DE4008343A1 - HAUNDBARE COMPOSITION - Google Patents

Abstract

This invention provides a curable composition comprising: I) a resin component containing as essential functional groups epoxy group, and silanol group and/or hydrolyzable group directly attached to silicon atom, II) at least one crosslinking agent selected from the group consisting of carboxylic acid compounds, polyisocyanate compounds and aminoaldehyde resins, and III) at least one curing catalyst selected from the group consisting of organometallic compounds, Lewis acids, protonic acids and compounds having Si-O-Al bond or bonds.

Description

The present invention relates to a novel curable Composition.

Known curable compositions are for. For example, those that a hydroxyl-containing resin and a crosslinking agent such as Example, a diisocyanate compound, a melamine resin or and containing the crosslinking agent are curable. These curable compositions have but disadvantages. For example, the usage leads a diisocyanate compound to a coating film, the Weather resistance is not satisfactory and which tends to yellowing. On the other hand, the requires Use of a melamine resin usually a burn-in at high temperatures of about 140 ° C or above and provides a coating film that is resistant to acids is little stable.

Other curable compositions are available. Thus, JP-A-67 553/1985 describes z. B. a curable Composition comprising an aluminum chelate compound and a vinyl polymer containing a monomer component Alkoxysilane compound such as. B. Methacryloxypropyltrimethoxysilane contains.

But also this described curable composition shows disadvantages. Since the silanol group, by the Hydrolysis of the alkoxy group bonded to the silicon atom is formed, the only functional group for the Networking is used to cure the composition needed large amounts of water. Consequently, big ones lead Quantities of by-products, e.g. B. Alcohols from the Hydrolysis, resulting in deteriorated properties of the cured product. If, on the other hand, the Composition only by the moisture in the air is cured, the composition is initially at the Surface hardened while the interior in general  incompletely cured leaves, so that the hardening with a high probability to a shrunken Product leads. Another disadvantage of this curable Composition is that they have a coating film with low adhesion to substrates and coating films supplies.

An object of the present invention is the creation a new curable composition, from the above Disadvantages is free.

Another object of the present invention is the Creation of a new curable composition that is Cures excellent and a coating film which leads in terms of weather resistance and Acid resistance, adhesion to substrates and Coating films, external appearance and such is outstanding.

These and other objects of the present invention will be apparent from the description below.

According to the invention, a curable composition for Provided comprising:

• (I) a resin component that is essential functional groups, an epoxy group and a Silanol group and / or directly to a silicon atom contains bound hydrolyzable group;
• (II) at least one crosslinking agent selected from carboxylic acids, polyisocyanate compounds and Aminoaldehyde resins, and
• (III) at least one curing catalyst selected from organometallic compounds, Lewis Acids, protic acids and compounds with Si-O-Al bond or bonds.

After intensive research in this area, it was found that a new curable composition containing a Resin component as essential functional groups a silanol group and / or one directly to a silicon atom bonded hydrolyzable group (these groups are hereinafter referred to as "silane group") and a Contains epoxy group that specified above Crosslinking agent and those specified above Curing catalyst comprises the above disadvantages of conventional hardenable compositions does not show Cures excellent and a coating film whose weathering and acid resistance, Adhesion to substrates and coating films, external Appearance and the like is excellent. The The present invention is based on these findings.

The term "directly attached to a silicon atom hydrolyzable group "as used herein refers to a group attached to a silicon atom is bound and in the presence of water or moisture hydrolyzed to result in a silanol group. Examples of such hydrolyzable groups are those which are represented by the following formulas:

In the above formulas, R 'is an alkyl group of 1 to 4 carbon atoms and R ", R" 'and R "", which are the same or are different, represent alkyl groups of 1 to 8 Carbon atoms, aryl groups and aralkyl groups.

Examples of C _1-8 -alkyl groups in the above formulas are methyl, ethyl, n -propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-octyl, isooctyl, etc Examples of aryl groups are phenyl, tolyl, xylyl, etc. Examples of aralkyl groups are benzyl, phenethyl, etc.

Another example of a hydrolyzable group, which is bonded directly to a silicon atom is the

The curable composition of the invention contains (I) the resin component, (II) the crosslinking agent and (III) the curing catalyst as described above. From These components will hereinafter be the resin component I), which as essential functional groups one Silane group and an epoxy group contains, closer described.  

Preferred examples of the resin component (I) are in With regard to good hardenability ones Resin components as essential functional groups Silane, epoxy and hydroxyl groups.

Suitable examples of silane groups in the Resin component (I) are the groups of the formula (1 ') and (2 ') and silanol groups, which improve the Hardenability, storage stability and the like as appropriate have proven.

Suitable examples of the epoxy group in the Resin component (I) are alicyclic epoxy groups which react quickly with silane groups and hydroxyl groups and which are useful for improving curability.

The resin component (I) is a resin or a resin mixture, each silane and epoxy groups or silane, epoxy and hydroxyl groups. Concrete examples of this are given below under (i) to (v):

• (i) a resin containing silane and epoxy groups (hereinafter referred to as "resin component (i)" designated);
• (ii) a resin mixture of a silane-containing Resin or a silane-containing compound and an epoxy-containing resin or a Epoxy-containing compound, wherein at least one of these components is a resin (im hereinafter referred to as "resin component (ii)");
• (iii) a resin containing silane, epoxy and hydroxyl groups contains (hereinafter referred to as "resin component (iii)" designated);  
• (iv) a resin mixture containing a resin component (ii) is in which a hydroxyl group in one or both of the silane-containing and epoxy containing resins (compounds) is present (hereinafter referred to as "resin component (iv)" designated); and
• (v) a resin mixture consisting of any of above resin components (i) to (iv) and a Hydroxyl-containing resin or a hydroxyl containing compound (hereinafter as "resin component (v)").

In the following, the resin components (i) to (v) become closer described.

Resin component (i)

The resin component (i) contains on average at least one epoxy group per molecule and at least one silane group and has one Number average molecular weight of about 1000 to about 200,000, preferably about 3000 to about 80 000, up. The resin component (i) with fewer epoxy and silane groups than stated above leads to a composition whose hardenability is worse and therefore is undesirable. The resin component (i) with a number average molecular weight of less than about 1000 leads to one Coating film, whose physical Properties, weatherability and the like are deteriorated, and the Resin component (i) having a number average of Molecular weight increased above about 200,000 the viscosity of the composition and power the composition for one  Coating process less suitable and is therefore undesirable.

Examples of the resin component (i) are, for. B. a reaction product that was prepared by reacting a resin (A) with a functional group, a compound (B) with Epoxy group and functional group, the complementary-reactive with the functional Group of the resin (A), and a compound (C) with silane group and functional group, the complementary-reactive with the functional Group of the resin (A) is.

The resin (A), the compound (B) and the Compound (C) will be described in more detail below described.

The term "functional group associated with the functional group is complementary-reactive ", as used here means that the functional groups react with each other can. Suitable groups may, for. B. from the to be selected in the following.  

table

The functional groups that are together may be complementary-reactive Way be selected from the list above, to form a combination. suitable Combinations are given below.

Combinations of Functional Groups of Resin (A) / Compound (B)
(1) / (5), (2) / (4), (3) / (3), (4) / (1), (5) / (1), (6) / (4), (6 ) / (8), (7) / (4), (7) / (5), (7) / (8), (8) / (1), (9) / (4), etc.

Combinations of Functional Groups of Resin (A) / Compound (C)
(1) / (5), (2) / (3), (2) / (4), (2) / (5), (3) / (3), (4) / (2), (4 ) / (6), (4) / (7), (5) / (1), (5) / (2), (5) / (6), (5) / (7), (6) / (4), (6) / (8), (7) / (4), (7) / (5), (7) / (8), (8) / (1), (9) / (4 ), etc.

The resin (A) can be used without special limitation suitably from conventional resins, which have the above functional groups, to be selected. Concrete examples of this Resin (A) are vinyl resins, fluorine-containing Resins, polyester resins, alkyd resins, silicone resins, Urethane resins, polyether resins, etc.

The resin (A) has on average per molecule at least one functional group with the functional group of the compound (B) is reactive, and at least one functional Group with the functional group of Compound (C) is reactive. The functional Groups in the resin (A) can be the same or to be different.  

When the resin (A) has identical functional groups has, then z. B. a resin (A), the on average at least two hydroxyl groups having, with the compound (B), which the Isocyanate group (5) contains, and the compound (C) containing the isocyanate group (5), be reacted or a resin (A), the on average at least two isocyanate groups (5) may be combined with the compound (B) containing the Hydroxyl group (1) contains, and the compound (C) containing the hydroxyl group (1), be implemented.

When the resin (A) is different functional Groups, then z. A resin (A), the average at least one Hydroxyl group (1) and at least one Carboxyl group (2) contains, with the compound (C) having the isocyanate group (5), and the compound (B) containing the epoxy group (4) owns, be implemented.

The functional group of the compound (B), which with the functional group of the compound (A) can be implemented, an epoxy group his. And the functional group of the compound (C) associated with the functional group of Compound (A) should be implemented, a Be silane group.

In the following, resins (A) are described which Hydroxyl, carboxyl, isocyanate, silane, Epoxy, mercapto, amino, acid anhydride and phenolic hydroxyl groups and the like contain.  

Hydroxyl-containing resin

Examples of such a resin are those described in (1) to (6) below be specified.

