FR2666822A1 - Composition of the type containing phosphoric acid and article treated with this composition - Google Patents

Abstract

Substantially nonaqueous phosphating composition of the type containing phosphoric acid. The article to be treated is placed in a reactor 2 comprising a solvent degreasing zone A, a treatment zone B containing the composition and heated by a heating device 4 with regulator device 5, and a dyeing zone C provided with a water-cooled condenser 6, the reactor being insulated with glass wool 3. The article is degreased in the zone A, treated in the zone B and then washed with solvent and dried in the zone C.

Description

The present invention relates to an acid type composition.

  phosphoric and an object treated with it and more particularly such a composition in a substantially non-medium

  water and an object treated with it.

  As a phosphating composition containing a chlorinated hydrocarbon medium, for example, Japanese Patent Publication No. 57-49111 describes a composition in which a metal surface is phosphated to improve the adhesion and moisture resistance properties of coatings so as to form a substantially insoluble iron phosphate film

  in water however, while a film of iron phosphate pre-

  has satisfactory properties in certain fields for the pretreatment of paints, it has the disadvantage that its corrosion resistance is lower than that of a zinc phosphate film formed with a composition containing an aqueous medium used in the automotive industry and the home appliance industry As a phosphoric acid composition containing an aqueous medium to form a zinc phosphate film, for example, Japanese Patent Application Laid-Open No. 52-107,244 describes an agent chemical treatment to form a zinc phosphate film comprising nitric acid and chlorate ions in an aqueous solution of zinc acid phosphate containing zinc ions and phosphate ions such that the ratio of ions

  nitrate to chlorate ions (N 03 / CLO) or 0.2 to 4.5 and the pro-

  portion of phosphate ions, chlorate ions and nitrate ions

  (P 043 / Cl O 3 / N 03) or 1: 0.08 0.53: 0.08 0.53.

  However, to form a zinc phosphate film using a treatment agent containing an aqueous medium, it is

  necessary to successively implement a step of degreasing-

  wise, a step of rinsing with water, a step of rinsing with pure water, a step of surface adjustment, a step of chemical treatment, a step of rinsing with water, a step of rinsing with pure water and a drying step, in this order, these steps being themselves complicated In addition, since a large amount of water is required in these steps, the above method has the disadvantage that the installations for treating waste water increases the cost price Or else, in the chemical treatment agent mentioned above, the nitrate ion is used as a catalyst and since the p H decreases when the concentration of nitric acid increases, the film cannot not to be

practically trained.

  Meanwhile, a composition is already known for forming a film of zinc phosphate without water as a medium. A Japanese patent publication No. 42-14051 has proposed a

  phosphating composition comprising an organic solvent oxy-

  gene, a compound of zinc and phosphoric acid However,

  in the phosphating composition with an organic solvent oxy-

  zinc is barely dissolved so that it forms

  sludge, etc. in the film obtained, making industrialization impossible

sation in practical application.

  An object of the present invention is to provide a

  composition of the phosphoric acid type to a sensitive medium

  non-aqueous and an object treated with it having an excel-

  slow corrosion resistance and excellent adhesion, all

  allowing the formation of a durable film of zinc phosphate.

  Another object of the present invention is to provide

  a composition of the phosphoric acid type to a medium sensitive to

  clearly nonaqueous which is capable of easily forming into a

  short-term zinc phosphate film on an object to be treated.

  According to the present invention, a composition of the phosphoric acid type is proposed in a substantially non-aqueous medium to form a film of the phosphate type on a metal, comprising as essential components:

  (a) 100 parts by weight of a first mixed solvent

  holding 100 parts by weight of a polar organic solvent having a boiling point of not less than 0 C / 760 mm Hg (1013 mmbar) and not more than 100 parts by weight of water; (b) 0.0001 to 7 parts by weight of phosphoric acid; (c) 0.01 to 5 parts by weight of zinc ions; and

  (d) 0.01 to 5 parts by weight of a solubilizing agent.

