JPH059454B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a process for introducing phosphoric acid groups into polyester resins used as paint binders. The effect of phosphoric acid groups in paint binders is generally known from a large body of literature. On the one hand, the interaction between these groups and substrates, in particular metal substrates, and also pigments and extender pigments is emphasized, which makes these coatings particularly suitable in terms of their adhesive and resistance properties. Significantly improve. On the other hand, this phosphoric acid group is also an excellent curing catalyst for acid contact mechanisms. These aspects are gaining importance in connection with the contemporary demands for pigments with as low a level of toxic substances as possible, such as chromium-containing corrosion-resistant pigments, and for coatings with low energy consumption for crosslinking. The above effects are due partly to the acidic phosphate groups and partly to the corresponding phosphate ions. In this invention, the term "phosphate group" is defined as
It is understood to mean acidic reactions of phosphoric acid and salts of phosphoric acid and organic or inorganic bases. It does not include nonionic derivatives of phosphoric acid, such as esters. In practical terms, the question of the corrosion-inhibiting effect or curing properties of paints cannot be considered separately from the many other paint properties such as storage stability, application behavior, or the possibility of obtaining coatings with bright shine. Can not. The improvements obtained must also be clearly observable under changing conditions as a practical matter. This also means that, conversely,
Requires the concentration of phosphate groups to be raised above the minimum level determined by the binder type. For example, according to Austrian Patent Publication No. 356,782, a level of about 0.3 mol/Kg is required for typical high solids binders to obtain good water resistance on untreated steel. When phosphoric acids or their low-molecular-weight derivatives are added to colored paints, the amount of phosphoric acid groups is 0.3 mol/Kg.
Lower and lower concentrations result in many serious defects, such as reduced gloss and reduced processing properties of cured films. This addition is therefore only made to "etching primers" to enhance adhesion in the production of flat anti-corrosion coatings with small film thicknesses. The introduction of phosphate groups into paint binders or combinations thereof is described in a number of documents, for example German Patent Publication No. 2204844, British Patent Publication No. 1377854 and US Patent Publication No. 3415766 and 3474566.
It is stated in the issue. The methods used in them are not aimed at the above-mentioned goals, but in particular at the possibility of producing binders that give scratch-free films with pigments that shine brightly even at high phosphoric acid concentrations. It's not a vine. U.S. Patent Publication No. 4178319; No. 4178320;
Nos. 4,178,323 and 4,178,324 describe combinations of oligomeric acidic phosphate esters and epoxy group-containing polymers with a molar ratio of acidified epoxy groups of 1:1. Although the reaction between the two groups solves the problem, the content of free phosphate groups decreases significantly. In other words, such a combination will not solve the problem. According to Austrian Patent Publication No. 356 782, the above-mentioned problems can be avoided by introducing phosphoric acid into the binder by a special method. This method essentially aims to substantially reduce the content of free phosphorylated, non-chemically bound, small molecule phosphoric acid derivatives. According to this document, acidic derivatives of phosphoric acid are reacted with amine-aldehyde condensation products, and the condensates obtained are mixed or partially reacted with hydroxy group-containing components. This process creates a binder for thermoset-component paints which, with proper pigmentation, exhibit a bright shine and give a scratch-free film with good corrosion resistance.
This process is particularly suitable for the production of high solids type paints. When producing high molecular weight binders according to the method of Austrian Patent Publication No. 356 782, problems with compatibility arise, especially when the hydroxy compound is of high molecular weight. For this reason,
For many end uses such as stenciling and pasteurising paints with extreme processing properties for coating aluminum collapsible tubes, and solvent-release drying paints. The synthesis of binders with chemically bound phosphate groups is quite limited. The possibility of producing high-molecular polyester resins is disclosed in DE 1745791,