• (1) Hydroxyl-containing vinyl resin
  The resin is a copolymer of a hydroxyl-containing polymerizable unsaturated monomer (a) described later and optionally another polymerizable unsaturated monomer (b).
  Hydroxyl-containing polymerizable unsaturated monomer (a)
  Typical of such monomers are the compounds represented by the formulas (1) to (4) wherein R¹ represents a hydrogen atom or a hydroxyalkyl group; in which R¹ is as defined above; wherein Z represents a hydrogen atom or a methyl group, m is an integer of 2 to 8, p is an integer of 2 to 18, and q represents an integer of 0 to 7; in which Z is as defined above, T₁ and T₂ are the same or different and each represents a divalent C _1-20 hydrocarbon group and S and U are each integers from 0 to 10, provided that the sum of S and U is 1 to 10.
  The hydroxyalkyl group in the formulas (1) and (2) has 1 to 6 carbon atoms. Specific examples of this are -C₂H₄OH, -C₃H₆OH, -C₄H₈OH, etc.
  Examples of the divalent C _1-20 hydrocarbon groups in the formula (4) are shown below Examples of the monomer component of the formula (1) are CH₂ = CHOH, CH₂ = CHOC₄H₈OH, etc.
  Examples of the monomer component of the formula (2) are, for. Those represented by the following formulas: CH₂ = CHCH₂OH, CH₂ = CHCH₂OCH₂CH₂OH,
  CH₂ = CHCH₂O (CH₂CH₂O) ₂H,
  CH₂ = CHCH₂O (CH₂CH₂O) ₃H examples of the monomer component of the formula (3) are z. B. the compounds represented by the following formulas: CH₂ = C (CH₃) COOC₂H₄OH, CH₂ = CHCOOC₃H₆OH, Examples of the monomer component of the formula (4) include the following compounds: It is likewise possible to use as monomer (a) an adduct of any hydroxyl-containing unsaturated monomers of the formulas (1) to (4) with ε- caprolactone, γ- valerolactone or a similar lactone.
  Polymerizable unsaturated monomer (b):
  Typical of such a monomer are those listed below under (b-1) to (b-6).
  • (b-1) Olefin type compounds such as. Ethylene, propylene, butylene, isoprene and chloroprene;
  • (b-2) vinyl ethers and allyl ethers, such as. Ethylvinylether, propylvinylether, isopropylvinylether, butylvinylether, tert-butylvinylether, pentylvinylether, hexylvinylether, isohexylvinylether, octylvinylether, 4-methyl-1-pentylvinylether and similar chainlike alkylvinylether, cyclopentylvinylether, cyclohexylvinylether and similar Cycloalkylvinylether, Phenylvinylether, o-, m- or p Tolyl vinyl ethers and like aryl vinyl ethers, benzyl vinyl ethers, phenethyl vinyl ethers and similar aralkyl vinyl ethers, etc.
  • (b-3) vinyl ester and propenyl ester such. Vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl pivalate, vinyl caprate and like vinyl esters, isopropenyl acetate, isopropenyl propionate and like propenyl esters, etc .;
  • (b-4) esters of acrylic acid or methacrylic acid, such as. C _1-18 alkyl esters of acrylic acid or methacrylic acid including methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate and lauryl methacrylate, C _2-18 Alkoxyalkyl esters of acrylic acid or methacrylic acid including methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate and ethoxybutyl methacrylate, etc .;
  • (b-5) vinyl aromatic compounds, such as. Styrene, α -methylstyrene, vinyltoluene, p-chlorostyrene, etc .; and
  • (b-6) acrylonitrile, methacrylonitrile, etc.
• (2) Hydroxyl and fluorine-containing resin
  The resin is a copolymer of the hydroxyl-containing polymerizable unsaturated monomer (a), a fluorine-containing polymerizable unsaturated monomer (c) and optionally the polymerizable unsaturated monomer (b).
  Fluorine-containing polymerizable unsaturated monomer (c):
  Typical of the monomer (c) are the compounds of the formulas (5) and (6). CX₂ = CX₂ (5) in which the groups X are the same or different and each represents hydrogen, chlorine, bromine, fluorine, alkyl or haloalkyl, provided that the compound contains at least one fluorine atom; in which Z is as defined above, R² is a fluoroalkyl group and n is an integer from 1 to 10.
  The alkyl group in the formula (5) has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples thereof are methyl, ethyl, propyl, isopropyl, butyl and pentyl. The haloalkyl group in the formula (5) has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Concrete examples thereof are CHF₂, CH₂F, CCl₃, CHCl₂, CH₂Cl, CFCl₂, (CF₂) ₂CF₃, (CF₂) ₃CF₃, CF₂CH₃, CF₂CHF₂, CF₂Br, CH₂Br, CF₃ Examples of the monomer of the formula (5) are the compounds CF₂ represented by the following formulas = CF₂, CHF = CF₂, CH₂ = CF₂, CH₂ = CHF, CClF = CF₂, CHCl = CF₂, CCl₂ = CF₂, CClF = CClF, CHF = CCl₂, CH₂ = CClF, CCl₂ = CClF, CF₃CF = CF₂, CF₃CF = CHF , CF₃CH = CF₂, CF₃CF = CH₂, CHF₂CF = CHF, CH₃CF = CF₂, CH₃CF = CH₂, CF₂ClCF = CF₂, CF₃CCl = CF₂, CF₃CF = CFCl, CF₂ClCCl = CF₂, CF₂ClCF = CFCl, CFCl₂CF = CF₂, CF₂CCl = CClF, CF₃CCl = CCl₂, CClF₂CF = CCl₂, CCl₃CF = CF₂, CF₂ClCCl = CCl₂, CFCl₂CCl = CCl₂, CF₃CF = CHCl, CClF₂CF = CHCl, CF₃CCl = CHCl, CHF₂CCl = CCl₂, CF₂ClCH = CCl₂, CF₂ClCCl = CHCl, CCl₃CF = CHCl, CF₂ClCF = CF₂ , CF₂BrCH = CF₂, CF₃CBr = CHBr, CF₂ClCBr = CH₂, CH₂BrCF = CCl₂, CF₃CBr = CH₂, CF₂CH = CHBr, CF₂BrCH = CHF, CF₂BrCF = CF₂, CF₃CF₂CF = CF₂, CF₃CF = CFC F₃, CF₃CH = CFCF₃, CF₂ = CFCF₂CHF₂, CF₃CF₂CF = CH₂, CF₃CH = CHCF₃, CF₂ = CFCF₂CH₃, CF₂ = CFCH₂CH₃, CF₃CH₂CH = CH₂, CF₃CH = CHCH₃, CF₂ = CHCH₂CH₃, CH₃CF₂CH = CH₂, CFH₂CH = CHCFH₂, CH₃CF₂CH = CH₂, CH₂ = CFCH₂CH₃, CF₃ (CF₂) ₂CF = CF₂, CF₃ (CF₂) ₃CF = CF₂ The fluoroalkyl group in the formula (6) has three to 21 carbon atoms. Concrete examples thereof are C₄F₉, (CF₂) ₆CF (CF₃) ₂, C₈F₁₇ and C₁₀F₂₁.
  Examples of the monomer of the formula (6) are the compounds represented by the following formulas:
• (3) Hydroxy-containing polyester resin
  The resin is prepared by esterification or ester interchange reaction of a polybasic acid with a polyhydric alcohol. Examples of suitable polybasic acids are compounds having two to four carboxyl groups or methylcarboxylate groups per molecule, such as. Phthalic acid or phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid or maleic anhydride, pyromellitic acid or pyromellitic anhydride, trimellitic acid or trimellitic anhydride, succinic or succinic anhydride, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dimethyl isophthalate, dimethyl terephthalate and the like.
  Examples of suitable polyhydric alcohols are alcohols having two to six hydroxyl groups per molecule, such as. For example, monobasic acids may be used to prepare the resin, examples of which include fatty acids of castor oil, soybean oil, tall oil, linseed oil, or the like and benzoic acid.
• (4) Hydroxyl-containing polyurethane resin
  The resin is an isocyanate group-free resin prepared by modifying a hydroxyl-containing vinyl resin, hydroxyl-containing polyester resin or the like with a polyisocyanate compound, such as e.g. Tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or the like.
• (5) Hydroxyl-containing silicone resin
  The resin is an alkoxysilane and silanol group-free resin prepared by modifying a hydroxyl-containing vinyl resin, hydroxyl and fluorine-containing resin, hydroxy-containing polyester resin or the like with a silicone resin, such as a silicone resin. Z-6018 or Z-6188 (trademark for products of Dow Corning GmbH) or SH 5050, SH 6018 or SH 6188 (trademark for products of Toray Silicone Co. Ltd.).
• (6) reaction product prepared by partial or complete hydrolysis a polyvinyl acetate or a  Copolymers of vinyl acetate and a further polymerizable unsaturated monomers.

Carboxy-containing resin

Typical examples of such a resin are given below under (1) to (3):

• (1) Carboxyl-containing vinyl resin
  The resin is a polymer of a carboxyl-containing polymerizable unsaturated monomer (d) and optionally the polymerizable unsaturated monomer (b).
  Carboxyl-containing polymerizable unsaturated monomer (d):
  Typical of the monomer (d) are the compounds represented by the following formulas (7) and (8) wherein R³ is a hydrogen atom or a lower alkyl group, R⁴ is a hydrogen atom, a lower alkyl group or a carboxyl group, and R⁵ represents a hydrogen atom, a lower alkyl group or a carboxy-lower alkyl group; in which R⁶ is hydrogen or methyl and m is as defined above.
  Preferred lower alkyl groups in the formula (7) are those having 1 to 4 carbon atoms, especially methyl.
  Examples of the monomer of the formula (7) are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and fumaric acid.
  Examples of the monomer (8) are 2-carboxyethyl acrylate or methacrylate, 2-carboxypropyl acrylate or methacrylate and 5-carboxypentyl acrylate or methacrylate.
  Also usable as the monomer (d) is an adduct of 1 mole of a hydroxyl-containing polymerizable unsaturated monomer (a) with one mole of an anhydride of a carboxylic acid, such as e.g. Maleic anhydride, itaconic anhydride, succinic anhydride, phthalic anhydride or the like.
• (2) Carboxyl and fluorine-containing resin
  The resin is a copolymer of the fluorine-containing polymerizable unsaturated monomer (c), the carboxyl-containing polymerizable unsaturated monomer (d) and optionally the polymerizable unsaturated monomer (b). These monomers may be any of the monomers listed above.
  Also usable is a resin prepared by reacting the fluorine-containing polyol resin with the carboxylic acid anhydride compound.
• (3) Carboxyl-containing polyester resin
  Examples of such a resin are a resin prepared by esterifying the polybasic acid or the corresponding anhydride with the polyhydric alcohol, a resin prepared by adduct formation between acid anhydride and hydroxyl-containing polyester resin, etc.

Isocyanate-containing resin

Examples of such a resin are those in following under (1) to (4) indicated.

• (1) Isocyanate-containing vinyl resin
  The resin is a polymer of the isocyanate-containing polymerizable unsaturated monomer (e) and optionally the polymerizable unsaturated monomer (b).
  Isocyanate-containing polymerizable unsaturated monomer (s):
  Typical examples of the monomer (e) are those represented by the formulas (9) and (10) in which R⁶ and n are as defined above, examples of the monomer of formula (9) being isocyanatoethyl acrylate or methacrylate; and in which R⁶ and n are as defined above and R⁷ is hydrogen or an alkyl group having 1 to 5 carbon atoms, a specific example of the monomer of the formula (10) is α , α- dimethyl-m-isopropenylbenzylisocyanat.
  Also usable as the monomer (e) is a reaction product of one mole of the hydroxyl-containing polymerizable unsaturated monomer (a) and one mole of a polyisocyanate compound. Examples of suitable polyisocyanate compounds are tolylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, dicyclohexylmethane-4 '4'-diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, bis (4-isocyanatophenyl) sulfone, isopropylidenebis (4-phenyl isocyanate), lysine isocyanate and isophorone diisocyanate, polymers thereof, biuret compounds thereof, etc.
  Also usable as the isocyanate-containing resin is a reaction product prepared by reacting a hydroxyl-containing vinyl resin with e.g. B. the polyisocyanate compound.
• (2) Isocyanate- and fluorine-containing resin
  The resin is one prepared by reacting the hydroxyl and fluorine-containing resin with the polyisocyanate compound.
• (3) Isocyanate-containing polyester resin
  The resin is one prepared by reacting the hydroxyl-containing polyester resin with the polyisocyanate compound.
• (4) Isocyanate-containing polyurethane resin
  The resin is one prepared by reacting a polyether polyol with the polyisocyanate compound. Examples of the polyether polyol are polyether polyols prepared by polymerization of glycols (such as ethylene glycol, propylene glycol and the like) and alkylene oxides (e.g., ethylene oxide, propylene oxide and the like), polytetramethylene ether glycols prepared by cationic polymerization of tetrahydrofuran, etc ,

Silane-containing resin

Examples of the resin are as follows given under (1) to (4).

• (1) A resin prepared by reacting the Hydroxyl-containing resin having a Isocyanate-containing silane compound, which will be described later.
• (2) A resin prepared by reacting the Isocyanate-containing resin having a Hydroxy-containing silane compound which will be described later.
• (3) A silicone resin used in the production of the hydroxyl-containing silicone resin was used.
• (4) A polymer of a silane-containing polymerizable unsaturated monomers (g), which will be described later, and optionally the polymerizable unsaturated monomers (b) and fluorine containing polymerizable unsaturated Monomers (c).

Epoxy-containing resin

Examples of this resin are as follows given under (1) and (2).

• (1) A resin prepared by reacting the Hydroxyl-containing resin having a Isocyanate-containing epoxy compound, which will be described later.
• (2) A polymer of an epoxy-containing polymerizable unsaturated monomers (f), which will be described later, and optionally polymerizable unsaturated monomers (b) and fluorine containing polymerizable unsaturated Monomers (c).

Mercapto-containing resin

The resin is one that has been produced by reaction of the hydroxyl-containing Resin or silane-containing resin with a mercapto-containing compound which will be described later.

Amine-containing resin

The resin is one that has been produced by reaction of the hydroxyl-containing Resin or silane-containing resin with an amine-containing compound, later is described.

Acid anhydride group-containing resin

Examples of such a resin are in following under (1) and (2) indicated.

• (1) A polymer of the monomer (d) with Acid anhydride group (such as Maleic anhydride, itaconic anhydride,  Succinic anhydride and the like) and optionally the polymerizable unsaturated monomers (b).
• (2) A resin consisting essentially of an acid anhydride (such as trimellitic anhydride, Pyromellitic anhydride and the like) and a polyhydric alcohol.

Phenolic hydroxyl group-containing resin

Examples of this resin are as follows specified under (1) to (4).

• (1) A phenol or cresol type resin (such as z. For example, a phenol type novolak resin Phenol-type resol resin, a novolak resin of the cresol type, etc.).
• (2) A polymer that is essential Monomer component a polymerizable phenolic hydroxyl-containing monomer (such as p-vinylphenol, etc.).
• (3) A resin made of the epoxy containing resin and a polyvalent phenolic compound (such as catechol, Resorcinol, hydroquinone, pyrrogallol, Hydroxyhydroquinone and the like) in such proportions that the resulting resin an excess polyhydric phenolic compound contains.
• (4) A resin prepared by reaction an eoxy-containing resin having a  phenolic hydroxy-containing Compound (such as hydroxybenzoic acid).

The compound (B), which is responsible for the Resin component (i) is useful in the molecule at least one epoxy group and at least one functional group with the functional Group of the resin (A) can react to. The functional group with the functional Group of the resin (A) can react, a Be epoxy group. If the functional group is an epoxy group, contains the compound (B) at least two epoxy groups in the molecule.

The following are typical examples of the Compound (B) described.

Hydroxyl-containing epoxy compound

Examples of such a compound are the Compounds represented by the formulas (11) to (21) be represented.

In the above formulas, R⁶ and n are as defined above, R⁸ is a divalent C _1-8 hydrocarbon group and the groups R⁹ are the same or different and each represents a divalent C _1-20 hydrocarbon group.

In the formulas (11) to (21), the divalent C _1-8 hydrocarbon group may be appropriately selected from the above divalent C _1-20 hydrocarbon groups, and the divalent C _1-20 hydrocarbon groups include the above examples of such Group.

Concrete examples of compounds of the formulas (11) to (21) are those that are governed by the following formulas are presented.

Silane-containing epoxy compound

Examples of such a compound are the Compounds represented by formulas (22) to (25) being represented.

In the above formulas, R⁶ and R⁸ have the same meaning as mentioned above, and the groups R⁸ may be the same or different, the groups Y are the same or different and each represents a hydrogen atom, a hydroxyl group, a hydrolyzable group, a C _1-8 alkyl group an aryl group or an aralkyl group, provided that at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Examples of hydrolyzable groups in the formulas (22) to (25) are those of the above formulas (1 ') to (6'). The examples of the C _1-8 alkyl groups, aryl groups and aralkyl groups in the formulas (22) to (25) include the above examples of these groups.

Concrete examples of compounds of the formulas (22) to (25) are the following Formulas represented:

Also usable is a condensation product each of the compounds of the formulas (22) to (25) with one described below Polysilane compound (such as the compounds of the formulas (38) to (40)). A concrete one Example of such a compound is the represented by the following formula

polyepoxy

Examples of such a compound are the Compounds represented by formulas (26) to (33) being represented

In the above formulas, R⁶ and R⁸ are as defined above. The groups R⁶ may be the same or different; the groups R⁸ may be the same or different; the groups R¹⁰ are the same or different and each represents a C _1-8 alkyl group, an aryl group or an aralkyl group; the groups R¹¹ are the same or different and each represents a hydrogen atom or a C _1-4 alkyl group; and w is an integer from 0 to 10.