  According to the invention, a composition of the phosphoric acid type with a substantially nonaqueous medium is also proposed for forming a phosphate type film on a metal, comprising as essential components:

  (e) 100 parts by weight of a second mixed solvent containing

  containing 100 parts by weight of a non-polar organic solvent and a boiling point of not less than 0 C / 760 mm Hg (1013 mbar), not less than 0.5 parts by weight of a solubilizing solvent and not more than the limit quantity of water forming a homogeneous phase; (f) 0.0001 to 7 parts by weight of phosphoric acid; Cg) 0.001 to 3.5 parts by weight of zinc ions; and

  (h) 0.01 to 5 parts by weight of a solubilizing agent.

  According to the invention, there is further provided an object treated with each of the compositions mentioned above and comprising a film

formed by each composition.

  The single attached figure schematically represents a glass apparatus for degreasing and rinsing a solvent used

  in Examples and Comparative Examples.

  The present invention is explained in more detail below. The composition of the phosphoric acid type of the present invention is intended to modify the surfaces of various metallic objects such as various irons, steels, galvanized iron,

  alloys of iron, aluminum or magnesium or other materials

metallic rials.

  A first composition of the phosphoric acid type according to the invention (hereinafter called "the first composition") contains as essential components (a) a first specific mixed solvent, (b) phosphoric acid, (c) zinc ions and (d)

  a solubilizing agent in the respective specified amounts.

  The first mixed solvent (a) in the first compound

  tion contains 100 parts by weight of a polar organic solvent having a boiling point of not less than O C / 760 mm Hg and not

  more than 100 parts by weight of water Organic solvents for

  laires having a boiling point of not less than 0 C / 760 mm Hg are solvents which are substantially soluble in water and are classified as polar protonic organic solvents and organic solvents

  non-protonic polar organic polar solvents proto-

  Niques can include, for example, alcohols up to C 4 such as methanol, ethanol, isopropanol, 2-butoxyethanol, n-propanol, n-butanol, sec-butanol, t-butanol or trifluoroethanol. Non-proton polar organic solvents can include ketones such as acetone, methyl ethyl ketone or diethyl ketone; the

  polyalcohol esters up to C 10 such as diethyl monoacetal

  leneglycol, glycerin monoacetal, glycerin diacetal, mono-

  glycerin butyrate, ethylene carbonate, propy carbonate

  lene, ethylene glycol monoformate, ethylene glycol diformate, ethylene glycol monoacetate or ethylene glycol diacetate; phosphates such as trimethyl phosphate; ethers of polyalcohols up to C 10 such as glycol ethers, for example

  dimethoxyethane, diethoxyethane, 2-methoxyethanol or 2-ethoxyetha-

  nol, diethylene glycol ethers, for example monomethyl ether

  diethylene glycol, diethylene glycol dimethyl ether

  or diethylene glycol monoethyl ether, glycerol ethers

  rine, for example methyl glycerin ether, trimethyl ether

  glycerin liquor or glycerin dimethyl ether, ethers

  of propylene glycol, for example 1-methoxy-2-propanol or 1-ethoxy-2-

  propanol; monoethers of monoesters of polyalcohols up to C 10, such as ethylene glycol monoethyl ether acetate or ethylene glycol monomethyl ether acetate; cyclic ethers such as tetrahydrofuran or dioxane; nitrogen compounds such as acetonitrile or propionitrile; and diacetone alcohol Among these, methanol, ethanol, isopropanol and n-propanol are particularly preferred. Organic solvents

  fleeces mentioned above can be used alone or in combination

  The water in the first solvent mixture acts as an accelerator.

  film formation and is in the form of water of crystallization The proportion of water is not more than 100 parts by weight, preferably 30 to 70 parts by weight per 100 parts by weight of the polar organic solvent Si the proportion exceeds 100 parts by weight, the solubility of the film increases by

  so that you don't get a substantially uniform film.