According to this, the esterification is carried out in a dilute solvent, if necessary under pressure, and the reaction can proceed beyond the theoretical gel point without producing unwanted products. Surprisingly, it has been found that by such a method, ie, polyesterification in dilute solution, it is possible to quantitatively introduce phosphoric acid groups into polyester resins. In this way it is possible to produce paint binders with a high content of phosphoric acid groups, which exhibit a bright shine with good coloring and are free from defects, exhibiting high corrosion resistance and good mechanical properties. Can produce coatings. The present invention involves an esterification reaction in a method for producing a polyester resin containing a phosphoric acid group by reacting a raw material polyester-forming component with a component containing a phosphoric acid group and bonding phosphoric acid or a derivative thereof to a polyester resin. carried out in a solution of one or more diluents inert to the raw materials,
The solution contains 40 to 80% by weight of the raw materials and the esterification reaction is continued until substantially all of the phosphoric acid or derivative thereof is bound to the polyester resin, and the intrinsic viscosity is 3.0 to 25.0 ml/ml/20° C. in DMF. g
The acid content in the reaction product ranges from 0.2 to 1.5 mol phosphorus per kg of reaction product in the form of phosphoric acid and/or acidic phosphoric esters of monohydric or polyhydric alcohols. Yes, and the molar parts of phosphorus in the form of components containing phosphoric acid groups extracted with water are in the reaction product.
It relates to a process characterized in that the amount does not exceed 0.2 mol/kg, and that, after the end of the esterification reaction, free phosphoric acid groups are blocked by salt formation with amines. Furthermore, within the scope of the claims, polyesters produced by the method of the invention with a specific phosphoric acid proportion and a specific intrinsic viscosity range are suitable for specific applications. This preferred range is for typical spray coating paints: 0.2 to 0.8 moles of phosphorus per kg of final product, intrinsic viscosity range of 3.0 to 5.0 ml/g (DMF, 20°C). For sterilization-resistant flexible spray or roller coating paints (e.g. for collapsible tubes): 0.3 to 1.5 moles of phosphorus and at least 6.0, preferably 8.0 to 1.5 moles of phosphorus per kg of final product.
Intrinsic viscosity of 25.0ml/g (DMF, 20°C). Here, "polyester" refers not only to polyesters themselves, but also to modified products such as alkyd resins, polymers of ethylenically unsaturated compounds, and polyesters containing polyether or urethane group moieties. I understand that it includes The raw materials that are compatible with these products are known to experts and are available in many manuals, e.g.
Winnacker and Ku¨chler's “Chemische Technology”
C.Hanser, Munich, 1972 (C.Hanser, Munich, 1972) or Ullmanns' Encyklopadie der Technischen Chemie, 4th edition, Volume 15, Hemy GmbH. Wine. It is described in Edition Chemie GanbH. Weinheim 1978. For the introduction of phosphate groups, polyphosphoric acid, e.g.
Preference is given to using those of the general formula H _o+2 P _o O _3o+1 having three or more phosphorous atoms and P-O-P bonds in the molecule. The introduced polyphosphoric acid has an anion represented by the general formula (P _o O _3o+1 ) ^(n+2)- ,
Since polyphosphoric acid is detected as an anion in the analytical method and the structure of polyphosphoric acid is generally complex, polyphosphoric acid is used hereafter for convenience in indicating the purity etc. of polyphosphoric acid used in this specification. Let the acid be P ₂ O ₅ or P ₄ O ₁₀ . These acids are usually technical mixtures with a P ₄ O ₁₀ content of about 80-90%. They are available in two preferred varieties: those with about 76% P ₂ O ₅ and those with about 84% P 2 O 5 . When we refer to phosphoric acid in this application,
It is a general term for acids produced by hydration of diphosphorus pentoxide (P ₂ O ₅ ), and includes the above-mentioned polyphosphoric acid. In addition to these, available mixtures of mono- and diesters obtained by reaction of phosphoric acid (84% P ₂ O ₅ ) with monohydric or polyhydric alcohols can be used.
The ester mixtures usually contain free phosphoric acid moieties. This reaction mixture follows the general principles known to experts for the production of phosphoric acid-free polyesters, such as those of H.G.
ELIAS) “Makromolekiile” [Hu¨thig and Wepf,
Basel-Heidelberg
Heidelberg (1971). To calculate the proportions of this reaction mixture, each mole of phosphorus in the phosphoric acid used is replaced by one mole of dicarboxylic acid, depending on its functionality; One can safely assume that there are additional moles of acid groups. Suitable inert solvents are those which exhibit substantially no chemical reaction under the conditions of the process of the invention, and are preferably those which are immiscible with water or which are used to produce polyesters by heat treatment of the solvent. Materials that are only slightly miscible with water, such as toluene, xylene, or the like, or whose boiling point is between about 150 and
There are solvents whose temperature is much higher than the minimum temperature of 200℃. In addition to the aromatic solvents listed above, 130 and 220
