JPS6076578A - Water-dilutable adhesive - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION An adhesive composition containing an elastomeric binder or an acrylate-containing binder when a suitable resin dispersed in water is added to the adhesive composition and applied to the two surfaces to be joined after dilution with water. It is also known that the adhesive strength of water-dispersed adhesives which develop a spontaneous adhesive force after overlapping and briefly pressing the parts to be joined can be improved.

Adhesives of this type are commonly referred to as contact adhesives.

To improve adhesive strength, various resins have traditionally been used alone or in combination, such as phenol formaldehyde resins, colophonium, coumaron/indene, terpene, cyclobentadiene resins or other unsaturated hydrocarbon resins. used.

A feature of all these resins is that they must first be emulsified or dispersed in water with suitable auxiliaries before being combined with the aqueous nidistomer or acrylate component.

These materials do not undergo post-reactions and crosslinking reactions with themselves and with the elastomer component or acrylate component after the emulsion or the dispersion has been prepared. This is because they do not have the chemical groups required for these reactions.

These drawbacks may be due to the resin used in the past.
This is also the basis for the fact that the increase in adhesive strength is not particularly large, especially at high temperatures. The action of these resins extends, first of all, to increasing the adhesive properties of the binder component.

This results in a physically strong interlocking of the individual molecules of the polymer or acrylate component during pressure applications.

The present inventor has proposed that (A) (&) a halogen-free polycarboxylic acid compound, Cb) an alkali metal salt, an alkaline earth metal salt, a quaternary-ammonium salt, an organic base, ammonia, or a combination thereof; Salt-forming substances of the group and at least one of the following compounds (Q,) OH
- Group-containing polymer (C2) A combination of epoxide compounds, provided that components (a) to (C2) are present as such or at least partially chemically bonded, and do not contain a catalyst. or containing a water-soluble reactive binder and (B) C31) an elastomer that is unmodified or at least partially modified with COOH groups, sulfonic acid groups or a combination thereof or 032) an acrylic copolymer. CB1) and (B2)), the proportion of the binder being from 5 to 40% by weight relative to the total solids content and that of component (B). The above-mentioned drawbacks have been overcome by water-dilutable adhesives, which are characterized in that the amount of water is between 60 and 95% by weight.

Surprisingly, it has been found that the binder (A), even without halogen, cures even at low temperatures, for example even at room temperature, and has even better light resistance.

It is advantageous for the binder (A) to at least partially react with the component (b) the uboricarboxylic acid units (,), which are expediently present in aqueous solution. That is, the component (a
) is preferably present in partially or fully salted form.

When used for adhesives, the binder (mu) is the component (
Formula (a) to (C2) using three types of girl spiders as pace
I) or a reaction product of at least 1 ff of Fi(1,), where B1 is a group of a polymer containing at least 11 II 0 groups, i.e., a polyester, a polymer, both of which have 20 to 300, respectively; in particular with an OH number of from 40 to 220 and from 100 to 800, especially from 150 to 300
The groups of the polymerization and/or straddle condensation products of the group of phenolic resins having a valence of
R5 means at least a dibasic carboxylic acid group having one C00H group ortho to the ester bond; In this case, R5 may have the same meaning as R2. ], provided that in this case the anhydride group of the above formula (I) or (Ia) may be at least partially replaced with an ester group, and the free (700H group is contained in a proportion of 1 to 200% of the component ( b) is present in the form of a salt.

Binder (A) may contain, in addition to the reaction product of formula (I) or ki (Ia), at least one unreacted unit of components <-> to (C2).

Depending on the proportion of components (a) to (C2) and whether the reaction of these components is absent, partially or completely, the binder (A) has hydrosilic properties. Exists in single or multi-component systems.

Therefore, the term "1-polycarboxylic acid compound" means a compound which may contain free carboxyl-1-anhydride- and ester groups, each singly or in combination.

Typical R4 groups include, for example, -(OH2)s (where θ is 2~
10, especially 2 to 4), 10H2-OH-OH2-, and also the formula (XI[).

Plants are suitable as R2. For example, formula (I)
Or in (Ia), 12 and R5 may be the same or different, and formulas (ff) to (■) and (X
I) ~ (XV) g=1,2 Shun (III) (IT) (V) (Va) (Wb) u=1-8 0 0 o 0 0 0 11M 0 = (OH2) p p = 2-8 ooo.

(XrV) r=1-8(XV), in which in these formulas the anhydride groups of formula (I) bonded to the R2 group each together and in the formula (n)~C■''), Rs.
Amituna7 talin, bicyclooctene, cyclopentane, nato2hydrofuran chain and R4 has 1 to 20, especially 1 to 15, especially 2 to 8 carbon atoms and optionally an oxygen bridge or -HC ,,O
#: taoon hydrogen radical, having an ester group interrupted at least once by a H-group or having 1 to 6, especially 1 to 3 O atoms, formula (XVI)
(Notification) 6 (XVI) (Shoulder) (Employment) (■) (XX) (Notification) An aromatic group having 6 to 43 C-atoms (
However, this aromatic radical is substituted by at least one radical R6 of the group consisting of alkyl, alkoxy and halogen groups each having 1 to 6 C atoms. ), a bizine group or a group of formula (XX+U) or αW), provided that in the above formulas (XX) and (XXI),
means one of the formulas, 2 is -(OH,)m-
(means an aromatic group represented by m; r and U each represent an integer from 1 to 8, especially from 1 to 4; y represents an integer from 1 to 3; and 2 represents 1 or 2).

Furthermore, R5 can also be a di- or tricarboxylic acid group, such as trimellitic acid, heptalic acid, 4-amino-phthalic acid, endomethylene-tetrahydroheptalic acid, hexa- and/or tetrahydrohectadalic acid, naphthalic acid, 4-
It may also mean a group of amitunaphthalic acid.

The binder mixture Jt, □-always has a high reactivity. This makes it possible to cure already at 0'c, ie to form a polymer network.