Examples of the compounds of the formulas (26) to (33) are those through the following Formulas are shown:

Further examples of the polyepoxy compound are those through the following formulas be represented:

Also usable as a polyepoxy compound is an adduct of

with a polyisocyanate compound. Examples for suitable polyisocyanate compounds organic diisocyanates, such as. B. hexamethylene diisocyanate, Trimethylhexamethylene diisocyanate and the like aliphatic diisocyanates; hydrogenated Xylylene diisocyanate, isophorone diisocyanate and similar cycloaliphatic diisocyanates; tolylenediisocyanate, 4,4'-diphenylmethane diisocyanate and the like aromatic diisocyanates; an adduct of organic diisocyanate with a polyvalent Alcohol, a low molecular weight polyester resin, Water or the like; a copolymer such organic diisocyanates; isocyanate Biurete, etc. Representative in trade available products for Polyisocyanate compounds are among the following trade names offered: "BURNOCK D-750, -800, DN-950, DN-970 and 15-455" (Products of Dainippon Ink and Chemicals Inc.), "DESMODUL L, NHL, IL and N3390" (Products Bayer AG, FRG), "TAKENATE D-102, -202, 110N and -123N "(Takeda Chemical Industries Ltd.), "COLONATE-L, -HL, -EH and -203 "(products of Nippon Polyurethane Kogyo K.K.), "DURANATE 24A-90CX" (product of Asahi Chemical Industry Co. Ltd.), etc. Also used as a polyepoxy compound are a Adduct of a compound of the formula

with a polybasic acid; a product that was prepared by oxidation of an ester with unsaturated group, such as. B. a group the formula

in the molecule with a peracid or the like, wherein an example of the ester is an ester with a number average molecular weight of 900, made by esterification of tetrahydrophthalic Trimethylolpropane, 1,4-butanediol and the like, is.

Isocyanate-containing epoxy compound

An example of this is a connection that was prepared by reacting the hydroxyl containing epoxy compound with the Polyisocyanate compound in such a way that the Epoxy and isocyanate groups in the reaction product remain. Examples of such Reaction product is the reaction product of Compound of formula (11) with hexamethylene diisocyanate

a reaction product of the compound of the formula (15) with tolylene diisocyanate

a reaction product of the compound of the formula (18) with isophorone diisocyanate  

a reaction product of the compound of the formula (20) with isophorone diisocyanate

and a reaction product of the compound of Formula (21) with xylylene diisocyanate

The unsaturated group-containing compound may be any of those described below Silane-containing polymerizable unsaturated monomers.

The compound (C) used for the Resin component (i) is suitable, has in Molecule at least one silane group and at least one functional group associated with the functional group of the resin (A) reactive is on. The functional group with the functional group of the resin (A) reactive is, can be a silane group. In this Case, the compound (C) contains at least two Silane groups in the molecule.  

The following are typical examples of the Compound (C) described.

Hydroxyl-containing silane compound

Examples of such a compound are those represented by formulas (34) to (36) being represented

In the above formulas, R⁸, R⁹ and Y are as defined above; the groups R⁸ can be the same or be different, the groups R⁹ can be the same or different and the groups Y can be the same or different, provided that at least one of the groups Y is a hydrogen atom, a hydroxyl group or is a hydrolyzable group.

Concrete examples of compounds of the formulas (34) to (36) are the ones that are used by the following formulas are presented  

Also usable as such compound is a condensation product of each Compound of formulas (34) to (36) having a described below polysilane compound. An example of such a Condensation product is a compound that represented by the following formula.

polysilane

The polysilane compound contains in the molecule at least two groups selected from directly bonded to a silicon atom hydrolyzable groups and silanol groups.

Examples of such a compound are those by the following formulas (38) to (40)  

In the above formulas, the groups Y 'are same or different and set each one Hydrogen atom, a hydroxy group or a hydrolyzable group, R¹⁰ is as above defined and the groups R¹⁰ are the same or different.

Concrete examples of compounds of the formulas (38) to (40) are dimethyldimethoxysilane, dibutyldimethoxysilane, Diisopropyl dipropoxysilane, diphenyldibutoxysilane, Diphenyldiethoxysilane, diethyldisilanol, Dihexyldisilanol, methyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, Propyltrimethoxysilane, phenyltriethoxysilane, Phenyltributoxysilane, hexyltriacetoxysilane, Methyltrisilanol, phenyltrisilanol, Tetramethoxysilane, tetraethoxysilane, Tetrapropoxysilane, tetraacetoxysilane, Diisopropoxydivaleroxysilane, tetrasilanol and the compounds by the following Formulas are presented  

Condensation products such Polysilane compounds with each other are also usable.

Epoxy-containing silane compound

Examples of such a compound are the above silane-containing epoxy compounds.

Isocyanate-containing silane compound

An example of such a connection is represented by the following formula (41) connection

In the above formula, R⁸ and Y are as above defined and the groups Y can be equal or to be different.

At least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group, and b ' is 0 or 1.

Examples of compounds of formula (41) are represented by the following formulas:

Also usable as the isocyanate containing silane compound is a compound, which was made by implementing the Hydroxyl-containing silane compound with the Polyisocyanate compound.

Examples of such an isocyanate containing silane compound are the Reaction products of the compound of the formula (34) and a hexamethylene diisocyanate or Tolylene diisocyanate, such as. The connections, which are represented by the following formulas become:  

A suitable isocyanate-containing Silane compound is still a Condensation product of the isocyanate-containing Silane compound with z. The polysilane compound, such as As by the following formula illustrated connection

Mercapto-containing silane compound

Examples of such a compound are the Compounds represented by the formula (42) being represented

in which R⁸ and Y are as defined above and the groups Y are the same or different, provided that at least one of the groups  Y is a hydrogen atom, a hydroxyl group or is a hydrolyzable group.

Concrete examples of the connection of Formula (42) are represented by the following formulas reproduced:

Also usable as the mercapto-containing silane compound is a reaction product prepared by reacting the hydroxyl-containing silane compound with the polyisocyanate compound and a thiocol compound (e.g., HS-C _m H _{2 m} -OH, m being the same as above). , such as For example, the compound represented by the following formula:

Also usable is a condensation product the mercaptosilane compound with z. B. one Polysilane.

NH- or NH₂-containing silane compound

Examples of such a compound are the Compounds represented by formulas (43) and (44) being represented

In the above formulas, R⁸ and Y are as above defined, the groups R⁸ can be equal or be different and the groups Y are the same or different, provided that at least one of the groups Y is a hydrogen atom, a Hydroxyl group or a hydrolyzable group is.

Concrete examples of compounds of the formulas (43) and (44) are the ones given by the following formulas are presented

Also usable is a condensation product the compound of formula (43) or (44) with the Polysilane compound, such as. B. a connection the formula

Unsaturated group-containing silane compound

Usable as such a compound a silane-containing polymerizable unsaturated monomer (g), which is below is described.

In addition to the resins, by reaction of the resin (A) with the compounds (B) and (C) are prepared as resin component (i) a copolymer which has been prepared by copolymerization of the hydroxyl-containing polymerizable unsaturated monomers (a), of the epoxy-containing polymerizable unsaturated monomers (f), the silane containing polymerizable unsaturated  Monomers (g) and optionally the polymerizable unsaturated monomers (b) and the fluorine-containing polymerizable unsaturated monomers (c).

The epoxy-containing polymerizable unsaturated monomers (f) is a compound in the molecule an epoxy group and a radically polymerizable unsaturated Group contains. The epoxy group can be a alicyclic or aliphatic epoxy group.

Examples of the radically polymerizable unsaturated group are the groups that pass through the following formulas are shown:

In the above formula, R⁶ is as defined above.

Examples of the epoxy-containing polymerizable unsaturated monomers with radically polymerizable unsaturated Group CH₂ = C (R⁶) COO- are the compounds which are represented by the following formulas (45) to (57) being represented:

In the above formulas, R⁶, R⁸, R⁹ and w are as defined above, the groups R⁶ may be the same or different, the groups R⁸ are the same or different and the groups R⁹ are the same or different.

Concrete examples of monomers of the formulas (45) to (57) are the following Represented formulas

Examples of the epoxy-containing polymerizable unsaturated monomer with radically polymerizable unsaturated group

are those through the following formulas (58) to (60) are shown:

In the above formulas, R⁶ and R⁸ are as above defined, the groups R⁶ are the same or different and the groups R⁸ are the same or different.

Concrete examples of compounds of the formulas (58) to (60) are the following Formulas represented:  

Examples of the epoxy-containing polymerizable unsaturated monomers with radically polymerizable unsaturated group

are those represented by the formulas (61) to (63) being represented

In the above formulas, R⁶ and R⁸ are as above defined, the groups R⁶ are the same or different and the groups R⁸ are the same or different.

Concrete examples of compounds of the formulas (61) to (63) are those by the following Formulas represented:

Examples of the epoxy-containing polymerizable unsaturated monomers with radically polymerizable unsaturated Group of formula  

are those represented by formulas (64) to (69) shown:

In the above formulas, R⁶, R⁸, R⁹ and w are as defined above, the groups R⁶ may be the same or different, the groups R⁸ are the same or different and the groups R⁹ are the same or different.

Concrete examples of compounds of the formulas (64) to (69) are the following Formulas shown:

Examples of the epoxy-containing polymerizable unsaturated monomers with radically polymerizable unsaturated Group CH₂ = CHCH₂O- are those by the formulas (70) to (73) are shown:

In the above formulas, R⁶ and R⁸ are as above defined and the groups R⁸ can be equal or to be different.

Concrete examples of compounds of the formulas (70) to (73) are by the following Formulas shown:

Examples of the epoxy-containing polymerizable unsaturated monomers with radically polymerizable unsaturated Group CH₂ = CHO- are by the following Formulas (74) to (76) shown

In the above formulas, R⁶ and R⁸ are as above defined and the groups R⁸ are the same or different.

Concrete examples of compounds of the formulas (74) to (76) are the following Formulas shown

Examples of the epoxy-containing polymerizable unsaturated monomers with radically polymerizable unsaturated Group CH₂ = CH- are compounds as they represented by the formulas (77) to (79) become:

In the above formulas, R⁶ and R⁸ are as above defined and the groups R⁸ can be equal or to be different.

Concrete examples of compounds of the formulas (77) to (79) are those that are governed by the following formulas are presented  

Examples of the epoxy-containing polymerizable unsaturated monomers with radically polymerizable unsaturated group

are compounds, as defined by the formulas (80) to (84)

In the above formulas, R⁶, R⁸ and R⁹ are as above defined, the groups R⁶ are the same or different and the groups R⁹ are the same or different.

Concrete examples of the compounds of Formulas (80) through (84) are as they are represented by the following formulas

The silane-containing polymerizable unsaturated monomers (g) is a compound the at least one silane group and one radically polymerizable unsaturated Contains group per molecule.

Examples of the radically polymerizable unsaturated group are those by the following Formulas shown  

in which R⁶ is as defined above.

Examples of the silane-containing polymerizable unsaturated monomers with radically polymerizable unsaturated Group CH₂ = C (R⁶) -COO- are compounds such as they are represented by the formula (85)

in which R⁶, R⁹ and Y are as defined above are, the groups Y are the same or different and at least one of the groups Y is one Hydrogen atom, a hydroxy group or a is hydrolyzable group.

Examples of compounds of formula (85) are

γ - (meth) acryloxypropyltrimethoxysilane,
γ - (meth) acryloxypropyltriethoxysilane,
γ - (meth) acryloxypropyltripropoxysilane,
γ - (meth) acryloxypropylmethyldimethoxysilane,
γ - (meth) acryloxypropylmethyldiethoxysilane,
γ - (meth) acryloxypropylmethyldipropoxysilane,
γ - (meth) acryloxybutylphenyldimethoxysilane,
γ - (meth) acryloxybutylphenyldiethoxysilane,
γ - (meth) acryloxybutylphenyl dipropoxysilane,
γ - (meth) acryloxypropyldimethylmethoxysilane,
γ - (meth) acryloxypropyldimethylethoxysilane,
γ - (meth) acryloxypropylphenylmethylmethoxysilane,
γ - (meth) acryloxypropylphenylmethylethoxysilane,
γ - (meth) acryloxypropyl trisilanol,
γ - (meth) acryloxypropylmethyldihydroxysilane,
γ - (meth) acryloxybutylphenyldihydroxysilane,
γ - (meth) acryloxypropyldimethylhydroxysilane,
γ - (meth) acryloxypropylphenylmethylhydroxysilane

and compounds by the formulas

being represented.

Examples of the silane-containing polymerizable unsaturated monomers with radically polymerizable unsaturated group

are compounds, as defined by the formulas (86) to (88)  

In the above formulas, R⁶, R⁹ and Y are as above and the groups Y are the same or different, wherein at least one of Groups Y is a hydrogen atom, a Hydroxyl group or a hydrolyzable group is.

Concrete examples of compounds of the formulas (86) to (88) are compounds produced by the following formulas are shown:

Examples of the silane-containing polymerizable unsaturated monomers with radically polymerizable unsaturated Group of the formula CH₂ = C (R⁶) - are compounds of formulas (89) and (90)

In the above formulas, R⁶, R⁹ and Y are as defined above and the groups Y can be the same or different, with at least one of the groups Y is a hydrogen atom, a Hydroxyl group or a hydrolyzable group is.  