Available aromatic or aliphatic hydrocarbon solvents or mixtures thereof having a boiling point between .degree. Examples of other inert diluents are ketones or chlorinated hydrocarbons. The diluent must be in homogeneous admixture with the reaction mixture at least at the reaction temperature and up to the end of the reaction. It is not necessary that the polyester resins be soluble in the diluent at room temperature. The process of the invention can be carried out in conventional reactors used in the production of synthetic resins. 〔for example,
As described in "Chemical Technology" by B. K. Winnaker and El Küchler, Tswe Hansen Publishing, Miluncheng 1972]. Even when relatively low-boiling diluents are used, the time to complete the reaction is comparable to that for the preparation of unmodified polyesters due to the strong catalytic action of the phosphoric acid groups. Special equipment, such as that disclosed in DE 17 45 791, for example, uses high temperatures or high pressures to accelerate this solution reaction to the range commonly used for undiluted reaction formulations by reaction. need not be used in the process of the invention. The chosen diluent is added to the reaction mixture at the beginning of the reaction or at a suitable time after the beginning, eg, after the raw materials have formed a clear melt. A stepwise addition is also possible, which makes it possible to shorten the reaction time and reduce the high temperatures applied at the beginning of the reaction. The amount of diluent used in the process of the invention is
It is selected so that the solid content during the reaction is within the range of 40 to 80%. In order to achieve the advantageous properties of the process of the invention, it is necessary to dilute the reaction mixture to such an extent that substantially all of the phosphate compound is bound without gel formation, especially in the final stage of the esterification. . The reaction mixture must have a low viscosity corresponding to the reaction temperature. To narrow the molecular weight distribution, it is necessary to further reduce the solids content. Fortunately, this reaction is monitored by the intrinsic viscosity [η] and acid number. An intrinsic viscosity [η] of 3 to 25 ml/g, measured in dimethylformamide, is targeted. The acid value of these products ranges from 10 to 80 mg.
A range of KOH/g is good. The properties of low molecular weight phosphoric esters or of free phosphoric acid serve as a basis for evaluating the conversion rate of the introduction of acidic phosphoric esters into polyesters. That is, their presence in polyester-aminoplast combinations containing titanium oxide pigments, even in small amounts, causes a decrease in brightness. In this way, by testing samples with various degrees of condensation in accordance with reality, the results of the introduction of phosphoric acid esters can be evaluated. At the end of the reaction, additional solvents may be added to the batch if necessary. These solvents must, of course, meet the criteria set forth above for diluents. If the entrainer has active hydrogen atoms or ester groups, the catalytic action of the free phosphate ester groups can cause polyester chain splitting even at ambient temperatures, resulting in a decrease in molecular weight. If reduction is not desired, the free phosphate groups must be at least partially converted to their salts with suitable bases such as amines before addition of the active solvents. This treatment can improve storage stability, for example when combined with amine-formaldehyde resins. The type and amount of blocking agent will be selected by the skilled artisan with regard to desired reactivity and storage stability. In this regard, the binder according to the invention, in combination with aminoplasts, only slightly reduces its reactivity even when low-volatile amines such as diethanolamine or 2-amino-2-ethyl-1,3-propanediol are added. It is noteworthy that only one person loses anything. The binder solutions produced in accordance with the present invention are applied to polyester resins, optionally with other resin components such as aminoplasts, and pigments, fillers, additives and solvents. It is commonly processed into paints. Compared to coatings of similar products without phosphate groups, the water resistance and corrosion protection are significantly increased. In combination with amine resins, low curing temperatures can be applied even if they are fully etherified. Selection of the appropriate ranges of the phosphorus content and intrinsic viscosity of this polyester within the specified ranges allows the formulation of paints that are particularly suitable for spray coating. Such paints exhibit the excellent properties already mentioned even at curing temperatures as low as about 100°C. In particular, the phosphorus content is between 0.2 and 0.8 mol per kg of polyester, which phosphorus is used according to the process of the invention in the form of phosphoric acid and/or acidic phosphate esters with monohydric or dihydric alcohols. Yes, the intrinsic viscosity is 0.2 or more.
Good results are shown in the range of 0.8 ml/g (DMF, 20°C). On the other hand, the process of the present invention is particularly suited to higher molecular weight products such as those required for severe processing. polyester
