JPS59207971A - Metal surface treatment with aqueous solution - 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 (Industrial Application Field) This invention relates to metal surface treatment, and in particular, metal ions selected from the group consisting of titanium ions, zirconium ions, hafnium ions, and mixtures thereof, and polyesters. The present invention relates to a technique for treating metal surfaces with a solution containing an acid salt of an alkenylphenol derivative or a polynolkenylphenol derivative. The solutions of the invention may also contain compounds selected from the group thiourea, thiourea derivatives, tannic acid, vegetable tannins and mixtures thereof.

BACKGROUND OF THE INVENTION The art of applying protective coatings to metal surfaces to improve their corrosion resistance and paint adhesion properties is well known in the metal finishing industry.

According to conventional techniques, metal surfaces are chemically treated to improve metal phosphate conversion coatings and/or metal acidity. In addition, the chemically coated metal surface was rinsed or post-treated with a solution containing a hexavalent chromium compound in an attempt to further improve the autoerotic properties and Bain 1 to naming properties. .

However, hexavalent chromium compounds are toxic, and it is necessary to remove chromate from the Jul solution used in metal surface treatment at plating plants and install pollution prevention equipment to prevent contamination of rivers and water sources. requires large capital investment. Therefore, if the metal surface that has been chemically coated is post-treated with a treatment solution containing a hexavalent chromium compound, its corrosion resistance and paint (q'4 properties) can be improved. Research and development of substitutes for post-treatment liquids for compounds has been actively conducted in recent years.1
It's me. One of them is disclosed in patent application No. 210.910 [Phosphorus M chloride conversion coating treated curved metal surface], which was filed in the United States on November 28, 1980. The post-treatment compounds of this application are based on the alkaline side p
Although used in post-treatment solutions with H, it is desirable for this compound to have a broader pH range, especially for acidic post-treatment solutions.

(Problems to be Solved by the Invention) The present invention aims to provide a new composition as a substitute for solutions containing hexavalent chromium compounds. J: Solve the problems of the conventional technology that requires sea urchin, and use a new composition in the post-treatment method of metal surfaces that have been subjected to phosphate chemical conversion treatment or chemical conversion coating treatment, causing pollution problems. The present invention also provides a treatment solution and method for treating untreated metal surfaces such as aluminum, steel, zinc, etc. Metal surfaces treated by the solution and method of the present invention, regardless of whether they have been previously treated with a chemical coating, will have excellent corrosion resistance and paint adhesion properties. 1′
Conversion coated and uncoated surfaces with excellent corrosion resistance and paint adhesion properties. In order to deepen the understanding of this invention, a detailed explanation will be provided later.
3C is % by weight, middle age or weight %, unless otherwise indicated.

(Means for Solving the Problems) In order to solve the above-mentioned problems, the gist of the present invention is the following points. That is, in the formula, R-R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms; Y is hydrogen, 7, CR4R50R6, CH2Cl, or an alkyl or aryl group having 1 to 18 carbon atoms; R1o hydrogen or alkyl, aryl,
is a hydroxyalkyl, aminoalkyl, mercaptoalkyl or phosphoalkyl moiety, and the R4 to R
1o is a carbon chain length equal to or less than the chain length that makes this compound insoluble or non-dispersible, and n is 2 or a number that makes this polymer insoluble or non-dispersible, and a number less than or equal to this chain length. an effective amount of a soluble or dispersible compound selected from the group consisting of a polymer of the formula: an acid salt of the polymer and mixtures thereof.

The solution in this invention is preferably an aqueous solution, and it is desirable that the above-mentioned 7 parts contain enough fleas to make the compound water-soluble or water-dispersible.

According to the invention, the metal surface contacted with the treatment solution has excellent corrosion resistance and paint adhesion properties.

Although the solutions of this invention can be effectively applied to treated or untreated metal surfaces, generally speaking, best results are obtained when the metal surface has been conversion coated. . Conversion coatings are well known, for example, [American Society for Metals]
"Metal Handbook" Volume 1I, 8th Edition, No. 529~
541 pages and [Metal Finishing Guidebook and Die Leftry, J <1972) 59
0 to 603, and these are also cited as references in this specification.

In a typical metal processing operation using the compositions and processes of this invention, the metal being processed is first cleaned by chemical or physical methods and rinsed with water to remove grease and dirt from its surface. except. The metal surface may then be contacted with the solution of the present invention, or the cleaned metal surface may be treated with a Mari conversion coating solution in a conventional manner to form a chemical coating without any contact step with the treatment solution following the cleaning treatment. After rinsing the chemically coated metal surface with water, it is immediately brought into contact with and immersed in the treatment solution of the present invention.

The present invention can be applied to various metal surfaces such as STV M iron,
Manganese phosphate, zinc phosphate, calcium, nickel,
or surface treatment of metals with surfaces that have been conversion coated with suitable conversion coating compositions such as magnesium-modified zinc phosphates, mixed metal oxides, and titanium or zirconium organometallic coatings]! 11 is extremely effective. Examples of suitable metal surfaces include lead, iron, aluminum,
This is the surface of pickled cold-rolled base steel, hot-rolled steel, galvanized steel, etc. Here, "metal surface 1" refers to both an untreated metal surface and a metal surface treated with a chemical conversion coating.

According to the present invention, a metal surface is treated with a treatment solution according to the present invention, which treatment solution comprises a polymer having the following general formula, an acid salt thereof, and a mixture thereof. ) an effective amount of a soluble or dispersible compound.