Concrete examples of compounds of the formulas (89) and (90) are those as defined by the following formulas are shown:

Examples of the silane-containing polymerizable unsaturated monomers with radically polymerizable unsaturated Group of the formula CH₂ = CHO- are compounds, as represented by the formulas (91) and (92) be represented

In the above formulas, R⁹ and Y are as above defined, the groups Y can be equal or be different and at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Concrete examples of compounds of the formulas (91) and (92) are the following:

Examples of the silane-containing polymerizable unsaturated monomers with radically polymerizable unsaturated Group of the formula CH₂ = CHCH₂O- are compounds of formulas (93) and (94)

In the above formulas, R⁹ and Y are as above defined, the groups Y can be equal or be different and at least one of the groups Y is a hydrogen atom, a hydroxyl group or a hydrolyzable group.

Concrete examples of compounds of the formulas (93) and (94) are the following:

Also usable as silane-containing polymerizable unsaturated monomer (g) a polysiloxane-unsaturated monomer containing a Silane group and a polymerizable contains unsaturated group and manufactured was achieved by implementing the above silane containing polymerizable unsaturated Monomers with z. A polysilane compound, such as B. the compounds of formulas (38) to (40).

Representative of the polysiloxane-unsaturated Monomers is a polysiloxane macromonomer, prepared by reaction of about 30 to about 0.001 mole percent of a compound of Formula (85) with about 70 to about 99.999 mole percent of at least one of Compounds of formulas (38) to (40) (eg. those described in GB-A-22 02 538 are). Also as polysiloxane-unsaturated Suitable monomers are the compounds which represented by the following formulas  

Resin component (ii)

The resin component (ii) is a mixture of a silane-containing resin or a silane containing compound (hereinafter referred to as "Resin (ii-1)") and an epoxy containing resin or an epoxy-containing Compound (hereinafter referred to as "resin (ii-2)" wherein at least one of the resins (ii-1) and (ii-2) is a resin.

The resin (ii-1) has on average per Molecule at least one silane group on and that Resin (ii-2) has on average per molecule at least one epoxy group. The resin or the Compound with less silane and epoxy groups as stated above reduces hardenability the composition and is therefore undesirable.

The resins (ii-1) and (ii-2) of Resin components (ii) each have one Number average molecular weight of about 1000 to about 200,000, preferably about 3000 to about 80 000, up.  

Suitably, as the resin (ii-1), for. B. a Silane-containing resin used, the was prepared from those for the resin component (i) useful starting materials in which Way that the resulting resin is free of Is epoxy groups.

Suitably used as resin (ii-2) z. For example, an epoxy-containing resin produced was made from the starting materials for the Resin component (i), in such a way that the resulting resin is free of silane groups.

The proportions for the resins (ii-1) and (ii-2) are chosen so that the resin component (ii) an epoxy / silane ratio of approximately 1:99 to about 99: 1, preferably about 1: 5 to about 99: 1. If the Resins (ii-1) and (ii-2) in an outside of above ratios are used this leads to a composition a low hardenability and you get one Coating film containing xylene resistance, Hardness and mechanical properties unsatisfactory and therefore undesirable.

Resin component (iii)

The resin component (iii) contains per molecule in Average at least one hydroxyl, Epoxy and silane group and has a number average of the molecular weight of about 1000 to about 200,000, preferably about 3,000 to about 80 000, up. With regard to a high Resistance to weather and water and the like is the number of hydroxyl groups average per molecule preferably in the  Range from about 2 to about 400. If less epoxy and silane groups than above specified, the hardenability suffers the composition, which is undesirable. On Number average molecular weight below about 1000 leads to deteriorated physical Characteristics, deteriorated Weatherability and the like and a Number average molecular weight of over about 200,000 leads to an increase in the Viscosity of the composition, what the Usability of the same for one Coating process is reduced and therefore is undesirable.

A hydroxyl group-containing resin component (i) is usable as the resin component (iii). The hydroxyl groups in the resin component (i) can be any of those in the Resin component (i) were introduced, those by reacting the resin (A) with the Compounds (B) or (C) were formed (eg. Reaction of epoxy and carboxyl groups) and those who through implementation of the Reaction product of the resin (A) and the Compounds (B) and (C) (eg of a product, that was made by implementing a Isocyanate-containing resin (A) with the Hydroxyl-containing compounds (B) and (C), in such a way that the resin on an excess Contains isocyanate groups) with a polyvalent Alcohol were introduced.

Resin component (iv)

The resin component (iv) is a resin mixture from those suitable for the resin component (ii) Resins (ii-1) and (ii-2), wherein one or  both of these resins contain hydroxyl. Examples for combinations of resins or compounds, which constitute the resin component (iv) are one Mixture of hydroxyl and silane-containing Resin / hydroxyl and epoxy-containing resin, a mixture of hydroxyl and silane containing resin / epoxy-containing resin or Compound, a mixture of silane-containing Resin or compound / hydroxyl and epoxy containing resin, etc.

The hydroxyl and silane-containing resin contains On average, at least each molecule a hydroxyl and a silane group and has a number average molecular weight of about 1000 to about 200,000, preferably about 3000 to about 80 000, up. Fewer as an average of one hydroxyl group per Molecule leads to a reduced hardenability the composition and is therefore undesirable. With regard to a high resistance to Weather, water and the like is the average number of hydroxyl groups per Molecule preferably in the range of about 2 to about 400. Less than a silane group leads to a deteriorated hardenability of the Composition and is therefore undesirable. A molecular weight below 1000 deteriorates the physical properties that Weatherability and the like and a Molecular weight over 200,000 increases the Viscosity of the composition and deteriorates their usefulness for one Coating process, which is undesirable.

The resin can be a silane and hydroxyl containing resin that has been prepared from those suitable for the resin component (iii)  Starting materials in such a way that the resulting resin is free of epoxy groups.

The hydroxyl and epoxy-containing resin contains On average, at least each molecule a hydroxyl and epoxy group and has one Number average molecular weight of about 1000 to about 200,000, preferably about 3000 to about 80 000, up.

Less than average, a hydroxyl group the hardenability of the molecule deteriorates per molecule Composition and is therefore undesirable. With regard to a high resistance to Weather, water and the like is the average number of hydroxyl groups per Molecule preferably in the range of about 2 to about 400. Less than one epoxy group leads to a deteriorated hardenability of the Composition and is therefore undesirable. A molecular weight below 1000 deteriorates the physical properties that Weatherability and the like and a Molecular weight over 200,000 increases the Viscosity of the composition and makes this therefore less suitable for one Coating process, which is undesirable.

The resin can be an epoxy and hydroxyl containing resin from those for Resin component (iii) suitable Starting materials was prepared in the Way that the resulting resin is free of Silane is.

The proportions of the two resins or Compounds in the resin component (iv) are chosen so that the resin component (iv) a  Ratio of epoxy / silane of about 1: 99 to about 99: 1, preferably about 1: 5 to about 99: 1. On Epoxy / silane ratio outside of the above specified area leads to a Low hardenability and composition provides a coating film whose Xylene resistance, hardness and mechanical Properties are not satisfactory and which is therefore undesirable.

Resin component (v)

The resin component (v) may be any of Resin components (i) to (iv) to be a Hydroxyl-containing resin or a hydroxyl contains containing compound.

The hydroxyl-containing resin or the hydroxyl containing compound contains average at least one hydroxyl group per molecule and has a number average molecular weight from about 1000 to about 200 000, preferably about 3,000 to about 80,000, on. Less than average one Hydroxyl group per molecule worsens the Hardenability of the composition and is therefore undesirable. With regard to a high Resistance to weather, water and like the average number of Hydroxyl groups per molecule preferably in Range from about 2 to about 400. A Molecular weight below 1000 worsens the physical properties and the Weatherability and a molecular weight over 200 000 increases the viscosity of the Composition and worsened by it  their suitability for a coating process, which is undesirable.

As the hydroxyl-containing resin is z. B. a Resin used as resin component (i) suitable is.

The hydroxyl-containing resin is in a used such amount that per silane or Epoxy group at least one hydroxyl group is present.

The resin components described above can be prepared by conventional methods. In particular can the reactions between hydroxyl and Isocyanate groups, the condensation reaction of Silane groups, the copolymerization reaction and be performed in the usual manner. For example, the reaction between isocyanate and Hydroxyl groups at a temperature between Room temperature and 130 ° C for about 30 to about 360 Minutes accomplished. The condensation reaction of Silane groups are carried out in the presence of an acidic Catalyst (eg hydrochloric acid, sulfuric acid, formic acid, Acetic acid or the like) with heating to one Temperature from about 40 to about 150 ° C for about 1 hour to about 24 hours. The Copolymerization reaction is the same way and under the same conditions as the reaction to Synthesis of conventional acrylic or vinyl resins performed. In such a synthesis reaction you go z. For example suggesting that the monomer component in an organic Solvent dissolves or disperses and the solution or Dispersion in the presence of a radical Polymerization initiator at a temperature of about Heated to about 180 ° C with stirring. The Reaction time is usually about 1 to about 10 hours. Suitable organic solvents are, for. B.  those that are opposite to the monomer or for the Polymerization compounds used are unreactive, such as z. For example, ether, ester or hydrocarbon solvents. The hydrocarbon solvent is with regard to a good solubility preferably in combination with another solvent used. The radical Polymerization initiator may be any of commonly used polymerization initiators be such as a peroxide such as benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and the like or a Azo compound such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like.

Resin components (I), in addition to epoxy, silane and Hydroxyl groups also have carboxyl groups are preferred because this leads to improved hardenability leads.

Also usable are modified resins prepared by chemical combination of the resin component used as Resin component (I) is usable, with another Resin (such as a vinyl resin, polyester resin, urethane resin, Silicone resin, epoxy resin or the like).

According to the invention, the resin component (I) can be dissolved or dispersed in a solvent or in the form of a non-aqueous dispersion of polymer particles which were prepared in the presence of this resin component as a dispersion stabilizer used. Examples suitable solvents include toluene, xylene and the like Hydrocarbon solvent; methyl ethyl ketone, Methyl isobutyl ketone and similar ketone solvents; Ethyl acetate, butyl acetate and like ester solvents; Dioxane, ethylene glycol diethyl ether and the like ether solvents; and butanol, propanol and the like Alcohol solvent.  

In the following, the non-aqueous dispersion becomes closer described.

The non-aqueous dispersion can be prepared by polymerization at least one radical polymerizable unsaturated monomers in the presence a polymerization initiator and the Dispersion stabilizer in an organic solvent, in which the monomer and the dispersion stabilizer are soluble but those produced by polymerization Polymer particles do not dissolve. The ones described above All monomers are used to make the polymer, in the non-aqueous dispersion in the form of Polymer particles is present, suitable.

Since the polymer used as a particle component in the nonaqueous dispersion is said to be insoluble in the organic solvent used, it is desirable to use a copolymer prepared by polymerizing a predominant amount of high polarity monomers. Preferred monomers for use in the present invention are e.g. For example, methyl acrylate or methacrylate, ethyl acrylate or methacrylate, acrylonitrile, methacrylonitrile, 2-hydroxy acrylate, 2-hydroxymethacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylamide, methacrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyl toluene, a- methylstyrene, N-methylolacrylamide or methacrylamide and similar monomers. The polymer particles contained in the non-aqueous dispersion may optionally also be crosslinked. The polymer particles may be internally crosslinked by various methods, such as by copolymerization of polyfunctional monomers such as divinylbenzene, ethylene glycol dimethacrylate, or the like.

That for the preparation of the non-aqueous dispersion suitable organic solvents is, for. Eg one, that is virtually impossible to get through To dissolve polymerized polymer particles, but the dispersion stabilizer and the radical polymerizable unsaturated monomers can solve well. Examples of suitable organic solvents are Pentane, hexane, heptane, octane, mineral spirit, naphtha and similar aliphatic hydrocarbons; Benzene, toluene, Xylene and similar aromatic hydrocarbons; Alcohol solvent, ether solvent, Ester solvents and ketone solvents, such as. B. Isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, Octyl alcohol, cellosolve, butyl cellosolve, Diethylene glycol monobutyl ether, methyl isobutyl ketone, Diisobutyl ketone, ethyl acyl ketone, methyl hexyl ketone, Ethyl butyl ketone, ethyl acetate, isobutyl acetate, acyl acetate, 2-ethylhexyl acetate, etc. These organic solvents can be alone or as a mixture of at least two be used. Preferably used Solvents containing a major part of aliphatic Hydrocarbons and a smaller part aromatic hydrocarbons or the above-mentioned Alcohol, ether, ester or ketone solvents contain. Trichlorotrifluoroethane, meta-xylene hexafluoride, Tetrachlorohexafluorobutane, etc. may optionally be used also be used.

The polymerization of the above monomers is carried out under Use of a radical polymerization initiator carried out. Suitable radical Polymerization initiators are z. B. 2,2'- Azobisisobutyronitrile, 2,2'-azobis (2,4- dimethylvaleronitrile) and similar initiators from the azo Type; and benzoyl peroxide, lauryl peroxide, tert-butyl peroctoate and similar initiators of the peroxide type. These Polymerization initiators are used in an amount of about 0.2 to about 10 parts by weight per 100  Parts by weight of the monomers to be polymerized used. The amount of for the polymerization too can be used over a dispersion stabilizer wide range can be varied, for. B. depending on the type of the dispersion stabilizer. Generally used you suitably the one or the radical polymerizable unsaturated monomers in an amount from about 3 to about 240 parts by weight, preferably about 5 to about 82 parts by weight, per 100 parts by weight of the dispersion stabilizer.