Phosphorus content of 0.3 to 1.5 mol per kg and 6
Products with an intrinsic viscosity exceeding ml/g (DMF, 20°C), such as deep-drawn and sterilizable enamels with very short curing times at curing temperatures of 120-140°C or conventional curing temperatures. The paints for collapsible aluminum tubes provide the desired properties for process enamels and have significant "crush resistance", i.e., good adhesion and processability in rapid deformation at low temperatures.
In this regard, the molecular weight of the products of the invention is:
For example, Punishu Patent Application No. 0025089 and No.
No. 0025478, German Patent Publication No. 2571791 and No.
2571791 and 2571792 and German Patent Publication Nos. 1807776, 2126048 and 2211059. This advantage greatly simplifies the handling of the binder solution and the production of paints, and at the same time allows for increased solids content during application. With proper formulation, polymeric binders made in accordance with the present invention also yield hard and flexible films upon drying by solvent evaporation at room temperature. In combination with amine resins additional chemical crosslinking occurs. Unlike conventional acid-curing paints, the level of amine resin can be reduced to low amounts that prevent coating embrittlement upon aging. The resulting coatings exhibit good water resistance and good corrosion protection. The following examples illustrate the invention without limiting its scope. Parts or percentages are by weight unless otherwise specified. All intrinsic viscosity measurements are made with dimethylformamide (DMF)
The temperature was 20°C. Test methods described in the examples Pendulum hardness: Ko¨nig DIN53157 Haze: Gonioreflectometer GR-
COMP - Measured with Vianova. β = −logI _S I _R I _S Diffused light intensity at 224° I _R Reflected light intensity at 20° relative to glass standard (n = 1.567); illumination orifice = measurement orifice = 0.6° White color Values above 2.3 for enamel were recorded as radiant by subjective standards. Indentation hardness: ERICHSEN DIN53156 Impact resistance: GARDNER standard (1
Measured in inches x 1 pound = 0.113 joules). Chip resistance A: The coated surface was placed at a 45° angle. 1000 g of nuts passed through a 38 mm diameter tube from a height of 5 m (type HM6-2980.100.
656) was dropped. After removing the detached particles of paint, the weight loss was recorded. 20
A loss of less than mg was recorded as very good. Chip resistance B: 500 g each of grit (4-5 mm) was fired at an angle of 45° from a distance of 20 cm onto the coated substrate. (Air pressure: 2 bar) The weight loss calculated per 100 cm ² of impact area was recorded. Values less than 25 mg were recorded as very good. Mandrel test: Tapered mandrel, minimum radius 6mm. Shatter resistance: After storage for 1 hour at -20°C, the coated panels were shattered with a single impact, warmed to room temperature and then stretched again. Rating: 1 No damage to coating 5 Coating substantially peeled Deep Draw Resistance: Round cups were produced on a Frichsen Paint Tester, Model 225. Rating: 1 No cracks 5 Strong peeling resistance (Pasteurising resistance): The above round cup was placed under a pressure of 1.4 bar (121
℃) for 1 hour. Rating: 1 No change in coating 5 Strong peeling and/or loss of gloss () Polyester resins used in spray paints ([η] = 3-5 ml/g; P = 0.2-
0.8) Analysis of the amount of phosphoric acid bound to the final product The total amount of phosphoric acid or their derivatives bound is defined as the molar parts of phosphorus per kg of the reaction product as components containing phosphate groups that are not extracted by water. Ru. The analysis method is carried out as follows. Dilute the resin solution with methyl isobutyl ketone,
40% solids by weight and extracted 3 times with water at 40°C. The extracted phosphoric acid component is measured using a conventional analytical method. The amount of phosphoric acid extracted with water is the unbound amount, and the difference between the introduced amount of phosphoric acid and the obtained unbound amount is the bound amount of phosphoric acid. Therefore, the mole parts of phosphorus per kg of reaction product (mol/Kg) is determined. Examples 1-4 In a typical resin reactor as described, for example, in Kerr Winnaker, El Küchler, "Chemical Technology", Tse-Hansel Publishers, Myung Heng, 1972, Vol. 5, p. 402. , the polyols and carboxylic acids shown in Table 1 are heated, and the helinic acid compound is added to the melt. Thirty minutes after a clear melt has formed, the batch is diluted to a solids content of 60%. The reaction was then carried out to final value by the azeotropic solvent method. Explanation of abbreviations in Table 1 PSA Phthalic anhydride THPSA Tetrahydrophthalic anhydride AS Adipic acid NPG Neopentyl glycol CON50 Industrial linoleic acid (approximately 50% conjugated fatty acids) TMP Trimethylolpropane PP84 Phosphoric acid (84% P ₂ O ₅ ) AKW2 aromatic hydrocarbon (boiling point range 162-176℃,
Kauri-butanol value approx. 90) DIBUK diisobutyl ketone