The reaction product (1) or (Ia) is a hydroxyl group-containing oligomeric compound or a monopolymer compound of formulas (II) to (■)1 (XI) and (XrlI).
It is produced by reaction with a dianhydride having a group represented by -(XV). Suitable knee anhydrides have the formula (m)
~(tl), formula (XI) and (xm) ~(XV
), and further examples include pyromellitic dianhydride, benzophenone-tetracarboxylic dianhydride, dianhydride, tetrahydrofuran-tetracarboxylic dianhydride, cyclopentane-tetracarboxylic acid - dianhydrides, as well as anhydrides according to formulas (II) and ωa), such as trimellitic anhydride and/or compounds of (ff)0 0 00, formulas (1 to (■)), and (X [)
-(XV) and/or other oligomeric dianhydrides.

If carboxylic acid units with free 000H- or ester groups are desired #'i, mixing with compound (C1) or Id (C2) before, during or after coupling the dianhydride to compound R1. It may also be expedient to carry out at least partial hydrolysis or esterification beforehand.

In general, the reaction product (I) or (Ia) contains at least two 0OOH- groups in salt form and at least one
ester groups, so that the molecule bound to the R1 group is present in the form of a partial ester, in particular a half ester, in which case the ester group is in place of the anhydride group. It's okay to exist together. Such ester groups include monohydric alcohols in the iso- or n-form, such as methanol, ethanol, hexanol, octatool, lauryl alcohol, stearyl alcohol. Each of the eight partial esters can be used alone or in a mixed state with other carboxylic acid units. These are likewise common reaction partners for epoxide compounds. However, the presence of free 000H groups is not necessarily required if the mixed components are reacted with each other in thinning layers and in the presence of atmospheric moisture. In many cases, a carboxyl group in the ortho position to the salt group or ester group acts as an initiator. These are bonded to component (C2) by reaction with the oquine ring of one component (C2), where moisture is required when the base reacts and liberates a secondary hydroxyl group, which forms the anhydride. group to generate a new carboxyl group that reacts with other oxy2-rings with ring opening. Here too, the reticulation is carried out, which according to embodiments of the invention can already be effected under mild conditions, for example under oh.

If the binder is present in a mixture, it is generally the case that a stable mixture consisting of the epoxide component (C2) and/or the OH-group-containing component (C1) is first prepared and then subjected to a short processing time. Formula (II) acting as a curing agent before time
- (■) and (XI) - (XV) acid units (a) or some other reactive salt conductor, for example in the form of its salt, are added, with component (b) being added to component (a). and may be added at the same time or after.

Furthermore, the binder mixture (mu) contains, in addition to the reaction product (I) or (I a), groups according to formulas (■) to (■), (XI) and (XIII) to (xv). at least one polycarboxylic acid unit and/or trimellitic acid not bonded to the polymer- or condensate chain, which is at least partially hydrolyzed or in the form of a salt; May contain. Other free acids include, for example, those listed under R5, as well as tetrahydro7
These include ran-tetracarboxylic acid, benzofuran-tetracarboxylic acid, and benzo7-ran-hexacarboxylic acid.

These J1 additive acids may also be hydrolyzed to form a carboxyl group in addition to the carboxyl group, or may be converted into a salt. In such cases too, the mixtures already cure under mild conditions, for example at room temperature or even at low temperatures, for example OC, resulting in coatings with characteristic properties.

Optionally, these additional acids may also be present in the form of their partial esters or partial salts.

The ester formation can be carried out on the reaction product (n) or on the anhydride (Ia) or on the anhydride or on the free 000H group already before its preparation.

Oligomeric acid anhydride component in free acid or salt form (Vl
) is 0.1 to 0.1 to the total amount of polycarboxylic acid.
Advantageously, the content is 99.9% by weight, in particular from 30 to 70% by weight.

If the polycarboxylic acid also contains trimellitic acid, its proportion relative to the total amount is from 0.1 to 50, in particular from 5 to 50.
It's a 20-fold threat.

The term "polymerization products and/or condensation products" in R' also includes oligomers.

The polyester which forms the residue R1 of the reaction product (I) or (1,) or which is present free in the binder (A) can be prepared in a manner known per se by known polycarboxylic acids, such as 7-talic acid. , isophthalic acid, terephthalic acid, halogen heptathalic acids such as tetrachloro- or tetrabromo-phthalic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, endomethylene-tetrahydroheptalic acid, trimellitic acid, etc. mono-carboxylic acid,
For example, benzoic acid, butylbenzoic acid, lauric acid, iso-
Nonanoic acid, a naturally occurring mixture of the above acids together with fatty acids, can also be prepared from its anhydride. Suitable alcohol components of such polyesters include, for example, polyhydric alcohols such as ethylene glycol, propanediol, phthanediol, bentanediol, hexanediol, neopentyl glycol, diethylene glycol, cyclohexane-dimetatool, trimethyl-pentanodiol, and trimethylol. Ethane-propane, chrycerin, pentaerythritol, dipenta-erythritol, bishydroxyethyl-iso-mika-terephthalate,
Tris-hydroxyethyl isocyanurate, etc., optionally combined with a monohydric alcohol such as butanol, octatool, lauryl alcohol, rylyl alcohol,
Together with ethoxylated or propoxylated phenols or their analogues, each used alone or in a mixture.

The polyester in binder (A) or the polyester of the reaction product (see formulas (I) and (Ia) above) is
High-molecular polyesters of aromatic nature, such as terephthalic acid-ethylene glycol- or monobutanediol-polyester, isophthalic acid-ethylene glycol-mata, can also be prepared by at least partially chemically decomposing hexane-diol polyester, etc. It may occur under the influence of control and/or polyhydric alcohols, esters, dicarboxylic acids or the like.

-In the case of a reaction that happens to be carried out with a hydric alcohol,
These can be overreacted.

Condensation resins - in the form of polyesters - are esters,
amides, imides, ethers, thioethers, sulfones,
Also included are those containing at least one member of the amine group. The hydroxyl group of residue R1 may also be phenolic, especially alcoholic. In particular, hydroxyl alkyl acrylates such as methacrylates or maleic acids are combined with olefinically unsaturated monomers such as styrene, α-methylstyrene, vinyltoluene, acrylic acid alkyl esters, allyl compounds, cyclobentadiene and their derivatives. Alternatively, polymer products prepared in known manner by copolymerization are suitable.

Furthermore, polymer resins in the form of polyvinyl alcohol, vinyl alcohol and unsaturated monomers, such as styrene and/or
Alternatively, copolymers of acrylic acid esters, provided that the copolymers are at least partially saponified, phenolic resins with free hydroxymethyl and/or pendant hydroxyethyl groups are suitable.