According to the invention, the dispersion stabilizer and the polymer particles combined, what about leads that the storage stability of the non-aqueous Dispersion is improved and the resulting Coating with regard to transparency, surface smoothness and mechanical properties is excellent. The Dispersion stabilizer and the polymer particles can be combined with each other by the one or the other radically polymerizable unsaturated monomers in Presence of the dispersion stabilizer with polymerizable double bond polymerized to at the same time the formation of polymer particles and the Bonding of the resin to these polymer particles too accomplish.

The polymerizable double bond can most easily be introduced into the dispersion stabilizer by adding to some of the epoxy groups present in the dispersion stabilizer acrylic acid, methacrylic acid, itaconic acid or similar α-, β- ethylenically unsaturated monocarboxylic acids. The introduction can also be achieved by adding to some of the hydroxyl groups in the dispersion stabilizer isocyanatoethyl methacrylate or similar isocyanate-containing monomers.

The dispersion stabilizer can also be characterized with the Polymer particles are combined, that one reactive  Monomer as a monomer component for the formation of Polymer particles used, such as. B.

γ- methacryloxypropyltrimethoxysilane,
γ- methacryloxypropyltriethoxysilane,
γ -acryloxypropyltrimethoxysilane,
γ- methacryloxybutyltriethoxysilane,
γ -acryloxypropyl trisilanol or the like.

When the dispersion stabilizer is a two- or Three-component resin or a two-or The three-component compound is the non-aqueous Dispersion produced by polymerization of the or radically polymerizable unsaturated monomers in Presence of such a mixture as Dispersion stabilizer. Optionally, the non-aqueous Dispersion can be prepared by polymerization of the radical-polymerizable unsaturated Monomers in the presence of part of the two- or Three-component resin (compound) (single or triple) Two-component resin (compound)) as Dispersion stabilizer and by mixing the remaining Resin or the remaining compound with the so formed Polymers.

The following describes the crosslinking agent (II) which is a substance selected from at least one of the following compounds: carboxyl compounds, Polyisocyanate compounds and aminoaldehyde resins and the with the resin component (I) and the curing catalyst (III) to form the curable invention Composition united.

The crosslinking agent is combined with the resin component (I), which is dissolved or dispersed in the solvent or as a dispersion stabilizer in the non-aqueous Dispersion of the polymer particles is present, mixed. The crosslinking agent (II) may be the non-aqueous Dispersion also by mixing with the resin component (I)  as a dispersion stabilizer before the preparation of non-aqueous dispersion are incorporated.

Carboxylic acid compounds for use as Crosslinking agents in the present invention are e.g. B. a resin or a compound with average at least two carboxyl groups in the molecule or a resin or a compound with an average of at least a carboxylic acid anhydride group in the molecule. The Carboxylic acid component has a number average of Molecular weight from about 100 to about 200,000, preferably about 100 to about 100,000.

Carboxylic acid compounds useful in the present invention are suitable, z. B. in the following under (1) to (8).

• (1) carboxylic acid
  Examples of suitable carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydroterephthalic, trimellitic acid, Hexahydrotrimellithsäure, pyromellitic acid, cyclohexanetetracarboxylic acid, methyltetrahydrophthalic acid, Methylcyclohydrophthalsäure, endomethylenehexahydrophthalic, methylendomethylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, suberic , Pimelic acid, dimer acid (dimer of tall oil fatty acid), tetrachlorophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-dicarboxybiphenyl and the like, as well as the corresponding anhydrides.
• (2) polyester resin
  Suitable polyester resins are, for. Resins which have been prepared from a mixture of a carboxylic acid selected from the examples given above under (1) and a polyhydric alcohol, examples of which are given below.
  Examples of suitable polyhydric alcohols are ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, hydroxypivalate neopentyl glycol, polyalkylene oxide, bishydroxyethyl terephthalate, adduct of (hydrogenated) bisphenol A with alkylene oxide, glycerol, trimethylolpropane, trimethylolethane, diglycerol, pentaerythritol, dipentaerythritol, sorbitol, etc.
  It is possible to use together with the above carboxylic acid compounds and polyhydric alcohols the following compounds: Cardula E 10 (trademark for a product of Shell Chemical Co. Ltd.), α- olefin epoxide, butylene oxide, Epon # 828 (trademark for a product of Shell Chemical Co. Ltd.), Epon # 1001 (trademark for a product of Shell Chemical Co. Ltd.), and similar epoxy-containing compounds, dimethylolpropionic acid, pivalic acid, 12-hydroxystearic acid, ricinoleic acid, and the like compounds having hydroxy and carboxy groups in the molecule ; ε- caprolactone, b -methyl- δ- valerolactone, γ- valerolactone, δ- valerolactone, ε- caprolactone, γ- butyrolactone and like lactones; Benzoic acid, p-butylbenzoic acid, abietic acid, acetic acid, propionic acid, butyric acid, caproic acid and like monocarboxylic acids; 2-ethylhexanol, lauryl alcohol, stearyl alcohol and similar monohydric higher alcohols; Coconut oil, cottonseed oil, rice seed oil, fish oil, tall oil, soybean oil, linseed oil, tang oil, rapeseed oil, castor oil, dehydrated castor oil, fatty acids thereof, dimers thereof, trimers thereof (which are optionally hydrogenated), etc.
• (3) Carboxyl-containing vinyl resin
  The carboxyl-containing vinyl resins described above as suitable for the resin component (i) can be used as such a resin.
• (4) Carboxyl and fluorine-containing resin
  The carboxyl and fluorine-containing resins described above as suitable for the resin component (i) can be used as such resins.
• (5) Carboxyl-containing urethane resin
  Suitable resins are for. A reaction product of a resin or a compound containing hydroxyl and carboxyl groups in the molecule (such as hydroxyl and carboxyl-containing compounds mentioned above in polyester resins (2) and the polyester resins, carboxyl-containing vinyl resins and carboxyl and fluorine-containing resins (all of which have been described above in (2), (3) and (4), respectively, prepared in such a manner that the resulting resin contains hydroxyl groups) with, for example, the polyisocyanate compound (U.S. such as the polyisocyanate compounds described above as suitable for the isocyanate-containing resin for use in the resin component (i)).
• (6) Carboxyl-containing silicone resin
  Suitable resins are for. Resins which have been prepared by modifying the polyester resins, carboxyl-containing resins and carboxyl and fluorine-containing resins, all of which have been described above under (2), (3) and (4), respectively, respectively in that the resulting resin contains hydroxyl groups, with a silicone resin or a hydrolyzable silyl-containing compound, such as. Methyltrimethoxysilane, methyltriacetoxysilane, dimethyldimethoxysilane or the like, examples of the silicone resin being those sold under the trade names Z-6018 and Z-6118 (trademarks for products of Dow Corning Ltd.) and SH-5050, SH-6018 and SH- 6188 (trademark for products of Toray Silicone Co. Ltd.) are available.
• (7) Carboxyl-containing polyether resin
  Suitable resins are for. B. adducts of the acid anhydride, for the examples given above, with a polyoxyalkylene polyol, such as. For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
• (8) Carboxyl-containing epoxy resin
  Suitable resins are for. B. adducts of polycarboxylic acids, for the above examples have been given, such as. Example, the polycarboxylic acid compound mentioned above under (1), with an epoxy compound such. Epon # 828 (trademark for an epoxy resin of Shell Chemical Co. Ltd.), Epon # 1001 (trademark for an epoxy resin of Shell Chemical Co. Ltd.), diglycidyl ether or the like.

The amount of used in the present invention Carboxylic acid compound is about 1 to about 40 parts by weight, preferably about 3 to about 30 parts by weight and more preferably about 5 to about 25 parts by weight, per 100 parts by weight of Resin component (I). The use of more than 40 parts by weight of the acid reduces the storage stability the curable composition and the use of less than one part by weight of the acid deteriorates the adhesion to metals and coating films and is therefore undesirable.

Polyisocyanate compounds used as crosslinking agents in the present invention are suitable, for. B. those in the molecule at least two, preferably two or three, containing isocyanate groups and any aliphatic, alicyclic, aromatic and aromatic-aliphatic compound. Examples of suitable polyisocyanate compounds are Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and similar aliphatic diisocyanates; (Hydrogenated) Xylylene diisocyanate, isophorone diisocyanate and the like alicyclic diisocyanates; and tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and similar aromatic Diisocyanates. Also suitable are an adduct of Diisocyanate compound with a polyhydric alcohol, low molecular weight polyester resin or water; a polymer of diisocyanate compounds with one another; isocyanate Biurets of such diisocyanate compounds, etc. Representative commercially available products for this Compounds are the ones below Trademarks available are: "BURNOCK D-750, -800, DN-950 and DN-970 "(products of Dainippon Ink and Chemicals Incorporated), "SUMIDUL L, N, HL IL and N-3390" (Products of Sumitomo Bayer AG), "TAKENATE D-102, -202,  -110N and -123N "(products of Takeda Chemical Industries Ltd.), "COLONATE-L, -HL, -EL and -203" (products of Nippon Polyurethane Kogyo K.K.), "DECORANATE 24A-90CX" (Product of Asahi Chemical Industry Co. Ltd.), etc.

Examples of the polyisocyanate compound are also blocked polyisocyanate compounds prepared by Blocking of the polyisocyanate compound with a Blocking agents such. As an aliphatic or aromatic monohydric alcohol oxime, lactam, phenol or like. Concrete examples of such compounds are "TAKENATE B-815N" (trademark for a product of Takeda Chemical Industries Ltd.), "BURNOCK D-550" (Trademark for a product of Dainippon Ink and Chemicals Incorporated), "ADITOL VXL-80" (Trademark for a product of Hoechst AG, FRG), "COLONATE-2507" (Trademark of a Nippon Polyurethane product Kogyo K.K.), etc.

A suitable amount of the polyisocyanate compound is in the Range from about 1 to about 30 parts by weight, preferably from about 2 to about 20 parts by weight, per 100 parts by weight of the resin component (I) (calculated as solids). A smaller amount than the one above specified range does not improve the mechanical properties of the coating film and the adhesion to plastic substrates (such as Urethane substrates) and is therefore undesirable.

Optionally, a curing catalyst for the Polyisocyanate compound can be used. examples for suitable curing catalysts are dibutyltin diacetate, Dibutyltin dioctoate, dibutyltin dilaurate and the like Organotin compounds as well as triethylamine, diethanolamine and similar amine compounds, etc. The amount of Curing catalyst is preferably about 0.01 to about 10 parts by weight per 100 parts by weight of the Resin component (I) (calculated as solids).  

Examples of aminoaldehyde resins useful as crosslinking agents in the present invention are a condensation product prepared by condensing an amino compound with an aldehyde compound by conventional methods; and an aminoaldehyde resin prepared by modifying the condensate with an alcohol. Examples of the amino compound are melamine, urea, benzoguanamine, spiroguanamine, acetoguanamine, steroguanamine, etc. Examples of the aldehyde compounds are formaldehyde, paraformaldehyde, acetaldehyde, etc. In view of low-temperature hardenability, C _{1-4 represent} monohydric alcohols as alcohols for For example, where the modification is desirable, 2-ethylhexanol, cyclohexanol, lauryl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and similar alcohols containing at least 5 carbon atoms may be used in combination therewith.

Melamine resins are among the above aminoaldehyde resins on best suited if a coating film with high Weather resistance is desired. examples for suitable melamine resins are hexamethyl etherified Methylol melamine, hexabutyl etherified methylol melamine, Hexamethylbutyl etherified methylol melamine, methyl etherified methylol melamine, n-butyl etherified Methylolmelamine, i-butylated methylolmelamine, etc. Im Commercially available such melamine products are Cymel-303, Cymel-235, Cymel-238, Cymel-1130, Cymel-254 and Cymel-327 (trademark for melamine resins of Mitsui Cyanamide Co. Ltd.), Sumimal M-55, Sumimal M-100 and Sumimal M-40S (trademark for melamine resins of Sumitomo Chemicals Co. Ltd.), U-Van 20SE-60, U-Van 225 and U-Van 28SE-60 (trademark for melamine resins of Misui Toatsu Chemicals Inc.), Superbeckamine G-840, Superbeckamine G-821-60 and Superbeckamine L-127-75  (Trademark for melamine resins of Dainippon Ink and Chemicals Inc.).

A suitable amount of aminoaldehyde resins is in the Range from about 1 to about 50 parts by weight, preferably about 3 to about 40 parts by weight and in particular about 5 to about 30 parts by weight, per 100 parts by weight of the resin component (I) (calculated as solids). An amount that is above the above range is, leads to a reduction in the hardenability of the Composition while a lot below the above Area to a deterioration of the suitability for a Coating with simultaneous use of an aminoalkyd (Polyester) coating composition or one Amino acrylic coating composition can lead and therefore undesirable.

The term "suitability for a coating," as used here Used is the adhesion between the top coat from the curable composition of the invention and the underlying coating of the aminoalkyl or Aminoacrylic coating composition as well as the outer Appearance of a coating film by Application of these compositions by a wet-on-wet Coating process is formed, denote.

It still has to be clarified why the inventive curable composition an excellent suitability for the coating with conventionally used Aminoalkyd- (polyester) -Beschichtungszusammensetzungen, Aminoacrylic coating compositions and the like Coating compositions shows.

Presumably, this is due to the compatibility of the Composition according to the invention with similar substances (Aminoaldehyd resins) due.  

The use of aminoaldehyde resin continues to lead a coating with good hardenability, due to the Reaction between the aminoaldehyde resin and the Hydroxyl groups in the curable composition are present, and by the self-condensation Reaction of the aminoaldehyde resin. These reactions can be accelerated by using a catalyst, this catalyst being any of the conventional ones Catalysts, such as. B. carboxylic acid compounds, Phosphoric acid compounds, sulfonic acid compounds, Salts of these compounds with basic compounds, etc. can be.