  The phosphoric acid (b) used in the first compound

  sition of the invention is not particularly limited, if it is a phosphorus oxacid Phosphoric acid can include for example orthophosphoric acid, pyrophosphoric acid and phosphorus pentoxide Orthophosphoric acid is especially preferred La mixing proportion of phosphoric acid is from 0.0001 to 7 parts by weight, preferably 0.001 to 2 parts by weight and better still 0.03 to 0.5 parts by weight per 100 parts by weight of the first solvent mixture Si the mixing proportion of phosphoric acid is less than 0.0001 parts by weight, it may be difficult to operate stably and continuously and provide the system to form a desired phosphate type film, while if the proportion of mixture exceeds 7 parts by weight, the phosphoric acid may not be dissolved homogeneously in the first solvent mixture and become cloudy or

  precipitates can separate by crystallization.

  The zinc ions (c) of the first composition of the invention

  tion are a component formed in the film The zinc ions (c) can be added to the composition in the form of an acid salt such as an inorganic acid salt such as zinc oxide, zinc carbonate, nitrate zinc, zinc chloride, zinc sulfate, zinc borate or zinc phosphate; or an organic acid salt such as zinc formate, zinc acetate, zinc citrate, zinc tartrate, zinc oxalate or zinc trichloroacetate Zinc oxide,

  zinc carbonate, zinc nitrate, zinc borate, phos-

  zinc lime and zinc citrate are especially preferred A portion of the zinc ions can be replaced by nickel ions, calcium ions, manganese ions, sodium ions, magnesium ions, copper ions or cobalt ions and so immediately The proportion of mixture of zinc ions in the composition is 0.01 to 5 parts by weight, preferably 0.01 to 2.0 parts by weight per 100 parts by weight of the first solvent mixture If the proportion of mixture of zinc ions is less than 0.01 part by weight, the desired film is not obtained, while at more than 5

  parts by weight, an excess of solubilizing agent attacks so strongly-

  metal that a practically uniform film is not obtained.

  The mixing proportions of the respective ions replacing a portion of the zinc ions range up to 2.5 parts by weight for the nickel ions, up to 2.5 parts by weight for the manganese ions, up to 2.0 parts in weight for calcium ions, up to 3.0 parts by weight for sodium ions, up to 2.0 parts by weight for magnesium ions, up to 2.0 parts by weight for copper ions and up to at 2.0 parts by weight for the cobalt ions,

respectively.

  The solubilizing agent (d) used in the first compound

  sition of the invention is a component which has the role of simultaneously dissolving both zinc and phosphoric acid in the solvent in the composition as well as a role of promoter

  to attack the metal surface to dissolve metal ions-

  lics such as iron ions (Fe 2 +) or zinc ions (Zn) 2 + so as to form a crystalline film of the zinc phosphate type on

  the metal surface The solubilizing agent may contain a halo

  hydrogen genide such as hydrogen fluoride or hydrogen chloride; an inorganic acid such as nitric acid, chloric acid, sulfuric acid, nitrous acid or chloric acid; and

  organic acids such as trichloroacetic acid, trifluoro-

  acetic or picric or nitroaniline They can be used alone or in combinations The solubilizing agent can be used in

  amount of more than 2 moles per one mole of zinc ions in the com-

  position if the solubilizing agent is a monoacid If the solubilizing agent

  bilisant is a diacid, it can be used in an amount of more than one mole Therefore, for example if we add zinc nitrate, zinc chloride and so on as a source of zinc ions mentioned above , we can add a smaller amount of

  the solubilizing agent The proportion of mixture of the solubilizing agent

  sant in the first composition is from 0.01 to 5 parts by weight, preferably from 0.02 to 3 parts by weight per 100 parts by weight of the first solvent mixture If the proportion of mixture is less than 0.01 part by by weight, the solubilizing agent is not dissolved when the zinc is combined with phosphoric acid, while if the proportion of mixture is more than 5 parts, the

  p H of the system becomes much too low and the metal is too strong-

ment attacked.