Suitable phenolic resins with free OH groups include, for example, resols. Suitable phenolic components are monovalent and polyvalent mononuclear or polynuclear phenols, such as phenol and the various cresols.

xylenol 5-butylphenol, naphthol, resorcinol, diphenylolmethane, having two hydrogen atoms in the ortho and/or para position relative to the hydroxyl group;
Diphenylopropanes, especially those with at least two reactive hydrogen atoms, such as phenol or resorcinol. Aldehyde components for phenolic resins include, for example, formaldehyde in the form of an aqueous solution, paraformaldehyde or in the form of other substances from which formaldehyde is separated, such as trioxane, acetaldehyde, etc., for example in the form of substances from which acetaldehyde is separated;
Higher aldehydes such as gropion-aldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde, etc. can be used.

Alkylphenols include trifunctional or trifunctional alkyl-7 enols with respect to formaldehyde, especially those having 1 to 20 C atoms in the straight chain or branched chain or in the alkyl group and having cyclic alkyl or aralkyl residues. 0-1 and tdp-alkylphenols, such as p-
Isopropyl-1p-tert-butyl-10-iso-octyl-1p-iso-nonyl-1p-iso-dodecyl-1
〇-Sect-butyl-10-isononyl-1O-iso-dodecyl-1p-cyclohexyl- and 6,5-diisopropyl- and 3,5-di-isobutylphenol are used.

All alkylphenols may also contain secondary amounts of highly alkylated phenols. However, preference is given to using the iso-compounds mentioned above, and also tert-butylphenol.

Suitable resols are those in which the molar ratio of phenol to formaldehyde during the condensation reaction was 1:(0.9-1,a), in particular 1:(0.95-1.4).

For example, from 4 to 20 suitable epoxide compounds - present in R1 or in free form in the binder,
In particular, it has a C-number of 4 to 12 and has a C-number of 2 to 6, especially 2 to 6.
Polyepoxide-alkanes with 4 oxirane rings; also epoxidized butadiene oils, their C-alkylated products, such as imprene oil; aliphatic glycidyl ethers, such as glycidyl ethers of polyols, such as ethylene glycol, di- and / or triethylene glycol, 2,2-dimethyl-propanediol, prono(diol-1,2 or -1,5, butanediol-1,4 or -1,3, pentanediol-1,
5. Hexanediol-1,6, as well as glycerin, trimethylolpropane, glycidyl ethers such as cyclohexyl dimethanol, glycidyl ethers containing chloroxane groups, epoxidized fatty acid esters, such as epoxidized soybean oil, epoxidized linseed oil, and mushrooms. dimerization and/or trimerization compounds of the type of compounds;
Alicyclic his-epoxides, such as vinylcyclohexene-dioxide, limonene-dioxide, bis-(epoxycyclohexyl)-methane, cyclopentadiene-dioxide, bis-(
(epoxy-cyclopentyl ether); epoxidized aliphatic- and/spanned alicyclic allyl ethers and/spanned allyl esters, e.g. - adipates; also glycidyl-acrylic- or -methacrylic esters of epoxidized polyesters or oligomers or polymers and/or these, such as acrylic- or methacrylic acids, maleic esters, ethylene, propylene,
Copolymers with butylene, styrene, vinyltoluene, α-methylstyrene, vinylfuclohexane; trimerized epoxide compounds, such as triglycidyl isocyanurate, etc., either alone or in a mixed state Can be used.

Additionally, mixtures of epoxide compounds or monoepoxides present alone or in mixtures can also be used. Suitable monoepoxides include, for example, olefin oxides such as octylene oxide, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-butyl-phenol glycidyl ether, cresyl glycidyl ether, S-(bentadeflu)-phenol glycidyl ether. , styrene oxide, glycidyl methacrylate, cyclohexene-vinyl monooxide, dipentene-monoxide, pinene oxide, and glycidyl esters of tertiary-carboxylic acids. In particular, unbound component (b) as a reaction product can be present in the form of at least one polyepoxide, optionally in a mixture with at least one monoepoxide.

The aforementioned epoxide compounds, especially the aliphatic and cycloaliphatic ones, both in the free state and in the bound state, are highly compatible with the carboxylic acid compounds (,) and the raw CoOH and/or bases under crosslinking and polymer formation. Reacts easily.

Suitable alkali or alkaline earth compounds are, for example, sodium, potassium, lithium.

hydroxides, oxides, carbonates or salts of calcium, magnesium, barium, zinc, aluminum or similar metals with carboxylic acids or amino acids with tertiary or quaternary N-atoms, such as acetic acid; salt or M, salt of H-diethylaminoacetic acid, salt of 2-(dimethylamino)-propionic acid, tri- or tetra-(
They are salts of (carboquinalkyl)-amines, and can be used alone or in combination. Suitable amino acids for forming salts are, for example, amines of the general formula % () where H6, R7 and R8
may be the same or different, and hydrogen,
Alkyl e.g. benzyl, 1-8.

In particular alkyl having 1 to 5 C atoms, cycloalkyl such as cyclohexyl or 1 to 5, especially 1 to 6
hydroxyalkyl having 5 C-atoms.

), morpholine compounds or quaternary ammonium salts of monocarboxylic acids having 1 to 5, in particular 1 to 3, atoms. Examples include trimethyl-, triethyl-,
Examples include tributylamine, N-dimethyl-cyclohexylamine, and N-dimethyl-benzylamine. In many cases, it may be necessary to use an excess of salt-forming organic base compared to the carboxyl group equivalent. Inorganic cations are generally used in insufficient amounts.

If the anhydride group of the reaction product (I) or (Ia) is 9
9:1~1:99. In particular, it can vary from 20:1 to 1:20.