【table】

[Table] Paint performance test (1) of binders produced according to Examples 1-4.
mill) to prepare a paint with the following composition. 100 parts titanium dioxide (rutin) 85 parts binder of Example 1 (as resin solids) 15 parts hexamethoxymethylmelamine (HMMM) 0.5 parts available paint additive (silicone resin base) This paint was mixed with EGLAC. BUAC (non-volatile content
67%, 25 min/130 °C) to a viscosity of 20 seconds (DIN53 211/20 °C) and degreased onto the steel by an air pressure spray gun.
Apply to form a dry film with a thickness of 35 to 40 μm. Table 2 shows the results for films cured for 25 minutes at the temperatures indicated in the table. In each case, the film exhibited a bright glow.

[Table] When the binder of Example 2 was similarly tested, the same results were obtained within the error range. (2) Tests were conducted on fillers with the following formulations. 50 parts titanium dioxide 50 parts precipitated barium sulfate (blank fixation)
blanc fixe) 1.5 parts highly dispersed diatomaceous earth 0.3 parts carbon black 85 parts binder of Example 3 (resin solids) 1.5 parts HMMM 0.5 parts paint additive (silicone resin base) 21 seconds viscosity (DIN53 The non-volatile material at 211/20°C was approximately 63%. This paint was spray coated to form a film with a thickness of 35 to 40 μm.
Baking temperatures (25 minutes baking) are shown in Table 3.

[Table] Degreased steel was used as a basis for pendulum hardness, dentability and impact tests. Chip resistance was tested on a coating system consisting of a cathodically deposited primer, a filler in the binder of the present invention, and a commercially available automotive finish based on a crosslinkable acrylic binder. (3) A variety of paints were made using the binder of Example 4. Paint 1: Bright gloss red finish Paint 2: Bright gloss white finish Paint 3: Automotive filler The paint compositions and test results are shown in Tables 4 and 5.

【table】

【table】

[Table] () Sterilized polyester resins for highly flexible baking paints ([η]) = 6ml/g or more;
P = 0.3-1.5 mol/Kg) Example 5 In the reactor described in Example 1, 62 parts of isophthalic acid, 20 parts of phthalic anhydride, 30 parts of neopentyl glycol, 28 parts of hexanediol-
1, 3, 18 parts of trimethylolpropane and 12
200 parts of available phosphoric acid ( _P2O5 content ₈₄ %)
℃, and at this time, the water vapor temperature in front of the receiver was made not to exceed 110℃. Thirty minutes after obtaining a clear melt, the batch was evaporated to 60% with a hydrocarbon solvent with a high aromatic content (boiling range 162-172°C, kauributanol number ASTMD-1133 approximately 90).
Diluted to solid content. This reaction with azeotropic entrainment is carried out at 58mgKOH/
The reaction was carried out at 170° C. until an acid value of 1.5 g and an intrinsic viscosity [η] of 12 ml/g were reached. After cooling to 110°C, 9 parts of dimethylethanolamine were added,
The batch was also diluted to 55% solids with monoethylene glycol monobutyl ether. The product contained 0.92 mol/Kg phosphoric acid. The molar parts of phosphorus extracted with water per kg of reaction product was 0.17 mol/kg. Example 6-14 According to Table 6, phosphoric acid-modified polyesters were produced in the same manner as in Example 5. The following abbreviations were used in the examples and test results. PSA Phthalic anhydride THPSA Tetrahydrophthalic anhydride IPS Isophthalic acid AS Adipic acid NPG Neopentyl glycol EXD Hexanediol-1,6 TMP Trimethylolpropane HPN Hydroxypipartic acid Neopentyl glycol ester PP84 Phosphoric acid (84% P ₂ O ₅ ) AKWI aromatic hydrocarbons (boiling range 186−205
°C, Kauri-butanol number 92.5) AKW2 aromatic hydrocarbon (boiling point range 162-176
℃, Kauributanol value approx. 90) DMEA dimethylethanolamine DOLA diethanolamine DEDEE diethylene glycol diethyl ether DEDME diethylene glycol dimethyl ether BUGL monoethylene glycol monobutyl ether BUDIGL diethylene glycol monobutyl ether BUAC butyl acetate EGL monoethylene glycol monoethyl ether EGLAC monoethylene glycol monoethyl ether acetate