  To prepare the first composition of the invention, the above components are mixed and stirred in a homogeneous manner.

  room temperature using a known mixer.

  A second composition of the phosphoric acid type of the invention (hereinafter called "the second composition") contains as essential components (e) a second specific mixed solvent, (f) phosphoric acid, (g) zinc ions and (h) an agent

  solubilizing in the respective specified quantities.

  The second mixed solvent (e) in the second composition contains 100 parts by weight of a non-polar organic solvent having a boiling point of not less than OC / 760 mm Hg, not less than 0.5 parts by weight of a solubilizing solvent and not more than the limit quantity of water forming a homogeneous phase Non-polar organic solvents having a boiling point of not less than 00 C / 760 mm Hg are solvents practically insoluble in water and may include hydrocarbon solvents having molecular weights of not more than 200 such as pentane, hexane, toluene or xy lene; halogenated hydrocarbons such as chloride

  methylene, trichloroethane, tetrachloroethy lene or trichlorotri-

  fluoroethane; ethers having molecular weights of not more than 200 such as diethyl ether, diisopropyl ether or 2,2 'dichlorodiethyl ether; alcohols having not less than 5 atoms

  carbon such as n-pentanol or hexanol; alipha ketones

  ticks with not less than 5 carbon atoms; and esters such

  as methyl formate or ethyl acetate so that the compound

  tion may be non-flammable, especially preferred is chloride

  methylene, trichloroethane and trichlorotrifluoroethane These

  These can be used alone or in combination.

  bilisant used in the second mixed solvent is a component which dissolves phosphoric acid, zinc, the solubilizing agent and water in the composition Mention may preferably be made of the compounds

  cited above as examples of polar organic solvents.

  Methanol, ethanol, isopropanol and n-propanol are especially preferred. The solubilizing solvent can be used alone or in combination. The proportion of mixture of the solubilizing solvent is not less than 0.5 part, preferably 5 to 50. parts by weight, better still 10 to 40 parts by weight per 100 parts by weight of the

  non-polar organic solvent If the proportion of mixture of the sol-

  The solubilizing agent is less than 0.5 part by weight, the phosphoric acid, the zinc, the solubilizing agent and the water are not dissolved. The water used in the second mixed solvent acts as a promoter to form a film and it is contained in the film in the form of water of crystallization The proportion of mixture of

  water is no more than the limit quantity forming a homo-

  gene, preferably from 1.0 part by weight to not more than the limit quantity forming a homogeneous phase The term limit quantity forming a homogeneous phase is understood to mean an amount which forms a non-cloudy state in the composition proper by mixing the essential components If the proportion of water mixture exceeds the limit quantity forming a homogeneous phase, the solubilization reaction is too strong to obtain a substantially uniform film. Phosphoric acid (f) and the solubilizing agent (h) in

  the second composition can be illustrated by phospho- acid

  rique (b) and the solubilizing agent (d) in the first composition.

  The mixing proportions of the phosphoric acid (f) and the solubilizing agent (h) in the second composition are the same

  than those in the first composition.

  The zinc ions (g) used in the second composition can be illustrated by the same compounds mentioned above in the first composition. The zinc ions can similarly be replaced by the other metal ions indicated above. The mixing ratio of the zinc ions is from 0.001 to 3.5 parts by weight, preferably 0.01 to 2.0 parts by weight

  per 100 parts by weight of the second solvent mixture If the proportion

  tion of the mixture is less than 0.001 part by weight, a desired film is not obtained while at more than 3.5 parts by

  by weight, it is not dissolved in the second solvent mixture.

  To prepare the second composition, the respective components can be mixed and stirred homogeneously with the

  room temperature using a known mixer.