Excellent crosslinks are often obtained even without catalysts even under mild conditions such as room temperature, e.g. 20 mm and slightly elevated hotbeds, e.g. 80 mm and/or baking conditions, e.g. 120 mm and above. It will be done. However, by increasing the temperature, e.g. from 30 to 210 t", especially from 80 to 190 t", the curing time is greatly reduced. Therefore, even under seven-yoke drying conditions, such as those used in coil- or can-coating processes, Basically 200-350
Excellent coatings are already obtained at a temperature of 100 mL and a very short time, for example from 10 seconds to 5 minutes. The free carboxyl group of the polycarboxylic acid unit (,) and the epoxide compound (02
) is 100:1 to 1:1.
00, especially 20:1 to 1:20. Within advantageous ranges, for example in the case of a ratio of 1:1, particularly good film-forming properties have been found. However, in many cases an excess of 0 is used, e.g. to improve adhesion.
OOH groups are also preferred. In some cases, for example in the case of strongly lipophilic systems, for example for primers, an excess of 7-do groups is also utilized. Therefore, the mutual proportions are adjusted depending on the desired purpose of use. However, it will typically be within the aforementioned range.

The binder (A) mixture may additionally contain at least one thermosetting resin from the group of melamine resins and urea resins, alone or in a mixture, up to 30% by weight of the total solids content, in particular from 2 to 15% by weight. It contains %. With such additives, a significant increase in chemical and solvent resistance can be achieved, especially when cured at high temperatures.

Suitable amine resins are urea and/or melamine resins containing free OH groups, optionally partially etherified with monohydric alcohols having 1 to 4 C atoms. The molar ratio of melamine/formaldehyde during the condensation reaction is usually 1:(2 to 4.5). As the melamine component, penta- and hexamethylol-melamine are preferred.

In order to accelerate the reaction of components (a) to (C2) and/or during curing, up to 5% by weight of catalyst, based on the solids content, may be added to the mixture, in particular from 0.01 to 0. It may be advisable to add it in a proportion of .5 parts by weight. Suitable basic catalysts include, for example, diaza-bicyclooctane, diaza-bicyclo-nonane or undecane, imidazole II? conductors such as 3-methyl-, phenyl- or fuclohexyl-imidazole, trialkylamines such as triethyl-, triphthyl-, tricyclohexylamine, N-alkyl-piperidines, N,N
'-dialkyl-piperazines, trialkyl- or triaryl-phosphines, N,N'-tetraalkyl-aminoalkyl-oxamides, N-dialkylaminoalkyl-oxamidic acid alkyl esters, and further as component (b) the above-mentioned Amines, alkali metal hydroxides, carbonates and organic acid salts.

Lithium fragrant, as well as addition compounds of these with rectified ethers or similar ligands and of the formulas (■) and (
There are alkali salts of the polycarboxylic acid units of Ia). Also suitable as catalysts are the chelate compounds of magnesium, aluminum and titanium which are disclosed, for example, in German Patent Application No. P 27 25 492.0 for carboxyl group acceptors. The amines or phosphines mentioned above may also be present in the form of quaternary hydroxides or halides. For example, N-dimethyl-N-lauryl-N-benzyl-ammonium chloride, tetraethylammonium-hydroxide, triphenyl-benzyl-phosphonium-bromide.

Furthermore, salts of the organic bases mentioned above with organic acids such as acetic acid, propionic acid, lauric acid or salicylic acid can also act as catalysts in the desired reaction. Mixtures of catalysts can also be used.

The catalyst for the formation of the reaction product (I) or (Ia) and the catalyst for the curing reaction may be the same or different.

A catalyst can be added to each reaction step of components (a) to (C2). However, this is not necessarily necessary.

The binder (A), especially the reaction product (I) or the binder (Ia)
are generally storage-stable and clear to milky-cloudy liquids, depending on their chemical structure, of low to high viscosity. Its solids content can vary within wide limits. But it can be. It exhibits very good wetting properties.

This material can be arbitrarily diluted with water without adding a solvent, without flocculating, and without exhibiting any viscosity abnormality. They are therefore advantageously present in aqueous solution or optionally in a mixture with water-soluble or water-insoluble solvents. Curable binders (A) u are generally well suited for a variety of application purposes.

Binding agent (A) can be used in at least one stage, simultaneously or in any order, to combine (a) a halogen-free polycarboxylic acid compound, (b)
Alkaline salts, alkaline earth salts, quaternary ammonium salts,
A substance of general formula (I) is prepared by reacting a substance forming a salt with an 0OOH group selected from the group consisting of an organic base, ammonia or a combination thereof with (c) an OH group-containing polymer and (c) an epoxide compound. The reaction product of (Ia) is formed by hydrolyzing the anhydride groups present or in any process step, at the latest during the salt formation. Hydrolysis can also be carried out partially.

The above reaction can be carried out in one stage or in multiple stages, in particular up to four stages. For example, (I) the OH group-containing polymer (cl) is reacted with the polycarboxylic acid compound (a) in the first step, the reaction product is hydrolyzed in the second step, and then the third step is carried out. epoxide compound (C2) and in the fourth step component (b).
) with salt formation, or (■) the first and second steps are carried out as in (I), the fifth step is carried out with salt formation with component (b), and In the fourth step, the epoxide compound (C2) is reacted, or in the first step, the polycarboxylic acid compound (,) in the anhydride state is hydrolyzed, or the polycarboxylic acid compound in the free acid state is directly hydrolyzed. Salt formation is carried out by starting from an acid compound (,) and reacting some hydrolysis product with an epoxide compound (C2) and then with component (b) or ■ in the first step. An OH group-containing polymer (cl) is reacted with a polycarboxylic acid compound (,) and the reaction product is converted into a second
hydrolysis in the first step and salt formation with component (b) in the third step or simultaneously with the hydrolysis, or (b) components (C1) and (C2) are simultaneously added to the polycarbonate in the first step. reaction with an acid compound (, ), followed by hydrolysis and salt formation (b) by reacting components (, ) to (C2) in one process step with simultaneous hydrolysis; or (b) the polycarboxylic acid compound is reacted with component (b) in the first step with salt formation and, insofar as component (, ) has 6 anhydride groups, is simultaneously subjected to hydrolysis and The product thus obtained is reacted in a second step with an epoxide compound (C2).

The binder (A)
) may contain unreacted portions of components (a) to (C2). However, it is also possible to additionally add other parts of these components to the reaction product, in which case the chemical structure of the reacted component and the chemical structure of the complementary added component are similar to those of the binder. They may be the same or different depending on the desired purpose or properties.

As the above-described embodiments of the process for preparing binder (A) show, it is also possible in many cases to omit the special process step of hydrolysis. In exactly the same way, it is also possible to omit the chemical reaction of component (c+)t or component (c2).