【table】

[Table] Example 15 Example 15 relates to the production of an acrylic modified alkyd resin containing phosphoric acid. In a common resin reactor, 100 parts of industrial isomerized linseed oil fatty acids, containing about 50% conjugated linoleic aliphatic;
50 parts of technical linoleic acid, 47 parts of glycerol and 30 parts of trimethylolpropane were heated to 160°C. Then 95 parts of phthalic anhydride and a mixture of 6 parts of phosphoric acid (84% _P2O5 ) and 6 parts _of ethanol were added. temperature within 90 minutes
Raise the temperature to 180℃ and reduce this temperature by 70% with AKW1.
Esterification was carried out using an azeotropic entrainer. The esterification reaction was stopped when an acid value of 17.0 ml/g and an intrinsic viscosity of 10.1 ml/g (chloroform, 20° C.) were reached. 107 parts of this 70% phosphoric acid modified alkyd resin and
58 parts of AKW1 were heated to 90°C. Then 19 parts methyl methacrylate, 6 parts styrene, 10 parts Shellsol AB and 2.4 parts dibenzoyl peroxide powder, active ingredient 50
%: The mixture desensitized with plasticizers was added continuously over 90 minutes. Three hours after the addition was complete, 1 part dibenzoyl peroxide, 50%, was added. After another 4 hours the reaction was complete. reaction products
The molar parts of phosphorus extracted with water per kg was 0.06 mol/Kg. Evaluation of paints (1) Manufacturing and testing of paints (1.1) Paints a-e; Comparative paints Va,
Vb and Vc (paints for collapsible tubes) Known methods (e.g. use of 3-roll mill)
Accordingly, the following compositions were manufactured from the resin of this example. 120 parts titanium dioxide (rutile) 90 parts resin (solids) 10 parts HMMM, 100%, or in butanol,
Available melamine resin partially etherified with butanol, 60% (BME, solids content) in butanol. 0.5 part of p-toluenesulfonic acid was added to comparative paint Va, and 3 parts of an equimolar mixture of phosphoric acid mono and dibutyl esters were added to comparative paint Vb. Comparative paint Vc does not contain any additives. These paints were diluted to 1.5-2 Pa.s with a mixed solvent (AKW1/BUGL, 2:1) and applied to aluminum collapsible tubes using a tube coater. These were pre-dried at 90°C for 4 minutes, printed and cured at 150°C for 4 minutes (the thickness of the dried film was 10 to 15 μm).

[Table] Printability was good except for (Vb). (1.2) Paint (f) (industrial baked enamels) 100 parts titanium dioxide (rutile), 91 parts Example
Polyester (solid content) in 13 and 9 parts
Manufacture paint from HMMM, EGLAC and
Viscosity of 22 seconds in 1:1 mixture with BUAC (DIN53
211/20°C). The paint was spray applied onto cleaned steel and cured at 120°C, 140°C and 160°C for 30 minutes each.

[Table] (1.3) Paints (g) and (h); Comparative paints (Vd) and (Ve) (roller coating paint) 100 parts titanium dioxide (rutile), 60 parts resin (solid content), 20 parts (solids) of available benzoguanamine-formaldehyde resin (etherified with butanol; 70% in butanol), 10 parts of epoxy resin (epoxy equivalent weight 180-192) and 86% vinyl chloride and 14% vinyl acetate. or each of the available copolymers of 83% vinyl chloride, 16% vinyl acetate and 1% maleic acid.
Paint was manufactured from the The comparative paint additionally contains 1% p-toluenesulfonic acid. A 1:1 mixture of EGL and BUDIGL produces this paint at a viscosity of 10 to 120 seconds (DIN53
The solution was diluted to 211/20°C) and roller coated onto a tinned steel plate. Curing: 15 minutes/140°C Dry film thickness: 13-17 μm A brightly shining film with a haze (β) exceeding 2.3 was obtained. Other properties are shown in Table 9.