Hereinafter, the curing catalyst 55038 00070 552 001000280000000200012000285915492700040 0002004008343 00004 54919 (III), the together with the resin component (I) and the Crosslinking agent (II) is used to the to provide inventive curable composition, described. The curing catalyst (III) is at least a compound selected from organometallic Compounds, Lewis acids, protic acids and compounds with Si-O-Al bonds.

The curing catalyst becomes essential with the other Ingredients of the curable invention Composition in a suitable manner without special Restriction mixed.

(1) Organometallic compound

Suitable organometallic compounds are, for. B. Metal alkoxide compounds, metal chelate compounds, Metal alkyl compounds, etc.

metal alkoxide

Suitable metal alkoxide compounds are, for. B. Compounds in which an alkoxide group is attached to a Metal such. As aluminum, titanium, zirconium, calcium,  Barium or the like is bound. These Compounds can be an association of molecules contain. Preferred metal alkoxide compounds are z. B. aluminum alkoxides, titanium alkoxides, Zirconium. Concrete examples of such Compounds are given below.

Suitable aluminum alkoxide are z. B. those by the following formula be represented:

in which the groups R¹² are the same or different and each represents an alkyl group of 1 to 20 Carbon atoms or an alkenyl group.

Examples of alkyl groups with 1 to 20 Carbon atoms are nonyl, decyl, undecyl, dodecyl, Tridecyl, tetradecyl, octadecyl and the like and the above-mentioned alkyl groups with 1 to 8 Carbon atoms. Examples of alkenyl groups are vinyl, allyl and the like.

Examples of aluminum alkoxides of formula (95) are Aluminum trimethoxide, aluminum triethoxide, Aluminum tri-n-propoxide, aluminum triisopropoxide, Aluminum tri-n-butoxide, aluminum triisobutoxide, Aluminum tri-sec-butoxide, aluminum tri-tert-butoxide and the same. Be among these Aluminum triisopropoxide, aluminum tri-sec-butoxide and aluminum tri-n-butoxide is preferred.

Examples of suitable titanium alkoxides are titanates the formula:  

in which w is an integer from 0 to 10 and R¹² is as defined above.

Examples of titanates of the formula (96) in which w is 0 are tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetra-n-pentyl titanate, tetra n-hexyl titanate, tetraisooctyl titanate, tetra-n-lauryl titanate, etc. Particularly favorable results can be obtained by using tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-t-butyl titanate and the like. Among the titanates in which w is 1 or more, particularly good results are obtained with those which contain dimers to hendecamers (w = 1 to 10 in the formula (96)) of tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-bis- tert-butyl titanate and the like.

Examples of suitable zirconium alkoxides are Zirconates of the formula

in which w and R¹² are as defined above.

Examples of zirconates of the formula (97) in which w is 0 are tetraethyl zirconate, tetra-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, Tetra-tert-pentylzirconate, tetra-tert-hexylzirconate, tetra-n-heptylzirconate, tetra-n-octylzirconate, tetra-n-stearylzirconate and the like. Particularly desirable results can be obtained using tetraisopropylzirconate, tetra-n-propylzirconate, tetraisobutylzirconate, tetra-n-butylzirconate, tetra-sec-butylzirconate, tetra-tert-butylzirconate, or the like. Among the zirconates with w = 1 or above, those giving particularly favorable results, the dimers to hendecamers (w = 1 to 10 in formula (97)) of tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-n-butyl zirconate, tetraisobutyl zirconate, tetra sec-butylzirconate, tetra-tert-butylzirconate and the like. The zirconium alkoxide compound may also contain an association of such zirconates as a constituent unit.

metal chelate

Preferred metal chelate compounds are, for. B. Aluminum chelate compounds, titanium chelate compounds and zirconium chelate compounds. Under these Chelated compounds become those extra preferred as a ligand for the formation of a stable chelate ring have a compound, the can form a keto-enol tautomer.  

Examples of compounds that can form a keto-enol tautomer are β- diketones (eg, acetylacetone), esters of acetoacetic acid (such as methylacetoacetate), esters of malonic acid (such as ethylmalonate), Ketones with hydroxy group in the β- position (such as diacetone alcohol), hydroxy-group-containing aldehydes in the β- position (such as salicylaldehyde), esters with hydroxyl group in the β- position (such as methyl salicylate), etc. Use of esters of acetoacetic acid or β- diketones can lead to particularly favorable results.

The aluminum chelate compound may, for. B. in appropriate By mixing about 3 mol or less Compound that forms a keto-enol tautomer can, with about 1 mole of the aluminum alkoxide, optionally followed by heating the mixture, getting produced.

Examples of preferred aluminum chelate compounds for use in the present invention are e.g. B.

Tris (ethylacetoacetate) aluminum,
Tris (n-propylacetoacetate) aluminum,
Tris (isopropyl acetoacetate) aluminum,
Tris (n-butylacetoacetate) aluminum,
Isopropoxybis (ethylacetoacetate) aluminum,
Diisopropoxyethylacetoacetataluminium,
Tris (acetylacetonato) aluminum,
Tris (propionylacetonato) aluminum,
Diisopropoxypropionylacetonatoaluminium,
Acetylacetonatobis (propionylacetonato) aluminum,
Monoethylacetoacetatbis (acetylacetonato) aluminum,
Tris (acetylacetonato) aluminum

and the same.

The titanium chelate compound may be suitably z. B. be prepared by adding about 4 mol or less of the compound that is a keto-enol Tautomeres can form, with about 1 mole of the  Titanium alkoxide mixed, optionally followed by Heating the mixture. Examples more preferred Titanium chelate compounds are diisopropoxy bis (ethylacetoacetate) titanate, diisopropoxy bis (acetylacetonato) titanate, etc.

The zirconium chelate compound may e.g. B. in appropriate Be prepared by making about 4 moles or less of the compound that is a keto-enol Tautomeres can form, with about 1 mole of the Zirconium alkoxide mixed, optionally followed from heating the mixture. Examples of preferred Zirconium chelate compounds for use in the present invention Tetrakis (acetylacetonato) zirconium, tetrakis (n- propylacetoacetate) zirconium, Tetrakis (acetylacetonato) zirconium, Tetrakis (ethylacetoacetate) zirconium and the like.

The aluminum chelate compounds, Zirconium chelate compounds and Titanium chelate compounds can be used individually or as Mixture of at least two of them used become.

metal alkyl

The compound has an alkyl group, preferably a C _1-20 alkyl group, attached to a metal, such as. As aluminum, zinc or the like is bound. Examples of such a compound are triethylaluminum, diethylzinc, etc.

(2) Lewis acid

Examples of suitable Lewis acids are Metal halides, compounds that are a metal,  Have halogen and other substituents, and Complexes of these compounds. Concrete examples of these compounds are:

(3) protonic acid

Examples of suitable protic acids are organic Protonic acids, such as. For example, methanesulfonic acid, Ethanesulfonic acid, trifluoromethanesulfonic acid, Benzenesulfonic acid, p-toluenesulfonic acid and the like and inorganic protic acids such as phosphoric acid, phosphorous acid, phosphinic acid, phosphonic acid, Sulfuric acid, perchloric acid and the like.

(4) Compound with Si-O-Al bond (s)

A concrete example of such a connection is aluminum silicate.

Among the curing catalysts described above are the metal chelate compounds are preferred because they have a Coating composition with very good hardenability can deliver.

An appropriate amount of the above in (1) to (3) described curing catalysts is in the range of about 0.01 to about 30 parts by weight per 100 Parts by weight of the total amount of resin component (I) and Crosslinking agent (II), calculated as solids. Fewer  reduced to about 0.01 parts by weight of catalyst possibly the hardenability, and more than about 30 Parts by weight cause part of the catalyst possibly remaining in the cured product and its water resistance decreases, which is undesirable is. A preferred amount of catalyst is in the range from about 0.1 to about 10 parts by weight and whole particularly preferred is an amount in the range of about 1 to about 5 parts by weight.

An appropriate amount of curing catalyst, above under (4) is in the range of approximately 1 to about 100 parts by weight per 100 parts by weight the total amount of resin component (I) and crosslinking agent (II), calculated as solids. A lot under the above range may cause the Hardenability is reduced, and a lot above the above Range could be the properties of the coating film affect what is undesirable.

Optionally, the curable Composition a chelating agent, one Polyepoxy compound, a polysilane compound, organic Solvent, pigment, additional resin and the like contain. The chelating agent is used to improve the shelf life and can be any the above given examples of chelate compounds his. The polyepoxy compound and the polysilane compound are used to increase the hardenability of the To improve coating composition and can be any of those links above have been described.

Preferred organic solvents are with regard to a high rate of cure of the curable Composition z. B. those with a boiling point of 150 ° C or less, but are not on these solvents limited. Preferred organic solvents are  Toluene, xylene and like hydrocarbon solvents; Methyl ethyl ketone, methyl isobutyl ketone and the like ketone solvent; Ethyl acetate, butyl acetate and the like Esterlösungsmittel; Dioxane, ethylene glycol diethyl ether and similar ether solvents; as well as butanol, propanol and similar alcohol solvents. While these solvents used alone or in the form of a suitable combination Become alcoholic solvents with regard to to a good solubility of the resin preferably in Mixture with another solvent used. The Resin concentration in the solvent may vary vary in purpose, but is generally in the range of about 10 to about 70 weight percent.

Suitable pigments may be inorganic or organic Be nature. Inorganic pigments suitable for the present Invention are suitable, for. B. pigments of the oxide type, such as Example, titanium dioxide, red iron oxide, chromium oxide and the like; Pigments of the hydroxide type, such as. B. Aluminum white and the like; Sulphate-type pigments, such as B. precipitated barium sulfate and the like; Carbonate-type pigments, such as e.g. B. precipitated Calcium carbonate and the like; Pigments of silicate Type, such as. Sound and the like; Pigments from Carbon type, such as. Carbon black and the like; and metallic powders, such as. B. aluminum powder, bronze powder, Zinc powder and the like. Organic pigments used for the present invention are suitable, for. B. pigments of the azo type, such as. B. "Lake Red", "First Yellow" and the like; and phthalocyanine-type pigments, such as. B. Phthalocyanine blue and the like.

Suitable additional resins may be any resins made of cellulose acetate butyrate, epoxy resins of Bisphenol type, petroleum resins, phenolic resins, etc. be selected, each with a view to the eye composed special application.  

The curable composition of the invention can optionally also other commonly used Contain additives such. B. means for improving the Surface, "cissing" inhibitors, Viscosity modifier, means for preventing Blistering, means of improving the Weathering resistance (absorbent for ultraviolet radiation, light stabilizers, Oxidation inhibitors, quenchers and the like), etc. For use, these additives can easily with the Resins are mixed or chemically bound to it. Optionally, they may also be added so that within the resin particles in the non-aqueous Dispersion are present.

The resin composition of the present invention can be easily by networking at low temperature of not higher be cured as 140 ° C, including z. For example, about 8 hours to about 7 days at room temperature without heating or about 5 minutes to about 3 hours by heating than about 40 to about 100 ° C are required.

The curable composition of the invention is suitable for use as a coating composition, adhesive, Printing ink and the like and may take the form of a Coating composition, which is at room temperature harden, and in the form of various Burn-in type coating compositions which are in a wide temperature range of low Temperatures from 60 to 100 ° C up to high temperatures from 100 to 160 ° C, provided become. Substrates containing the curable invention Composition can be coated, z. B. all types of substrates previously used for coatings were used, such. For example, those made of iron, Plastics, wood and similar materials. The The curable composition of the invention is particularly  suitable for application on body panels of Automobiles and the like.

For use as topcoat composition (topcoating composition), the inventive curable Composition in a full-color, metallic or clear Be formulated coating composition and be applied by a wet-on-wet Coating process (so-called coating process with two coating and one baking stage) or by a coating process that becomes a single Layer leads or the like. The inventive curable composition can be used to make a Intermediate coating on automotive panels or a topcoat or base coat on automobile parts made of plastics, To form metal or the like.

The curable composition of the invention Use as a coating composition can by conventional coating process without special Restriction be applied, such. B. by Air spraying, electrostatic spraying, airless Spraying, electrostatic bell coating, electrostatic mini-bell coating, Roll coating, brushing and the like.

The curable composition of the invention may be added to the following remarkable results.

• 1. It shows excellent hardenability low temperatures.
• 2. It provides a coating film whose Resistance to weathering, acids and the like is excellent.
• 3. It leads to coating films with excellent  Adhesion to various substrates or Coating films.
• 4. It forms a coating film with excellent external appearance.

The present invention will now be described with reference to the following production examples, examples and Comparative examples described in more detail.

Preparation Example 1 Preparation of Copolymer 1 '

The above mixture was dissolved in 100 parts by weight of xylene Presence of 2,2'-azobisisobutyronitrile (AIBN) at a temperature of 90 ° C for 3 hours radically polymerized, resulting in a solution of a copolymer (Copolymer 1 ') containing non-volatile Constituents of 50 weight percent resulted. The Copolymer 1 'had a number average molecular weight of 5000 (determined by gel permeation chromatography, as also all other molecular weights, in the following be specified), on.  

Preparation of Copolymer 2 '

The above mixture was under the same conditions as reacted for the preparation of copolymer 1 ', resulting in a solution of a copolymer (copolymer 2 ') with a Non-volatile content of 50% by weight led. The copolymer 2 'was included Number average molecular weight of 6200.