  To form a film using the first and second compositions of the invention, immersion treatment, spray treatment or flow coating methods can be used. For example, the known system of degreasing and chemical phosphating sold can be used. under the brand name "COOLPHOS" by NIPPON DACRO SHAMROCK CO, LTD or a solvent degreasing and rinsing apparatus of the type with one or more baths In particular, after having loaded the present composition into an apparatus, the respective solvent components in the composition are heated between room temperature and boiling points, preferably at a temperature of 10 C below boiling points to boiling points to thereby produce solvent vapors Then, after maintaining a metallic article, that is to say an object to be treated, in the solvent vapor zone preferably for 10 S to 1 min, better ncore from 15 to 30 seconds to carry out the degreasing treatment, the metallic article is immersed in the composition at the boil and preferably maintained for 10 seconds to 30 min, better

  still for 1 to 20 min to carry out the chemical treatment.

  The chemically treated article is then washed in boiling solvents to separate the unreacted materials, then

  dried The conditions for chemical treatment are not particular

  strictly limited and can be freely chosen according to the weight and thickness of the films formed by the composition of the

  phosphoric acid type and the concentration of each compound

health.

  In the present composition of the phospho- acid type

  The specific mixtures and solvents and the solubilizing agent capable of simultaneously dissolving zinc and phosphoric acid are used in specific quantities, a phosphate film

  durable zinc with excellent corrosion resistance and excel-

  slow adhesion can be formed In addition, the present phosphoric acid type composition is in a substantially non-aqueous medium so that a zinc phosphate film is easily formed in

  a short time on an object to be treated.

  The present invention is illustrated in more detail by the following Examples. It will however be noted that these Examples are not

  not intended to limit the scope of the invention.

Example 1

  Mixed and stirred in a glass beaker at room temperature.

  ambient temperature 89.7 parts by weight of ethanol, 10.3 parts by weight of water, 0.48 parts by weight of zinc borate or 0.11 parts by weight of Zn 2 +, 0.17 parts by weight of pyrophosphoric acid and 1.1 parts by weight of nitric acid at 61% by weight To prepare

  a homogeneous composition of the phosphoric acid type In use

  sant an apparatus represented in figure 1, one then applied the

  composition to a SPCC-SD steel sample of 0.8 x 70 x 150 mm.

  With reference to the figure, this Example will be explained in more detail

detail below.

  In the figure, the reference 1 designates a glass apparatus manufactured for the experiments for degreasing and washing solvents. The glass reactor 2 comprises a solvent degreasing zone A, a chemical treatment zone B provided with a heating device 4 connected to a heat regulator, the heating device 4 being placed around the reactor 2, and a drying zone C provided with a refrigerant 6 capable of circulating cold water around the upper portion of the reactor 2 To avoid cooling the solvent vapor by air and keeping the solvent vapor warm, wool

  glass 3 is placed around the reactor 2.

  First, after adding the type composition to phosphoric acid in chemical treatment zone B, the

  temperature of the liquid in the composition was raised by the provision

  heating sitive 4 to 44 ° C. (boiling point) Then, when the composition has produced solvent vapor, a test tube or test piece 7 can be moved up or down in the solvent degreasing zone A the bottom and attached to a stainless steel wire and the solvent degreasing treatment was carried out for 20 s The vapor released from the composition was cooled by contact with the test piece 7 and the refrigerant 6 The piece test 7, degreased at the same time, was immersed in The composition of the phosphoric acid type heated at 44 ° C. for 10 min and chemically treated in chemical treatment zone B Then, test piece 7 was removed from reactor 2 and washed using a solvent having

  components of solvents similar to those of the composition.