[Table] (1.4) Paint (i): Automotive filler 50 parts titanium dioxide (rutile), 50 parts barite (precipitated), 0.2 parts carbon black, 90 parts (solid content) Polyester in Example 7, 10 parts
A paint was prepared from an antisettling agent based on HMMM, 2 parts DOLA and 0.6 parts montmorillonite. This paint was prepared with a 1:1 mixture of EGLAC/BOAC to a viscosity of 22 seconds (DIN53
211/20°C), spray painted onto cleaned steel panels and cured at 120°C, 140°C and 160°C for 30 minutes.

Table: Evaluation of the three-layer system: The paint was spray applied onto a phosphorous suboxide steel panel with an ED-primer and cured at 140°C. A commercially available automotive finish (curing temperature: 135°C) was then applied. For comparison, a commercially available automotive sealer based on a 7:1:2 combination of DCO alkyd, epoxy resin, and urea resin was similarly used.

[Table] (1.5) Paints (i) and (K): Urea resin paint A colored paste with the following composition was prepared. (i) (K) Titanium dioxide (rutile) 30 60 Barite (precipitated) 030 −− Carbon black 0.2 −− Binder (solid content) of Example 10 70 70 In a 1:1 mixture of EGALO and BUAC This paste was diluted to approximately 50% solids. Before painting
Add 30 parts of available urea-formaldehyde resin to each paste and adjust the viscosity (DIN53
211/20℃) was adjusted to 25 seconds. This paint was cured at room temperature.

[Table] (1.6) Paint (1): Folding tube enamel without amine resin 120 parts TiO ₂ (rutile), 100 parts resin in Example 15 (solids) and 0.05 part cobalt (cobalt octoate) paint was produced from This paint was diluted with AKW1 to a viscosity of approximately 2 Pa.s and applied to a collapsible aluminum tube. After 6 minutes of pre-drying at 80°C, the tubes were printed and cured at 160°C for 6 minutes. This coating had a pendulum hardness of 36 seconds, a haze of 2.45 and a crush resistance of 1.

Claims (1)

[Scope of Claims] 1. A method for producing a polyester resin containing a phosphoric acid group by reacting a polyester-forming component as a raw material with a component containing a phosphoric acid group and bonding phosphoric acid or a derivative thereof to the polyester resin, The esterification reaction is carried out in a solution of one or more diluents inert to the raw materials, the solution contains 40 to 80% by weight of the raw materials, and the esterification reaction is carried out in a solution of one or more diluents that are inert to the raw materials, and the solution contains 40 to 80% by weight of the raw materials. until substantially all of the polyester resin is bonded,
Forms a reaction product with an intrinsic viscosity of 3.0 to 25.0 ml/g at 20°C in DMF, but the acid content in the reaction product is in the form of phosphoric acid and/or acidic phosphate esters of monohydric or polyhydric alcohols. from 0.2 to 1.5 mol phosphorus per kg of reaction product, and the molar part of phosphorus in the form of components containing said phosphoric acid groups extracted with water does not exceed 0.2 mol per kg of reaction product. , and further characterized in that, after completion of the esterification reaction, free phosphoric acid groups are blocked by salt formation with amines. 2. Process according to claim 1, characterized in that the inert diluent is an aromatic or aliphatic hydrocarbon solvent with a boiling point between 110 and 220°C. 3. The method according to claims 1 and 2, characterized in that the diluent is added stepwise during the reaction. 4. The method according to any one of claims 1 to 3, wherein the amine is an alkanolamine. 5 The reaction product is 0.2 to 1 kg per kg of reaction product.
From claim 1, which contains 0.8 mol of phosphorus, has an intrinsic viscosity (in DMF, 20°C) of 3.0 to 5.0 ml/g, and is suitable as a binder component of a baking paint for spraying. The method described in any of paragraphs up to 4. 6 The reaction product is 0.3 to 1 kg per kg of reaction product.
Contains 1.5 moles of phosphorus and has an intrinsic viscosity of at least 6.0, preferably between 8.0 and 25.0 ml/g (in DMF at 20°C)
5. A method according to claim 1, characterized in that it is suitable for sterilization-resistant flexible baking paints, in particular for collapsible tubes and the like.