Preparation of Copolymer 3 '

The above mixture was under the same conditions as reacted for the preparation of copolymer 1 ', resulting in a solution of a copolymer (copolymer 3 ') with a Non-volatile content of 50 Weight percent resulted. The copolymer 3 'had Number average molecular weight of 5,800.  

Preparation of copolymer 1a

The above mixture was under the same conditions as reacted for the preparation of copolymer 1 ', resulting in a solution of a copolymer (copolymer 1a) with a Non-volatile content of 50 Weight percent resulted. The copolymer 1a was included Number average molecular weight of 6000 on.

Preparation of Macromonomer *)

The above mixture was at 117 ° C for 3 hours followed by dehydration. The obtained polysiloxane macromonomers had a number average molecular weight of 7000 and contained average per molecule one vinyl group and 5 to 10 silanol groups.  

Preparation of Copolymer 1b

The above mixture was under the same conditions as reacted for the preparation of copolymer 1 ', resulting in a solution of a copolymer (copolymer 1b) with a Non-volatile content of 50 Weight percent resulted. The copolymer 1b was included Number average molecular weight of 6000 on.

Preparation of Copolymer 1c

The above mixture was under the same conditions as reacted for the preparation of copolymer 1 ', resulting in a solution of a copolymer (copolymer 1c) with a Non-volatile content of 50  Weight percent resulted. The copolymer 1c was included Number average molecular weight of 7000.

Preparation of Copolymer 2a

parts by weight FM-3 monomer **) 30 Macromonomer *) 30 CH₂ = C (CH₃) COOC₄H₉ 30 CH₂ = CHCOOC₂H₄C₈F₁₇ 10

Note: FM-3 monomer **) is a trade name for a hydroxyl-containing caprolactone modified esters of methacrylic acid with an average molecular weight of 472 and a theoretical hydroxyl number of 119 KOH mg / g, product of Daicel Chemical Co., Ltd.

The above mixture was under the same conditions as reacted for the preparation of copolymer 1 ', resulting in a solution of a copolymer (copolymer 2a) with a Non-volatile content of 50 Weight percent resulted. The copolymer 2a was included Number average molecular weight of 5000 on.

Preparation of Copolymer 2b

parts by weight FM-3 monomer **) 30 Macromonomer *) 30 CH₂ = CHCOOC₂H₄C₈F₁₇ 40

The above mixture was under the same conditions as reacted for the preparation of copolymer 1 ', resulting in a solution of a copolymer (copolymer 2b) with a  Non-volatile content of 50% by weight led. The copolymer 2b had a Number average molecular weight of 4900.

Preparation of Copolymer 3

The above mixture was under the same conditions as reacted for the preparation of copolymer 1 ', resulting in a solution of a copolymer (copolymer 3) with a Non-volatile content of 50 Weight percent resulted. The copolymer 3 had a Number average molecular weight of 10 500 on.

Preparation of Copolymer 4

A stirrer-equipped 400 ml glass flask was fitted with the the following components are charged:

The mixture was stirred at 100 ° C for 5 hours reacted to add the hydroxyl group to the  To cause isocyanate group. Then it was confirmed that the NCO value decreases to 0.001 or below had been. The reaction resulted in a copolymer (Copolymer 4), the OH groups, Si (OCOCH₃) ₃- and

contained.

Preparation of Copolymer 5

A stirrer-equipped 400 ml glass flask was fitted with the the following components are charged:

The mixture was stirred at 100 ° C for 5 hours reacted to add the hydroxyl group to the To cause isocyanate group. Then it was confirmed that the NCO value has been reduced to 0.001 or less was. The reaction resulted in a copolymer (copolymer 5), the

contained.

Preparation of copolymer 6

A stirrer-equipped 400 ml glass flask was fitted with the the following components are charged:

The mixture was stirred at 110 ° C for 6 hours implemented to add the COOH groups to the

to effect. Thereupon it was confirmed that the Acid value had been reduced to 0.01 or below. The reaction resulted in a copolymer (copolymer 6) with Si (OCH₃) ₃ group.

Preparation of Copolymer 7

A glass flask equipped with stirrer and water cutter was charged with the following ingredients:

parts by weight phthalic anhydride 192 hexahydrophthalic 256 adipic acid 107 neopentylglycol 357 trimethylolpropane 88

The temperature became within a period of 3 Hours raised from 160 ° C to 230 ° C. after the Temperature had been kept at 230 ° C for 1 hour 50 g of xylene were added and the mixture was reacted, until the acid number reached 8. The Reaction mixture was cooled and washed with a Solvent mixture of xylene / n-butanol (4/1 parts by weight) to a resin solids content of 50 percent by weight diluted.

The thus obtained copolymer (copolymer 7) had Number average molecular weight of about 3500.  

Preparation of Copolymer 8

A stirrer-equipped 400 ml autoclave on stainless Steel was charged with the following components:

After displacement with nitrogen, solidification by cooling and venting were 45 parts by weight of the compound CF₂ = CFCl placed in the autoclave, in which the temperature gradually raised to 60 °. The mixture was Stirred for 16 hours or longer. As soon as the pressure inside the autoclave to 1 kg / cm² or below, the autoclave was with Water cooled to stop the reaction. The obtained Resin solution was added to an excess of heptane to precipitate the resin. The precipitate was washed and dried and yielded 91 g of resin (copolymer 8) in a yield of 91%. The copolymer 8 was included Number average molecular weight of 6300. The Copolymer 8 was dissolved in an equal amount of xylene, to a resin solution containing non-volatile To deliver ingredients of 50 weight percent.

Preparation of Copolymer 9

The same procedure as in the preparation of copolymer 8 was applied, with the exception that the following Monomers instead of the monomers for the copolymer 8  were used, resulting in a solution of a copolymer (Copolymer 9) containing non-volatile Constituents of 50 weight percent resulted. The copolymer 9 had a number average molecular weight of 7200 on.

Preparation of Copolymer 10

The same procedure as in the preparation of copolymer 8 was used, with the exception that instead of the Monomers for the copolymer 8 the following monomers were used, resulting in a solution of a copolymer (Copolymer 10) containing non-volatile Constituents of 50 weight percent resulted. The copolymer 10 had a number average molecular weight of 6800 on.

Preparation of Copolymer 11

The process for producing copolymer 8 was repeated, with the exception that instead of for the Copolymer 8 monomers used the following monomers Use, resulting in a solution of a copolymer (Copolymer 11) containing non-volatile Constituents of 50 weight percent resulted. The copolymer 11 had a number average molecular weight of 5,000 on.

Preparation of Copolymer 12

A stirrer-equipped 400 ml glass flask was fitted with the the following components are charged:

The mixture was stirred at 96 ° C for 9 hours implemented. The disappearance of absorption of SH groups in the infrared absorption spectrum confirmed that  Reaction to a copolymer (copolymer 12) out had into which OH and epoxy groups as well as groups of Formula Si (CH₃) (OCOCH₃) ₂ were introduced. The copolymer 12 had a number average molecular weight of 8100 on.

Preparation of the non-aqueous dispersion (1)

A stirrer-equipped 400 ml glass flask was fitted with the the following components are charged:

parts by weight Solution of Copolymer 8 (Non-Volatile Content: 50%) 200 CH₂ = C (CH₃) COOC₂H₄NCO 3.1 hydroquinone 0.02 xylene 3.1

The mixture was stirred at 100 ° C for 5 hours subjected to an addition reaction. After that was confirms that the isocyanate value is 0.001 or below had been humiliated. The solution thus obtained contained a copolymer (dispersion stabilizer (1)) into which a polymerizable molecule per molecule Double bond had been introduced.

A glass flask was made with the following ingredients charged:

parts by weight heptane 95 n-butyl acetate 5 Solution of Dispersion Stabilizer (1) (Non-Volatile Content 50%) 244

The resulting mixture was heated to reflux. Then, the following particle-forming monomers became and the following polymerization initiator dropwise placed in the flask for over 3 hours, whereupon the Mixture was allowed to stand for 2 hours.

(The total amount of particle-forming monomers was 100 parts by weight. relationship Particle / Dispersion Stabilizer = 45/55, calculated as Solids).

The non-aqueous dispersion (1) thus obtained was milky-white and stable, had a non-volatile content Components of 50 percent by weight on and contained polymer particles with an average Particle size of 0.15 μm (determined by a device Colter-N4, trade name for a Colter product Company Ltd.). Even after the dispersion 3 months had been allowed to stand for a long time at room temperature neither precipitation formation nor formation of coarser particles are observed.

Preparation of the non-aqueous dispersion (2)

A stirrer-equipped 400 ml glass flask was charged with the following components are charged:

parts by weight Solution of copolymer 8 (non-volatile content 50%) 200 CH₂ = C (CH₃) COOH 1.6 4-tert-butylpyrocatechol 0.02 diethylaminoethanol 0.1 xylene 1.6

The mixture was subjected to an addition reaction with stirring at 120 ° C for 5 hours, and then it was confirms that the acid value of the resin is 0.001 mg KOH / g or below it had been reduced. The reaction resulted to a solution of a copolymer (dispersion stabilizer (2)), in which an average of 0.6 per molecule polymerizable double bonds were introduced.

A flask was charged with the following ingredients:

parts by weight heptane 80 n-butyl acetate 10 Solution of Dispersion Stabilizer (2) (Non-Volatile Content 50%) 200

The mixture was heated to reflux. thereupon were the following particle-forming monomers and the following polymerization initiator over a period of time of 3 hours dropwise added to the flask. Thereafter, the mixture was allowed to stand for 2 hours and 10 parts by weight of n-butyl acetate were added thereto.

(The amount of the particle-forming monomers was total 100 parts by weight. relationship Particle / Dispersion Stabilizer = 50/50, calculated as Solids).

The non-aqueous dispersion (2) thus obtained was neutralized with n-butyl acetate to a content of volatiles of 50% by weight set. The non-aqueous dispersion (2) was milky-white and stable and contained polymer particles with an average particle size of 0.25 μm (determined by a Colter-N4 device). after the Dispersion allowed to stand for 3 months at room temperature could neither precipitation formation nor a formation of coarser particles are observed.

Preparation of epoxy and alkoxysilane-containing connection

A provided with stirrer 1 liter glass flask was with the following components are charged:

The mixture was stirred at 90 ° C for 3 hours reacted, resulting in a solution of a compound of the formula

with a non-volatile content of 80% led.

Preparation Example 2 Preparation of carboxylic acid compound (C)

parts by weight methacrylic acid 10 styrene 20 n-butyl methacrylate 60 2-hydroxyethyl methacrylate 10

The above mixture was mixed in a solvent of xylene / n-butanol (80/20, parts by weight), in the presence radically polymerized by AIBN, resulting in a solution of a resin (compound (C)) containing volatiles of 50 weight percent resulted. The compound (C) had a number average of Molecular weight of 8000 and its acid number was 62.

Preparation of carboxylic acid compound (D)

parts by weight itaconic 15 styrene 20 n-butyl acrylate 30 1,4-butanediol monoacrylate 10 n-butyl methacrylate 30

The above mixture was mixed in a solvent of xylene / n-butanol (50/50, parts by weight), in the presence radically polymerized by AIBN, giving a solution of a Resin (compound (D)) containing non-ionic volatiles of 50 percent by weight. The compound (D) had a number average of Molecular weight of 15 500 and had an acid number from 62.

Preparation of carboxylic acid compound (E)

parts by weight phthalic anhydride 19.5 adipic acid 19.3 hexahydrophthalic 20.3 trimethylolpropane 18.0 neopentylglycol 32.3

The above mixture was put in a flask. The Temperature was gradually increased to 230 ° C and at this temperature was the condensation reaction causes while the bound water was distilled off. As soon as the acid number had reached 30, the Reaction mixture cooled to 160 ° C. To this mixture 5.4 parts of trimellitic anhydride were added and the mixture was at the above temperature for 1 hour kept and then cooled. The mixture was with a solvent mixture of xylene / n-butanol (60/40, Parts by weight), resulting in a solution of a resin (Compound (E)) containing non-volatile Constituents of 50 weight percent resulted. The Compound (E) had a number average molecular weight of 2800 and their acid number was 55.

Preparation of carboxylic acid compound (F)

A flask was charged with the following ingredients:

parts by weight phthalic anhydride 18.0 hexahydrophthalic 18.7 adipic acid 11.8 trimethylolpropane 12.3 neopentylglycol 29.8

The temperature was gradually raised to 230 ° C and at this temperature, the mixture became a Subjected to condensation reaction. Once the acid number had reached 25, the mixture was cooled. Xylene was added to the mixture in such an amount that is a concentration of 70% by weight resulted. The resulting mixture was at 100 ° C cooled and kept at this temperature. thereupon were 12.3 parts by weight of hexamethylene diisocyanate added and the mixture was for 1 hour at 100 ° C implemented to introduce urethane bonds. The Reaction mixture was mixed with a solvent mixture from xylene / n-butanol (50/50, parts by weight) to a solution of a resin (compound (F)) with a Non-volatile content of 50 percent by weight deliver. The compound (F) showed a number average molecular weight of 12,000 and possessed an acid number of 22.

Preparation Example 3

Using the in the above production examples prepared copolymers and non-aqueous dispersion were the curable compositions according to the invention, the one carboxylic acid compound as a crosslinking agent contained, to full color (white) - Coating compositions and clear  Topcoat compositions for use in one Coating process with two coating and one Stirring stage formulated.