  Then, the test piece 7 was fixed in the drying zone C and dried for 15 S to form a film of zinc phosphate on the surface of the test piece On the surface of each of the films formed on the pieces test 7, a paint was baked in front of a synthetic resin of the melamine to alkyd type manufactured by Nippon Oi L and Fats Co, Ltd, sold under the name of "MELAMINE NO 1, WHITE EXTERIOR USE" (hereinafter abbreviated to "MELAMI NO 1") under baking conditions of 130 ° C. for 20 min to form a film 20 μm thick and a solvent-based paint of acrylic synthetic resin manufactured by Nippon Oi L and Fats Co, Ltd. under the name of "BELCOAT N 1 100 WHITE" (hereinafter abbreviated as "BELCOAT") under baking conditions of 1500 ° C. for 20 min to form a film 20 to 30 μm thick. Salt spray tests have were carried out on each of the baked test pieces In the test, each baked test piece was first cut in diagonal braces with an NT "A-300" cutter so that the cutter blade reaches the metal surface through The coating Then, The test was carried out on each coating on each of the test pieces baked according to Japanese standard JIS Z 2371 for a predetermined period Then, The test pieces were washed with water and left as which for 24 h An 18 mm wide adhesive tape manufactured by Nichiban Co, Ltd, under the brand name "CELLOTAPE" was brought into contact and fixed on the cross-section on each test piece The tape was torn off at an angle of 45 and we have my uré The maximum width on the tear-off side of the cross-sections of the coating The measured values are indicated in Table 2 The salt spray durations in Tests

  were 48 hours for MELAMI N 1 and 240 hours for BELCOAT, respectively-

  The proportions of each composition are indicated in Table 1 and the conditions of the chemical treatment, the weight of the films and the measured values of the salt spray tests are

shown in Table 2.

Examples 2 to 4

  Three types of phosphoric acid type composition were prepared according to each composition indicated in Example 1 Then, using each of the compositions, the chemical treatment was carried out with each test piece under the conditions indicated in the table 2 by a process similar to that described in Example 1 Each treated test piece was baked under similar conditions described in Example 1 to obtain each baked test piece Each baked test piece was subjected to the salt spray test according to Example 1 The proportions of each composition are indicated in Table 1 and the chemical treatment conditions, the weight of the films and the measured values of the salt spray tests are indicated in

table 2.

Comparative Example 1

  Using a phospho- acid type composition

  risk containing 72.6 parts by weight of methylene chloride, 25.5 parts by weight of methanol, 1.9 parts by weight of water, 0.5 parts by weight of phosphoric acid, 3.1 parts by weight of N, N- dimetylformamide and 0.07 part by weight of dinitrotoluene, the chemical treatment was carried out under the treatment conditions indicated in table 2 and the test piece was fired in a similar manner to Example 1 to prepare the cooked test piece The salt spray test has been carried out

according to Example 1.

  The conditions of the chemical treatment, the weight of the film and the measured value of the salt spray test are indicated

in table 2.

  Comparative Example 2 A test piece was prepared without chemical treatment

  and fired The fired test piece has been subjected to the projection test

  tion sa Line La va Their measured projection test sa Line is

indicated in The Leau tab 2.

Example 3

  We mixed and then stirred in a glass beaker.

  ambient temperature 72.6 parts by weight of chlorine methylene loride, 25.5 parts by weight of methanol, 1.9 parts by weight of water, 0.5 parts by weight of phosphoric acid, 0.1 parts of zinc oxide, 3.1 parts by weight of N, N-dimethyl Lformamide and 0.007 parts by

  weight of dinitrotoluene However, the solubilizing agent of the present invention was not contained in the composition so that the

  zinc phosphate was formed and the homogeneous solution was not obtained Therefore, the composition was not suitable for the

chemical treatment.

Examples 5 to 13

  Each composition of the phos- acid type was prepared.

  phoric according to each composition indicated in table 3.

  Then, each test piece was chemically treated under each of the conditions indicated in table 4 and cooked in a similar manner to Example 1 to obtain cooked test pieces. The salt spray test was carried out on each baked test piece The proportions of each composition are indicated in Table 3 The conditions of the chemical treatment, the weight of the films and the measured values of the projection tests

  saline are shown in Table 4, respectively.