The amount of water used in the hydrolysis may be up to 500% of the theoretically required amount, especially from 5 to 300%.

Due to their various chemical structures, binders (A) are suitable for a wide variety of applications, for example for the production of coating systems that cure at room temperature or under heated conditions. The binder (A) is
Aqueous synthetic resin dispersions, such as thermoplastics, such as polyvinyl acetate, polyvinyl chloride, acrylic and/or methacrylic polymers, polyvinyl ether, polyvinyl chloroprene, polyvinyl acrylonitrile and ethylene-butadiene-styrene copolymers. It can also be combined with those based on coalescence. This can be done in particular using suitable monomers, such as hydroxyalkyl acrylates or methacrylates, provided that the hydroxyalkyl group is, for example, hydroxyethyl-acrylate.
or - propyl group - acrylic acid, maleic acid or esters thereof, saturated - or unsaturated aliphatic -
It is particularly compatible with dispersions of copolymers such as those which have been strongly polarized by grafting with vinyl esters of cycloaliphatic and/or aromatic carboxylic acids or analogs thereof. Optionally, the dispersion is used together with dispersion aids.

A binder (A)K exhibiting excellent stability against ultraviolet rays,
Pigment-free or pigment-containing or pigment-containing coating systems, such as paints, can be produced. The coating system cures sufficiently quickly even at room temperature, optionally under the action of a catalyst, and gives a coating with good mechanical properties. 14+ coatings with high mechanical strength and high chemical stability.

The binder (A) can be used as long as it can withstand the curing temperature of the coating material.
Applied on all types of substrates.

Suitable substrates include, for example, ceramics, wood, glass, concrete, synthetic resins, in particular metals such as iron, zinc, titanium, copper, aluminium, steel, bronze, magnesium or similar materials. The substrate can optionally be rendered adhesively compatible or corrosion-stable by suitable mechanical and/or chemical pretreatment. However, binder (A) adheres well to various metal substrates even without an adhesion promoter or intermediate layer. The good adhesion of such coating systems corresponds to the values GT OA to GTIA according to the test formulation according to DIN 55151. Furthermore, the coatings are very well shaped and exhibit high weather resistance and good chemical stability.

The binders (A) are also suitable for various fields of application, in particular for producing corrosion-resistant coatings and/or interlayers as durable and matte coatings. Furthermore, it is suitable for the coating of objects in contact with fuels and solvents, as well as protection against atmospheric influences, such as street markings, structures or structural elements for electrical industrial purposes, and in particular for electrical cables. A coupling agent (
Due to its excellent properties, A) is also excellently suitable for single-layer coatings. Depending on the selection of the respective components, metal sheets coated with a bonding agent can be subsequently deep drawn, corner bent, profiled, stamped or similar without significant damage to the remaining good properties. It can be shaped by any means. The deposited coating layer can remain unchanged, but can also serve as an intermediate layer, in short as a substrate for other coatings, which may also consist of the same or other customary coating materials.

The coatings obtained are glossy or matte coatings, as desired, with excellent mechanical and chemical stability and good weather resistance. On the other hand, it is also possible to produce matte paints with excellent mechanical and chemical properties.

Surprisingly, large amounts of pigments and fillers are not required for this purpose.

Other uses of binders are based on their ability as crosslinking resins or protective colloids with emulsifying action, through aqueous dispersions. Due to the binder #'i, good dilutability and other good properties, it is suitable for use in electrocoating.

Binder (A) #'i Can also be used as a binder for organic and/or inorganic fiber materials. Binders (A) are also suitable for cellular or porous materials such as curable molding compositions, casting resins, putties, foams and as insulating coatings.

The adhesives of the invention are thus polymerized with such reactive water-soluble binders (A) which can be used in various fields, in which case the resin of the synthetic resin dispersion is optionally at least partially 0OOOH. - and/or elastomeric polymer resins modified with sulfonic acid groups (B
1) and/or (B2) of the acrylic copolymer, provided that the proportion of the reactive binder (A) is from 5 to 40, in particular from 10 to 20% by weight, based on the total solids content, and component(
The proportion of B) is from 60 to 95, in particular from 80 to 90% by weight, and A plus B corresponds to 100 weight i*.

Reactive water-soluble binder (A) used according to the invention
Compared to conventionally used binders, the adhesive has the advantage that it is already present in a water-soluble or dilutable state before being processed into an adhesive, and does not need to be emulsified or dispersed in water. have. Furthermore, the binder (A) contains reactive chemical groups which can react with each other and/or with the elastomer components or with the acrylic resin components if selected accordingly under specific conditions. However, as a result, true chemical crosslinking reactions can occur between the individual molecules of each component of the reactive binder as well as between these components and the elastomeric or acrylic component.

Thus, the bond strength at room temperature and at elevated temperatures is many times greater than with conventional chemically unreactive resins dispersed in water.

A suitable elastomer (B
+) #'i, for example natural or synthetic rubber latexes, such as those based on polybutadiene, acrylonitrile rubber, butadiene-styrene copolymers, chlorosulfonated polyethylenes, especially poly-2-chloro- Butadiene, carboxylic acids such as poly-2-chlorobutadiene combined with acrylic and/or methacrylic acid.

Suitable acrylic copolymers (B2) include, for example, acrylic-spliced methacrylic acid, maleic acid or derivatives thereof, such as esters, amides, nitriles, in particular those containing 1 to 6 alkyl or hydroxyalkyl groups. C-
There are copolymers of acrylic compounds such as alkyl- and/or hydroxyalkyl-acrylates or monomethacrylates having atoms.

Suitable copolymerizable monomers for component (B2) include side-illuminated maleic esters, vinyl esters of saturated or unsaturated aliphatic, cycloaliphatic and/or aromatic carboxylic acids, styrene, α-methyl Styrene, vinyl doluenkaal.

Iv in at least one of the components (B1) and ω2)
y rt snore hi 7-4IAIlge0OOH-卦1t de/
d sulfonic acid group and optionally additional OH
The presence of the group significantly increases the adhesive strength of adhesives made with the adhesives of the invention. Ingredient CB1) Too much or (
If B2) contains polymerized carboxylic acid groups, e.g. of acrylic-spread methacrylic acid, these components as well as the reactive polymer mixture can be used when crosslinking the adhesive at elevated temperatures. It can react with the existing epoxide group while forming a crosslinked product of α-oxycarboxylic acid ester.