Preparation of full color (white) coating composition

The following Table 1 shows the components and the Quantities thereof, used for the production of Full Color (White) Coating Compositions (# S-1 to S-6) were used. In Table 1, the given values the quantities in parts by weight again and the amounts of the copolymers and non-aqueous dispersions are expressed as parts by weight of resin solids (These definitions also apply to the following Tables). Titanium Dioxide (Titanium White CR-95, trade name for a rutile titanium white, product of Isihara Sangyo Kaisha Ltd.) was used as a white pigment. Before the The titanium dioxide was used using a Paint shaker for 1 hour in the copolymer solution dispersed. The coating composition No. S-4 was prepared by similarly giving the Titanium dioxide dispersed in the copolymer solution, followed from the addition of a non-aqueous dispersion. The Amount of pigment used was 80 parts by weight per 100 parts by weight of the resin solids.  

Table 1

Preparation of clear coating compositions for the use in a coating process with two Coating and a baking stage

Table 2 shows the components and the quantities same for the production of the clear  Coating compositions (Nos. M-1 to M-7) suitable for the use in a process with two coating and a baking step are used.

Table 2

Examples 1 to 6

Coating compositions S-1 to S-6 were used for Examples 1 to 6 used.

Comparative Example 1

The process for producing the Coating Composition S-6 was repeated, with with the exception that no carboxylic acid compound used to give a coating composition S-7 for Comparative Example 1.  

Comparative Example 2

A coating composition S-8 (Lugabake White, Trade name for a coating composition polyester / melamine resin type, manufactured by Kansai Paint Co. Ltd.) was used for Comparative Example 2 used.

Examples 7 to 13

The coating compositions M-1 to M-7 were used for Examples 7 to 13 used.

Comparative Example 3

The process for producing the Coating Composition M-7 was repeated, with with the exception that no carboxylic acid compounds used to give a coating composition M-8 for Comparative Example 3.

Comparative Example 4

A coating composition M-9 (Magicron # 1000 Clear, trade name for one Acrylic / melamine resin type coating composition, manufactured by Kansai Paint Co. Ltd.) was for the Comparative Example 4 is used.

Preparation of Basecoat Composition A

A basecoat composition for use in the wet-on-wet coating became the following Ingredients manufactured:

parts by weight Copolymer 1a (solution) 200 Tris (acetylacetonato) aluminum 2 EAB-551-02 (trade name for cellulose acetate butyrate, product of Eastman Kodak Co.) 20 toluene 30 butyl 30 Aluminum paste # 4919 (trade name for a product of Toyo Aluminum Co. Ltd.) 5 Aluminum paste # 55-519 (trade name for a product of Toyo Aluminum Co. Ltd.) 10

The resulting composition was before application with a solvent mixture of toluene / xylene / n-butanol (40/40/20) to a viscosity of 15 seconds (Ford cup No. 4, 25 ° C).

Preparation of the substrate to be coated

The with the coating compositions to coated substrates were prepared as follows.

On a zinc phosphate treated steel sheet with dull finish became a coating composition epoxy resin type for cationic electroplating applied in a film thickness of about 25 microns and cured by heating at 170 ° C for 30 minutes. Lugabake AM (Trade name for a product of Kansai Paint Co. Ltd.) was applied to the primed sheet as Intermediate coating composition in a dry Applied film thickness of about 30 microns and the coated sheet was baked at 140 ° C for 30 minutes. The surface of the coating was sandpaper No. 400 wet sanded, dried and with a piece of cloth,  which was saturated with petroleum spirit, abraded to to deliver a substrate sheet.

Examination of the properties of the coating film Full-color coating composition

The in Examples 1 to 6 and the comparative examples 1 and 2 were obtained coating compositions with Swasol # 1000 (trade name for a product of Cosmo Oil Co. Ltd., petroleum type solvent) a viscosity of 22 seconds (Ford Cup No. 4, 20 ° C) set. Each composition was on Substrate sheet in a dry film thickness of 40 to 50 microns applied, at room temperature for 10 minutes allowed to stand and baked for 30 minutes at 120 ° C (the Substrate sheets associated with the coating compositions were used for the comparative examples were 30 Heated to 140 ° C for several minutes) to coated test panels to deliver. The coated test panels were compared their properties examined. Table 3 gives the Test results again.  

Table 3

Clear coating compositions for use in Coating process with two coating and one baking step

The base coating composition A was applied to Substrate sheets applied. After about 5 minutes The coated substrate sheets were each with a the coating compositions of Examples 7 to 13 and Comparative Examples 3 and 4, with Swasol # 1000 diluted viscosity of 22 seconds, coated. The dry density of the films from the Basecoat composition was 15 to 20 μm and the one of the movies from the clear Coating composition 35 to 45 μm. Then were the coated substrate sheets at room temperature let stand for about 10 minutes and then 30 minutes baked at 120 ° C, (the substrates with the Compositions coated for the comparative examples were baked at 140 ° C for 30 minutes) and provided so coated test sheets. The coated ones Test panels were used in terms of their properties examined. Table 4 shows the test results.  

Table 4

Preparation Example 4

Using the in the above production examples prepared copolymers and non-aqueous dispersions were the curable compositions according to the invention, the one polyisocyanate compound as a crosslinking agent contained in the form of full-color Coating compositions (white) and clear Topcoating compositions for a process with two coating and a baking stage.

Preparation of Full Color Coating Compositions (White)

The following Table 5 shows the components and quantities same for the production of full color (white) - coating compositions (Coating Compositions Nos. S-9 to S-14) were used. As found in Preparation Example 3 Titanium dioxide as a white pigment use.  

Table 5

The preparation of clear coating compositions for Use in processes with two coating and one baking step

Table 6 below shows the components and quantities same for the production of clear Coating compositions suitable for processes with two coating and a baking stage are suitable (Coating Compositions No. M-10 to M-16).  

Table 6

Examples 14 to 19

The coating compositions S-9 to S-14 were used for Examples 14-19.

Comparative Example 5

The coating composition S-15 is identical to the coating composition S-14, but contains no TAKENATE B-815N and no dibutyltin dilaurate. These Composition was for Comparative Example 5 used.

Examples 20 to 26

The coating compositions M-10 to M-16 were used for Examples 20 to 26.

Comparative Example 6

The coating composition M-17, which is identical with the coating composition M-16, but no Contains TAKENATE B-815N and no dibutyltin dilaurate, was used for Comparative Example 6.  

Comparative Example 7

For Comparative Example 7, the Coating Composition M-18 (Trade Mark, Magicron # 1000 Clear, product of Kansai Paint Co. Ltd., Acrylic / melamine resin type coating composition) used.

Preparation of Basecoat Composition B

Using azobisisobutyronitrile as Polymerization initiator became the following monomer mixture in a xylene / n-butanol solvent mixture (80/20, Parts by weight) free-radically polymerized, resulting in a Vinyl copolymer solution resulted. The vinyl copolymer had a number average molecular weight of 18,000. The vinyl copolymer solution had a non-volatile content Constituents of 50% by weight and one Viscosity Z1 (determined by a Gardner-Holdt bubble viscometer).

parts by weight methyl methacrylate 40 ethyl acrylate 20 n-butyl acrylate 20 2-hydroxyethyl methacrylate 18 acrylic acid 2

A basecoat composition B for wet-on-wet Coating was made from the following components manufactured.

parts by weight Vinyl copolymer solution as obtained above (nonvolatile content of 50% by weight) 160 U-Van 28SE-60 (trade name, Mitsui Toatsu Chemicals Inc., melamine resin, non-volatile content 60% by weight) 33.3 EAB-551-2 (trade name, Eastman Kodak Co., cellulose acetate butyrate) 20 toluene 30 butyl 30 Aluminum paste # 4919 (trade name, Toyo Aluminum Co. Ltd.) 5 Aluminum paste # 55-519 (trade name, Toyo Aluminum Co. Ltd.) 5

Using a solvent mixture Toluene / xylene / n-butanol (40/40/20, parts by weight) the coating compositions to a viscosity of 15 seconds (Ford cup # 4, 25 ° C).

Production of the substrate to be coated

A treated with zinc phosphate steel sheet with blunt Finish was treated in the same way as above, to give a substrate sheet.

Examination of the properties of the coating film Full-color coating composition

The in Examples 14 to 19 and in Comparative Example 5 prepared coating compositions were on the same viscosity as set above and on Substrate sheets applied and the coated Substrate sheets were allowed to stand in a similar manner  and baked to provide coated test panels. The coated test panels were compared with their Properties examined. Table 7 shows the Test results.

Table 7

Clear coating compositions for use in Method with two coating and one baking step.

Base coat composition B was applied to Surface of the substrate sheets applied and the coated Sheets were allowed to stand for 5 minutes. Then the with Swasol # 1000 to a viscosity of 22 seconds set coating compositions of Examples 20 to 26 and Comparative Examples 6 and 7 to the coated substrate sheets applied and the coated  Sheets were made in the same way as above allowed to stand and baked to coated test sheets deliver. The coated test panels were compared with their Properties examined. Table 8 shows the Test results.  

Table 8

Preparation Example 5

Using the in the above production examples obtained copolymers and non-aqueous dispersions were the curable compositions according to the invention, which contain an aminoaldehyde resin as a wetting agent, in the form of full-color coating compositions (white) and clear topcoat compositions for Use in processes with two coating and one Burn-in stage produced.  

Preparation of Full Color Coating Composition (White)

Table 9 shows the components and the quantities the same for the production of full-color Coating compositions (white) (Coating Compositions No. S-16 to S-21) were used. As found in Preparation Example 3 Titanium dioxide as a white pigment use.

Table 9

Preparation of clear coating compositions for the use in two coating and process a baking stage

Table 10 shows the components and quantities thereof, for the production of the clear Coating compositions for use in processes with two coating and one baking stage (Coating Compositions Nos. M-19 to M-25) were used.

Table 10

Examples 27 to 32

Coating compositions S-16 to S-21 were used for Examples 27 to 32 used.  

Comparative Example 8

The coating composition S-22, which is identical to the coating composition was S-21, but none U-Van 28SE was used for Comparative Example 8 used.

Examples 33 to 39

Coating compositions M-19 to M-25 were used for Examples 33 to 39 are used.

Comparative Example 9

The coating composition M-26, which is identical to the coating composition was M-25, but none U-Van 28SE was used for Comparative Example 9 used.

Production of the substrates to be coated

A treated with zinc phosphate steel sheet with blunt Finish was the same way as above further treated to give a substrate sheet.

Examination of the properties of the coating film Full-color coating compositions

The in Examples 27 to 32 and in Comparative Example 8 coating compositions were prepared the same viscosity as set above and on the Substrate sheets applied. The coated ones Substrate sheets were allowed to stand in a similar manner and baked to provide coated test panels.  

The coated test panels were based on their properties examined. Table 11 shows the test results.  

Table 11

Clear coating compositions for use in Method with two coating and one baking step

Base coat composition B was applied to Substrate sheets applied and the coated sheets were allowed to stand for 5 minutes. Then the Coating compositions of Examples 33 to 39 and of Comparative Example 9, with Swasol # 1000 on a Viscosity of 22 seconds diluted on the coated Sheets applied. The coated sheets were on the same way as above left and burned, to provide coated test sheets. The coated ones Test panels were examined for their properties. Table 12 shows the test results.  

Table 12

Claims (11)

1. A curable composition containing:

• (I) a resin component containing as essential functional groups an epoxy group and a silanol group and / or hydrolyzable group bonded directly to a silicon atom;
• (II) at least one crosslinking agent selected from carboxylic acid compounds, polyisocyanate compounds and aminoaldehyde resins; and
• (III) at least one curing catalyst selected from organometallic compounds, Lewis acids, protonic acids and compounds having Si-O-Al bond (s).

2. Composition according to claim 1, characterized characterized in that the resin component (I) also a hydroxyl group as essential functional Group contains. A composition according to any one of claims 1 and 3 2, characterized in that the epoxy group in the resin component (I) is an alicyclic epoxy group is. 4. Composition according to any one of claims 1 to 3, characterized in that the resin component (I) dissolved in a solvent or dispersed form or in the form of a non-aqueous Dispersion of polymer particles in the presence this resin component as a dispersion stabilizer were prepared is used.   5. A composition according to any one of claims 1 to 4, characterized in that the crosslinking agent (II) is a carboxylic acid compound and in a Amount of about 1 to about 40 parts by weight per 100 parts by weight of the resin component (I), calculated as solids. A composition according to any one of claims 1 to 4, characterized in that the crosslinking agent (II) is a polyisocyanate compound and in amounts from about 1 to about 30 parts by weight per 100 parts by weight of the resin component (I) calculated as solids. A composition according to any one of claims 1 to 4, characterized in that the crosslinking agent (II) is an aminoaldehyde resin and in an amount of about 1 to about 50 parts by weight per 100 Parts by weight of the resin component (I), calculated as Solids, is used. A composition according to any one of claims 1 to 7, characterized in that the curing catalyst (III) at least one organometallic compound is that has been selected Metal alkoxide compounds, metal chelate compounds and metal alkyl compounds. 9. Composition according to claim 8, characterized characterized in that the curing catalyst (III) a metal chelate compound. A composition according to any one of claims 1 to 9, characterized in that the curing catalyst (III) is at least one compound selected was prepared from organometallic compounds, Lewis Acids and protonic acids, and in an amount of about 0.01 to about 30 parts by weight per 100  Parts by weight of the total amount of resin component (I) and crosslinking agent (II), calculated as solids, is used. A composition according to any one of claims 1 to 9, characterized in that the curing catalyst (III) is a compound having Si-O-Al bond (s) and in an amount of about 1 to about 100 Parts by weight per 100 parts by weight of the total on resin component (I) and crosslinking agent (II), calculated as solids.