MDPAP: methyl-di-p-anisylphosphine
DPPDAPP: Diphenyl-p-dimethylamino-phenylphosphine
THMP: trishydroxymethylphosphine
TCEP: Tris-2-cyanoethylphosphane
TDAMP: tris-diethylaminomethylphosphine
TDAIP: Tris-dimethylamino-1,1-dimethylbenzyliminophosphorane
TBIP: tributyl-1,1-dimethyl-benzyliminophosphorane
TPP: triphenylphosphine
DBU: 1,8-diazabicyclo- [5,4,0] -undec-7-ene
DBN: 1,5-diazabicyclo- [4,3,0] non-5-ene
TMG: N, N, N ′, N′-tetramethylguanidine

V) Discussion of the results

As can be seen from Table 1, the products of Examples 1 to 38 high chemical resistance and high Hardness, d. H. they are fully networked, although the Hardening z. T. only occurred at room temperature. On the other hand they still have favorable pot lives, compare in particular Examples 6 to 9, 16-18, 22, 23, 27, 30. The last mentioned examples show that by suitable Selection of the catalysts a pot life in the range of 5 can be achieved up to about 20 h. Examples 11 to 13 and 16, 19-21, 24, 28, 33 to 37 indicate that at forced drying (hot curing 30 min / 80 ° C) already high hardness values are obtained after 1 day.

Compared to Table 1, Table 2 shows that the pot lives of the pigmented systems are somewhat shorter that but they are still sufficient for safe processing. As can be seen from Examples 39 to 49, the films harden completely at room temperature. The chemical resistance of the products according to Table 2 is on average higher than that of unpigmented ones Systems of Table 1.

Examples 12, 13, 50 and 51 show that the amine and mercapto compounds as component B a complete one Hardening and good chemical resistance of the products in the case of Examples 13 and 51 even without Catalyst is working. The physical values of the Comparative experiments V1 to V4 leave a low xylene resistance recognize and also a little pronounced Degree of hardening. The products according to the invention are therefore superior to the comparison samples.  

Formula sheet

Claims (11)

1. 2-component paint consisting of

• A) Compounds with at least two groups of the formula (I)
• B) Connections that
  • B1) at least two active H atoms, or
  • B2) at least two groups with active H atoms of the type AH (II), or
  • B3) contain or form at least one active H atom and at least one group of the formula (II),
• in what mean
  X -CO- which is bonded to another R 1 R 2 C = CR 3 group either directly or via residues of a polyhydric alcohol or an amine formed by removing two hydrogen atoms,
  R¹ is hydrogen or the monovalent radical of a hydrocarbon having 1 to 10 carbon atoms
  R² is hydrogen, the monovalent radical of a hydrocarbon having 1 to 10 C atoms, an ester group -CO-OR¹⁴ with the radical R¹⁴ of a monohydric alcohol having up to 12 C atoms, -CN, -NO₂, -CO- NHR¹- or CO -R¹,
  R³ is the same as R² and hereby the same or different, and
  AH in formula (II) one of the groups <CH-, <NH or -SH, and
• C) a catalyst from the group consisting of halides of quaternary ammonium compounds, alone or in a mixture with silicic acid esters or organic phosphonium salts with 1 to 20 carbon atoms in the alkyl radical and / or aryl radical, and also phosphanes, alone or in combination with customary additives.

2. 2-component paint according to claim 1, characterized in that the Catalyst C) a fluoride of quaternary ammonium compounds or Is phosphine. 3. 2-component paint according to claim 1, characterized in that the catalyst C) is a phosphane of the general formula P (CH₂-Y) ₃, in which the radicals Y may be the same or different and the radical -OH, -CH₂CN or -N (Z) ₂ mean, where Z is an alkyl radical having 1 to 5 carbon atoms, or a tertiary phosphane of the general formula P (R⁴, R⁵, R⁶) in which the radicals R⁴, R⁵ and R⁶ are an alkyl radical with 1 to 12 carbon atoms or a phenyl radical, unsubstituted or substituted with at least one alkyl, alkoxy or dialkylamino group each having 1 to 4 carbon atoms in the alkyl radical, R⁴, R⁵ and R⁶ are identical or different, but at least one of the radicals is a phenyl group, or an aminophosphorane of the general formula (R⁷, R⁸, R⁹) P = NC (R¹⁰, R¹¹, R¹²)
in which R⁷, R⁸, R⁹ are the same or different and are an alkyl radical having 1 to 12 carbon atoms or a phenyl radical, unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each having 1 to 4 carbon atoms in the alkyl radical and R¹⁰, R¹¹, R¹² are the same or different and are an alkyl radical having 1 to 5 carbon atoms or a phenyl radical. 4. 2-component paint according to claim 1, characterized in that the Catalyst C) trishydroxymethylphosphine, trisdimethylaminomethylphosphine, Tris-p-anisylphosphine, methyl-diphenylphosphine, methyl-di-p-anisylphosphine or α, α-dimethylbenzyliminotributylphosphorane. 5. 2-component paint according to claim 1, characterized in that in the Compound A) the radical R¹R²C = CR³-X (I) is derived from acrylic acid and the compound B) contains ester-like malonic acid fractions. 6. 2-component paint according to claim 1, characterized in that the Radical R¹R²C = CR³-X (I) wherein X is -CO- and R³ is hydrogen or alkyl with 1 to 8 carbon atoms mean one or more unsaturated, at most dibasic carboxylic acid with 2 to 10, preferably 3 to 6, carbon atoms, preferably acrylic acid, methacrylic acid and / or maleic acid is derived. 7. 2-component paint according to claim 1, characterized in that in the Compounds A) the groups (I) to the rest of a polyol or polyamine, preferably of an oligomer and / or polymer are bound. 8. 2-component paint according to claim 1, characterized in that the Compound A) from a polyester, acrylic resin, epoxy resin, each OH groups containing, and / or amine resin is derived. 9. 2-component paint according to claim 1, characterized in that the grouping AH (II) of the compound B)

• aa) for the meaning <CH- of a compound with the grouping -CO-CHR¹-CO-, NC-CHR¹-CO-, NC-CH₂-CN, = PO-CHR¹-CO-, = CHR¹-CN, = PO -CHR¹-PO =, -CO-CHR¹-NO₂,
• bb) for the meaning <NH of a primary and / or secondary polyamine,
• cc) for the meaning -SH derived from a thioalcoholic acid ester, amide and / or a mercaptan.

10. 2-component paint according to claim 1, characterized in that the Compound B) from an at least divalent compound from the group polyols, Derives polyamines and / or polymercaptans. 11. Use of the two-component lacquer according to one of claims 1 to 10 for the production of coatings on substrates of organic or inorganic Natural, especially on metal, preferably in a thin layer.