When using binders (A) for adhesives, polycarbo/acid units (a) based on trimellitic anhydride and alkylene glycols having 2 or 3 C-atoms in the alkylene groups are incorporated. It is for a good purpose that it is done.

If the reactive bond #J(A) used for the adhesive contains a reaction product of the above-mentioned formula (I) or (Ia) - in which case the explanation of the above-mentioned formula applies - is a branched polyester group based on at least one dicarboxylic acid, an aliphatic diol and a triol, in which the group R1 in formula (I) or (1a) is free of R2 and/or R5 groups The 000H group is partially esterified with a polyhydric alcohol, and the remaining anhydride group or 0
It is expedient for the 00H group to be present in the form of a quaternary ammonium salt and for the epoxide compound (C2) to be present in the form of an epoxidized fatty acid ester.

Suitable binders (A) are, for example, (C1) those based on polyesters containing OH groups, such as phthalic anhydride, neopentyl glycol, trimethylolpropane;
(C1) an epoxidized oil, such as soybean oil and/or linseed oil, and (b) ammonia and/or trialkylamine. Manufactured from.

The adhesives of the invention can be applied to the surfaces to be bonded and cured without or using high temperatures - for example from 80 to 150 mm, especially from 100 to 120 mm. In general, curing at high temperatures is preferred. To further improve the adhesion effect, apply 4 coats of adhesive before applying the adhesive to the surface to be bonded.
Activation is advantageously carried out by heat treatment at 0 to ao'F, in particular 55 to 651.

In this case, the details are as follows: polymer (B),
For example, polymerized carboxylic acid groups, e.g. acrylic-
or poly-2-chlorobutadiene without or with methacrylic acid groups, or a mixture of unmodified poly-2-chlorobutadiene and poly-2-chlorobutadiene with polymerized carboxylic acid; copolymers ω2) of various acrylic esters (optionally with further comonomers) or of such copolymers with corresponding copolymers modified with carboxylic acids. The colloidal aqueous dispersion of the mixture is mixed with the aqueous hydrosil of the reactive binder, for example under vigorous stirring, until homogeneous, and, if required, the auxiliaries or fillers mentioned below may be added.

Next, add 60 to 110 tl of this adhesive, especially 70 to 90 tl.
It can be contact-applied to the surfaces to be joined and cured at temperatures of '.

This adhesive mixture can be used immediately for adhesive purposes if very high demands are not made on the adhesive strength. However, if extreme strength (i.e., no cracking of the bonded material and adhesive layer during inspection of the bond site) is desired, the applied adhesive is generally stored for a few weeks at room temperature or sealed. 40-8 in container
It is necessary to heat to 0 mm, especially 55 to 65 mm.

During these times, the crosslinking reaction between the 000H group and the epoxide group and the associated reactive binder (A) have already occurred.
An increase in strength occurs within the binder (A) or between the binder (A) and the nidistomer or acrylic component, but this must occur only incompletely. This is because otherwise the adhesive properties would no longer be sufficient for later use as an adhesive. Sui
#j or can be stored in a sealed container at room temperature for several months before use without losing its potency. Adhesion is carried out in the manner that is customary for contact adhesives - that is, the parts to be joined are roughened, thoroughly cleaned of any dust that may be present, for example by planing and spraying, and then joined together. Apply adhesive to the desired area.

However, contrary to the previously used water-based contact adhesives, the water of the dispersant does not evaporate after application of the adhesive, but this evaporation is accelerated by the supply of heat and the surface coated with adhesive then Wait for the two to simultaneously heat to a temperature of 100C or higher. In this case, as the water evaporates, the tack increases until a decrease in tack occurs due to the crosslinking reaction, which develops by further reactions between the carboxyl groups and epoxide groups that are still present. The range of maximum tack and ultimate bond strength depends on various actors, such as the amount of adhesive, the heat used, the surfaces to be joined, or the like. This range is easily determined in time.

After such a predetermined heating period, the adhesive-coated and heated parts are overlapped while still hot and immediately heated for a short time, e.g. 20-30 seconds 0-5-0.5
Press together under mPa. Thereafter, the bonded material, eg, layered material, is removed from the compressor and cooled. This adhesive layer can be loaded immediately or can be further processed. This is because the adhesive already has maximum ultimate strength.

In this way, a large number of materials can be laminated into a very tight composite in a short time with the adhesive mixture underlying the invention. Examples of such materials include rubber, synthetic resin, leather,
Wood, chip 7% board laminate, fiber, felt, textile,
freeze.

Carpet, cork, paperboard, metal or similar materials are laminated together singly or in combination with each other.

In order to achieve certain properties, the adhesive mixture may also contain small amounts of customary additives 5 such as antifoaming agents, wetting agents, thickening agents, antiaging agents, fillers or the like. The adhesive may be used in a variety of applications, resulting in a finished contact adhesive suitable for a wide variety of applications.

In the following formulations and examples, unless otherwise specified, parts refer to parts by weight and % by weight. These relate to the content of non-volatile solids, unless otherwise indicated.

The structures of the anhydride and the acid obtained from the anhydride by hydrolysis were determined by gel permeation chromatography.

Unless otherwise indicated, the polycarboxylic acid component (a) is an anhydride mixture prepared by the reaction of trimellitic anhydride and propanediol-1,2, respectively - trimellitic anhydride and anhydride (MV ) and (XV)
and the OH group-containing component (c) is phthalic anhydride, isophthalic acid, maleic anhydride,
A polyester produced on the basis of propatool and glycerin is used.

The following is used as the epoxide compound (C2): A:
Eboxidized linseed oil.

B: soybean oil, C: butadiene oil, D: pentanesiol-1,5-cyf') cidyl ether E: 5,4-epoxychlorhexylmethyl-3
', 4'-Evoxine chlorhexane-carboxylate, II' Nidiphenylolpropane-bis-glycidyl ether, G: Tetrahydro-phthalic acid-bis-glycidyl ether, H Nidicyclopentadiene-dioxide, Engineering: Hexafluor roudiphenylolpropane-bisuglycidyl ether, J: epoxide ester/phenol/formaldehyde/novo2c, K: 1,3-his-r3(2,3-1 poxyflohoxy)-propyltetramethyl-disiloxane.