TABLE 1

  Composition Example 1 Example 2 Example 3 Example 4 Methanol 42.1 Ethanol 89.7 Isopropano L 52.6 68.6

t-Butanol 76.5 -

Ethylene carbonate 21.9 -

  Acetonitrile 24.5 Water 10.3 5.3 1.6 6.9 Water _ 1.3.3 _, _ 6.9 Compound of Zn 2 + Zinc borate Zinc nitrate Zinc oxide Zinc nitrate

0.48 1.05 0.1 0.3

(0.11) (0.23) (0.01) (0 064)

  Composed of Ni 2 + Nickel carbonate Nickel nitrate

0.03 0.098

(0.015) (0.02)

  Composed of Na + Monosodium phosphate Sodium carbonate

0.01 0.098

___ (0.00 ,, _ 16) (O 2)

  Ortho acid Pyrophosphoric acid Phosphoric acid Pyrophosphoric acid 85% to 85% phosphoric acid

0.17 0.32 0.05 0.49

  Agent solubi Acetic acid at 61% Chloric acid at 36% Trichloroacetic acid Nitric acid at 61% reading 1.1 0.53 0.77 0.98 The numbers are these parts in podas numbers in parentheses indicate quantities of K ions ) OM OM al

TABLE 2

  Example Duration of treatment temperature Weight of fi Lm Salt spray test treatment g / cm 2 MELAMI N 1 BELCOAT Ex 1 10 min Boiling point 2.5 2.5 mm or less 1 mm or less 44 C Ex 2 18 min Point boiling point 3.7 O mm O mm 59 C Ex 3 20 min 43 48 C 1.5 3 mm or less 2 mm or less Ex 4 5 min Boiling point 2.3 1 rm or less 1 mm or minus 42 C Ex Comp 1 2 min Boiling point 0.2 8 mm 8 mm 39 c Ex Comp 2 8 mm or more 8 mm or more

  * Processing temperature measured under atmospheric pressure.

  * The treatment duration is the duration of contact with the chemical treatment liquid, excluding the time necessary before or after

treatment process.

  Un to 0) 0) 0) t O t O Composition Methylene chloride Ex 5 Ethyl oxide Trichloroethane

FURON 13

  Methanol Ethanol Ethylene carbonate Acetonitrile t-Butanol Water Co 2 dosed from Zn Compo 'from Ni Coosed from Ca Coposed from Mn- Corpose from Na

- 23.3

2.2 Zinc carbonate 0.13

(0.076)

0.13 nickel carbonate

(0.062)

Ex 6 31.25 1.5 Zinc oxide 0.063

(0.05)

Calcium carbonate 0.03

(0.01)

TABLE 3

Ex 7 23.2

_'-, 2 ':

* 0.21

Zinc oxide 0.026

(0.02)

Manganese carbonate 0.01

(0.048)

Ex 8 Ex 9 Zinc carbonate 0.7

(0.4)

Sodium carbonate 0.15

(0.07)

1.6 Zinc chloride 0.1

(0.05)

  Phosphoric acid 0.11 0.38 0.03 1.5 0.21

Nitric acid 0.39 0.38 1.2 2.5 -

  Chloric acid 0.53 Other t oa, K) M M M al K) K) T.ABLEAU 3 (continued) Composition Ex 10 Ex 11 Ex 12 Ex 13

  Ch Methylene Loride 100 100 100 -

  Ethyl oxide 74.2 Tri chloroethane

FURON 13 _ -

  Methanol, 8 -, 1 Ethanol 83 Ethylene carbonate Acetonitrile 54 t-Butanol L _ Water 2.3 0.45 6.7 4.7 Co 2 dosed with zinc nitrate Zinc oxide Zinc carbonate Zinc oxide Zn 0 .7.0.056 1.7 1.0

(0.15) (0.044) (0.95) (0.1)

  Nickel nitrate compost Nickel carbonate Nickel carbonate Ni nickel carbonate 0.046 0, 11 2 0.2

(0.009) (0.05) (0.93) (0.11)

Coeose of.