In an example relating to use for adhesives, after cooling the adhesive layer to room temperature, the peel strength of the adhesive was measured at a peel angle of 180° and a peel rate of 200 Mm/min (starting peel strength) fIll + constant did. The measured values are listed in Table 1.

shellfish (I) reaction product (1) or (Ia); 11.
7--E, 苧□□-1A-SunnyXh---i□□Drunkness 1□→
忰□−に□←−(su (4-step batch process) 100 parts of anhydride mixture (acid number = sys,.

=560) and 30 parts of acetone are homogenized under -50. To this, 70 parts of methyl ethyl ketone and 1
A solution of 27 parts of polyester (OH number=107) is added dropwise over the course of 1 hour. Stir under 9 oz. until the reaction mixture reaches an acid number in water of 197 (based on 100 g of resin). Then 15 parts of water are mixed in. After stirring for 6 hours at 80-90 ml, the acid number is at 1 AO (for 1 AO % resin) in butanol.

The mixture temperature is lowered to 60 mm and 133 parts of epoxidized linseed oil (epoxide number=8.9) are added dropwise over the course of 2 hours. This mixture has an acid value of 90 in butanol.
Stir until the temperature drops.

Thereafter, a mixture of 56 parts of dimethyl-aminoethanol in 540 parts of water is introduced and stirred. A pale yellow solution is obtained which emits protein light. 0.1% - 40
The organic solvent is then distilled off. After filtration, a yellowish, substantially transparent aqueous resin solution is obtained. This one is clearly visible under an ultraviolet microscope.

A folded disc is shown. The solids content (125υ, 1 hour) was approximately 39cm.

In some cases, the organic solvent may be processed such that it remains at least partially in the final product.

(2)-(24) The reaction products according to Examples 2 to 24 are also prepared analogously to Example 1.

(25) (Two-step method) 151.4 parts of epoxide compound A (epoxide value 8.
9) is homogenized for 30 minutes at 40°C with 183.6 parts of a 66.7 part solution of polyester having free OH groups (0H(i [ [i, , , 107)].
part of powdered anhydride mixture (acid, value/H20=550
) is introduced in small batches over the course of 1 hour. The mixture is stirred under 50-70 T until the sample is clearly dissolved in water/25% aqueous ammonia (3:1). This corresponds to approximately 5 hours later. The reaction mixture was stripped of the solvent under reduced pressure (0.1 par) and 57 parts of 2
A mixture of 450 parts of aqueous ammonia and 450 parts of water is introduced and stirred.

A pale yellow resin solution with a slight protein glow is obtained. The solids content was approximately 41%.

(26) (3-step method) 185 parts of epoxide compound B (epoxide value = 6.
4) 188 parts of polyacrylate with free OH groups (OH number = 7Q) and 30 parts of water are stirred at 30°C. After addition of 0.1 part of triethylamine and 0.5 part of acetic acid, 90 parts of the anhydride mixture (
Oxidation/H,0=498) is introduced.

In the course of 4 hours the temperature was increased to 55 t'' and at this temperature a sample of the reaction mixture was dissolved in aqueous ammonia (see Example 25) until dissolved to a luminescent state. do.

After introducing and stirring a mixture of 60 parts of dimethylaminoethanol and 600 parts of water, a milky resin solution with a solids content of 42.8% is obtained.

Table 1 listed later shows the reaction product (I) or (Ia)
1 shows an overview of the production and structure of the binder (A) of the present invention in the state of .

MjliK: Methyl ethyl ketone, Acnia7ton, TOl: Toluene, XyJ: Xylene, OHX Nidiclohexane, MIK: Methyl isopropyl ketone, PM8A: Pyromellitic anhydride, DABO didiaza-biachlorooctane, NP engineering: N-
Phenyl-imidazole, DMA dimethylamine.

TMA:) Listylamine 1 DMAE Nidimethylaminoethanol, TDMAP
: ) Lis-dimethylaminophenone, 0HEA :
N-cyclohexyl-N-ethylamine, BPTDA: benzophenone-tetracarboxylic anhydride, DMP: N,N'-dimethyl-piperazine, TMA
j! i: N, N-tetramethylaminoethane, 'r
'+LlkT5 + SshiJ 411- Ding noprobanol-1.

In Table 1, “Starting-SZ” refers to OH-polymer (C1
) and the polycarboxylic acid unit (1) before hydrolysis. ″″Final-8Z
1" means the acid value of the product after hydrolysis. 1Final -822' means the acid value after reaction with the epoxide compound (C2).

(If) Preparation of binder (mu) for adhesives (27) Starting from polyester, which is combined with ethylene glycol and 2 moles of trimellitic anhydride)
dianhydride according to the methods described herein. and the hydrolysis product so obtained (in the form of a polymeric carboxylic acid) is partially reacted with epoxidized soybean oil, resulting in still 70
The OH group is present in free form. This is neutralized with ammonia to give a product with a value of about 7.5.

(28) Proceed as in example (27). However, 0OOH
Trimethylamine is used instead of ammonia for neutralization of the groups, forming a product with a value of about 7.4.

(29) Proceed as per Example 2υ. However, instead of epoxidized soybean oil, use a mixture of epoxidized linseed oil and epoxidized soybean oil in a weight ratio of 1=2. Neutralize Therefore, 70% ammonia and 30%
A mixture with % by weight of trimethylamine is used. A product with a state value of 7.0 is obtained.

(m) Preparation of Adhesives (30) An amount containing 700 parts of solids of an aqueous dispersion of a 2-chloro-butadiene polymer is mixed with a hydrosilicone comprising the reactive water-soluble binder of Example (27). , containing 300 parts of solids, are mixed by vigorous stirring with the addition of 0.2% of a defoamer in the form of a higher alcohol having 8 C-atoms. The adhesive thus obtained is then brushed in a thin layer onto a 2.alpha. wide sole rubber test specimen, which has been roughened briefly before and coated with plastic.

Just then place the specimen under a 250 watt red light lamp with the layer side parallel to the lamp and
Irradiate for minutes.

The test specimen had a temperature of 10'0 to 110 mm. Next, the test specimen with the adhesive layer in a still hot state was
Overlap and press with a pressure of 0.3 mPa for 20 minutes.
Compress for seconds.