  Ca Coqosé of Mn Cocpose of Sodium carbonate Sodium nitrate Sodium nitrate Na 0.3 0.44 4.8

(0.14) (0.12) (1.3)

  Phosphoric acid 0.6 0.28 0.42 0.3 Nitric acid 0.77 0.11 1.7 0.9 Chloric acid Other * 1 * 2 * 1 (Vn :: trott A |, n * z tn br Pf: n / "1 vil 1 41 - a IL IC LU ^ 1 VCIII Iai, * 2 The sodium nitrite was dissolved immediately before immersing the iron plate in The Liquid

  _ The numbers are parts by weight.

* _ The numbers in parentheses indicate quantities of ions.

treatment.

-, d 61 i

TABLE 4

  Example Duration of treatment temperature Weight of film Salt spray test treatment g / cm 2 MELAMI N 1 BELCOAT Ex 5 15 min 55-v 60 C 4.5 1 mm or less 1 mm or less Ex 6 10 min Boiling point of 3.0 3 mm or less 1 mm or less 73 C Ex 7 20 min 65 'v 70 C 1.2 5 mm or less 2 mm or less Ex 8 8 min Boiling point of 1.5 5 mm or less 2 mm or less 77 C Ex 9 5 min Boiling point of 0.8 3 mm or less 2 mm or less 49 C Ex 10 3.5 min Boiling point of 0.6 5 mm or less 3 mm or less 56 C Ex 11 2 min Boiling point 4.5 4.5 mm or less 1 mm or less 42 C Ex 12 8 min 15-, 25 C 1.2 2 mm or less 2 mm or less Ex 13 3 min Point d boiling of 0.4 5 mm or less 3 mm or less 400 C

  * Processing temperature measured under atmospheric pressure.

  * The treatment duration is the duration of contact with the treatment liquid

  chemical, excluding the time required before or after the treatment process.

  * In Example 11, we treated a sheet of galvanized iron.

C O K) M M M al K) K)

Claims (5)

  1 Composition of the phosphoric acid type with a sensitive medium   slightly nonaqueous to form a phosphate-like film on a   metal, characterized in that it comprises as essential components tiels:   (a) 100 parts by weight of a first mixed solvent   holding 100 parts by weight of a polar organic solvent having a boiling point of not less than 0 C / 760 mm Hg (1013 mbar) and not more than 100 parts by weight of water; (b) 0.0001 to 7 parts by weight of phosphoric acid; (c) 0.001 to 5 parts by weight of zinc ions; and   (d) 0.01 to 5 parts by weight of a solubilizing agent.   2 Composition according to claim 1, characterized in that a portion of said zinc ions (c) is replaced by nickel ions, calcium ions, manganese ions, sodium ions,   magnesium ions, copper ions, cobalt ions or their mixtures.   3 Object characterized in that it comprises a film formed by the composition of the phosphoric acid type according to the claim 1 or 2.   4 Composition of the phosphoric acid type with a sensitive medium   slightly nonaqueous to form a phosphate-like film on a   metal, characterized in that it comprises as essential components tiels:   (e) 100 parts by weight of a second mixed solvent   holding 100 parts by weight of a non-polar organic solvent having a boiling point of not less than O C / 760 mm Hg   (1013 mbar), not more than 0.5 part by weight of a soluble solvent   reading and not more than the limit quantity of water forming a homogeneous phase; (f) 0.0001 to 7 parts by weight of phosphoric acid; Cg) 0.001 to 3.5 parts by weight of zinc ions; and   (h) 0.01 to 5 parts by weight of a solubilizing agent.   Composition according to Claim 4, characterized in that a portion of the said zinc ions Cg) is replaced by nickel ions, calcium ions, manganese ions, sodium ions,   magnesium ions, copper ions, cobalt ions or their mixtures.   6 Object characterized in that it comprises a film formed by the composition of the phosphoric acid type according to the claim 4 or 5.