(31) Example (3) is repeatedly illuminated with the exception of an aqueous colloidal elastomer dispersion, half of which is an aqueous dispersion of 2-chlorobutadiene polymer and the other half of which is an aqueous dispersion of 2-chlorobutadiene polymer. aqueous dispersion of Jen-methacrylic acid-copolymer)
They differ in that they consist of

(32) Example 01) is repeatedly illuminated. However, the difference is that the adhesive mixture is heated to 60 mm for 4 days before its use.

(35) Repeat example (32). However, in the dispersion, 2-
The ratio of chlorbutadiene homopolymer to copolymer is 75
The difference is that it is 725.

(34-35) Examples (32) and (53) are repeatedly illuminated.

However, the difference is that the solid content of the reactive binder is 10 yen of the total solid content.

(36) Example (35) is repeatedly illuminated. However, the difference is that the ratio of 2-chlorobutadiene homopolymer to copolymer in the dispersion is 25:75.

(37) Example (3) is repeatedly illuminated. However, if the aqueous dispersion is 70-
The difference is that it is made of an acrylate copolymer consisting of 20% of ethylhexyl acrylate), 20% of butyl acrylate, and 10% of acrylonitrile.

(38) Example (37) is repeatedly illuminated. However, the difference is that the solid content of the reactive binder is 10% of the total solid content.

(39) Repeat example (38). However, the aqueous acrylate dispersion used is 61 ethyl acrylate), 2
The difference is that it is a copolymer consisting of 2% octyl acrylate, 10% acrylonitrile and 7% acrylic acid.

(40) Repeat example (39). The difference, however, is that the adhesive mixture is heated to 60 υ for two days before its use.

All examples are carried out using the binders of Examples (28) and (29). In this case, adhesives of equally good properties are obtained.

(V) Adhesive test examples (30) to (40) for adhesives manufactured according to the above are stored at room temperature for 7 days and then tested for heat resistance strength. Furthermore, it was preheated to 70 mm on a heating shelf, and after reaching this temperature, one side was fixed to a clamp attached to the lid of the shelf.

300g of the other side of the adhesive was preheated to 70mm.
A weight with a weight of

Table 2 shows the heat resistance values for individual adhesive examples, comparing the adhesive strength values to conventional resinous water-based contact adhesives.

Table 2 30 40-50 20 31 40-50 40 52 50-60 140 33 50-60 280 54 70-80 420 55 90-I DO840 3670-80600 3740-5050 3850~ 60 120 39 60-70 260 40 70 -80 480 Table 3 shows the maximum initial stage of rubber/rubber-adhesives that can be achieved with poly-2-chloro-butadiene- or polyacrylate-dispersions and contact adhesives made of conventionally utilized resins. It shows the peel strength.

Table 5 Alkylphenol resin 20-30 Terpene phenol resin 50-40 Polyterpene resin 20-30 Colophonium resin 50-40 Coumaron/indene resin 30-40 Hydrocarbon resin
2O-30 (Vl) Discussion of the Results As can be seen from Tables 2 and 3, adhesives in which reactive binders were used according to the invention contained similar polymeric two-stomer dispersions or polyacrylate dispersions. It is significantly superior in terms of heat resistance and initial peel strength compared to adhesives using conventional resins.

Agent Hikaru Esaki Agent Mitsushi Ezaki

Claims (5)

[Claims] (1) (A) A group consisting of (a) a halogen-free polycarboxylic acid compound, (b) an alkali metal salt, an alkaline earth metal salt, a quaternary ammonium salt, an organic base, ammonia, or a combination thereof. salt-forming substances and at least one of the following compounds (cl) am
- group-containing polymer (C2) A combination of epoxide compounds, provided that components <a> to (C2) are present as such or at least partially chemically bonded, and do not contain a catalyst. fc is a water-soluble reactive binder containing (B) (B1) an unmodified or at least partially modified 000H group, and a sulfonic acid group (9) is a diistomer or (B2) modified with a combination thereof; acrylic copolymer or a combination of (B5)C1) and (B2), the proportion of binder (mu) being from 5 to 40% by weight based on the total solids content and the components (B) is characterized in that it is 60 to 95% by weight. Adhesive that can be diluted with water. (2) Component (t>), (b) and compound (C1)
Formula (I) based on at least one of and (C2)
6 or (I a) (I) (Ia) [wherein R1 is a polyester, a polymer, both of which each have an OH value of 20 to 300], and 100
a group of at least one OH group-containing polymer of the group of phenolic resins having an OH value of ~800, a group of an epoxide compound or a combination thereof; R2 is one 000H- in the ortho position to the ester bond; R5 means at least a dibasic carboxylic acid group having one 0OOH- group in the position ortho to the ester linkage, in which case R5 is
It may have the same meaning as 2. ], with the proviso that the above (I)
Alternatively, the anhydride group of (Ia) is at least partially 0O
The OH group, the ester group or a combination thereof may be substituted, and the 0OOH group may be at least partially substituted with an ester group, and in this case Free C! OOH group is component (b)
The adhesive according to claim 1, wherein the adhesive is present in the salt form in a proportion of 1 to 100%. (3) In addition to the reaction products of formula (r) and (Ia), (
The binder according to claim 3, which contains at least one unreacted substance of components a) to (c2). (4) Polycarboxylic acids C00 of the following formula group which, in addition to the reaction product (I) or (Ia), are not further bonded to the polymer-spanning condensation resin chain K or to the epoxide compound. Oor = 1-8 (W) (but in at least partially hydrolyzed state or as a salt) or a combination thereof, provided that it has the above formula (%) and 2 digits (CH2')m-(m=2~B
) or (5) The main proportion of component (B1) is unmodified or at least partially C! Synthesis of chlorbutadiene polymers modified with OOH groups and component CB2)
is mainly composed of acrylic copolymers), the R1 group in formula (I) or (Ia) is a branched polyester group based on at least one dicarboxylic acid, aliphatic diol and triol, and the group R2 or The free CtOOH groups of R2 and R5 are partially esterified with the polyhydric alcohol, and the remaining anhydride C00I'i groups are present in the form of quaternary ammonium salts. 5. The adhesive according to claim 2, wherein the epoxide compound (C2) is present in the form of an epoxidized fatty acid ester.