In the formula, R1 to R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms; Y is hydrogen, ZlCR4R50R6, C)-12CI, or an argyl or aryl group having 1 to 18 carbon atoms; and R4 to R1o hydrogen or alkyl, aryl,
hydroxyalkyl, aminoalkyl, mercaptoalkyl or phosphoalkyl moiety, and the R4 to R1
o is a carbon chain length that is less than or equal to the chain length that makes this compound insoluble or non-dispersible, and n is 2 or a number that makes this polymer insoluble or non-dispersible and a number that is less than or equal to this chain length. The solution in this invention is preferably an aqueous solution, and it is desirable that the above-mentioned 7 parts are present in an amount sufficient to make the above-mentioned compound water-soluble or water-dispersible.

The alkyl group of the polymer backbone or chain in the above formula can be located at the ortho, meta or para position to the hydroxyl group on the aromatic ring of the phenol; is preferably selected from para and or type 1.

In polymeric form, the treated compounds of this invention consist of a single unit of a number of specific monomers in each of the above general formulas, e.g.
It has a general formula like ggi.

where Y is defined as above (not hydrogen) and A
, B, C, and D are the numbers at or below which the polymer is insoluble or non-dispersible in the solution under the conditions of use. B + C is at least 2, and when water is the solvent, the medilene amine moiety, i.e. 7 moieties, as defined above must be present in sufficient quantity so that the acid Once neutralized, the polymer becomes water-soluble or water-dispersible.

The mole percentage required for water-solubility or water-dispersibility is based on the molecular weight of the polymer and R4 in the polymer.
This is due to the ~R10 portion. Generally speaking, a mole percent of 7 per amine or phenol group is 1oχ
Although the amount varies from 200% to 200%, it is usually in the range of 50% to 150%, with 1 phenol group per 7 mer.

Naturally, the treatment compounds of this invention are based on polyalkenylphenol polymer derivatives.
Polyalkenylphenols or substituted polyalkenylphenol polymers useful in this invention include, for example, isoprobenylphenol, isobutenylphenol, dimethylvinylphenol, and the like.

Suitable derivatives of the above general formula can be obtained, for example, by Mannich reaction. For example, poly-4-vinylphenol can be reacted with formaldehyde and a secondary amine, and neutralized with an organic or inorganic acid to form an aqueous or dispersible solution or emulsion of the treatment compound of this invention.

In this invention, the molecular weight range of the polyalknylph'-nol used for the preparation of the claimed derivatives is from 6 dimer to
Low molecular weight oligomers or molecules *i30,000 or larger than high molecular weight polymers. The upper limit of the molecular weight is determined by the functional constraints imposed on the derivative to be water-soluble or dispersible.

The molecular weight of the derivative resulting from J in the above formula is approximately 200.0.
00, but preferably from about 700 to about 70,00
It is in the range of 0. The formula assigned to these derivatives is 83
In this case, the upper value for II n+1 is about 850, preferably about 10 to about 300. Similarly, R
The carbon chain length of the to R1o substituent is about 1 to 18, preferably about 1 to 12. Naturally, in each case, (1a, the value of the carbon chain length,
The percentage of II Z 11 moiety is selected to give the desired (6) water solubility and/or water dispersibility.

The processing compound of this invention is soluble in an organic solvent, and is used as a processing solution by dissolving it in an organic solvent such as ethanol. However, the solutions of the invention can very advantageously be used as aqueous solutions.
In order to make the compound water-soluble or water-dispersible, 7
Organic or inorganic acids are used to neutralize the moieties.

Acids useful for this purpose are acetic acid, citric acid, oxalic acid, ascorbic acid, phenylphosboxic acid, poly[]10-methyl small sulfonic acid, mono-, di- and trichloroacetic acid, triflic 121-bosphonic acid, Nitric acid, phosphate, hydrofluoric acid, sulfuric acid, boric acid, hydrochloric acid, hexafluorosilicic acid, hexafluoro[1 titanic acid, hexafluorΔ1]zirconate, and the same effects.

By adding water to the above-described neutralized, over-neutralized, or partially neutralized IC processing compound, a water-soluble or water-dispersible solution or emulsion useful for metal processing can be obtained.

Aqueous solution 0 month) 11 is +1110. ! It can range from 1 to 12, but in practice it should be kept between 2.0 and 8.0 to ensure solution stability and to obtain the best results on the treated metal surface. Ru.

In practical use, the treatment compounds of this invention may be used, for example, at about 0.
It is used as an IIA degree solution diluted from 0.01 to about 5% by weight. The preferred working solution is 1lfa degree.
It is 0.025% to 1%. However, polishing may be increased for transport and storage purposes. The solution may also contain a pigment that is a paint composition with a film-forming compound that is itself a treatment compound;
Additionally, it can contain solvents, organic or inorganic pigments.

Of course, the treatment solution of the present invention can contain other components in addition to the above-mentioned compounds. For example, the processing solutions of this invention are often referred to as solutions containing metal ions and soluble or dispersible processing compounds. For example, the metal ions in this treatment solution are about 0001% by weight - about 1% by weight.
．． It is present in an amount of 0% by weight and can be selected from the group consisting of titanium ions, zirconium ions, hafnium ions and mixtures thereof. These ions are ions of transition metals of group TV B of the periodic table, for example water-soluble acids such as hexafluorotitanic acid, hexafluorozirconic acid or hexafluorohafnic acid, or e.g. Prepared by addition of salts such as nitrates, sulfates, fluorides, acetates, citrates and/or chlorides. By adding the metal ions to the treatment compound, the efficiency and performance of the treatment solution used can be increased, reducing the treatment time required to apply the treatment solution on the coil line to the metal surface from about 2 seconds to 5 seconds. It can save seconds.

In addition to the metal ions mentioned above, or in addition to the above,
For example, ions such as ditanium, zirconium, hafnium, mixtures thereof, etc., and the treatment solution contains a group consisting of alkyl or aryl diourea compounds, tannic acid, vegetable tannins 87i or pentad tannins and mixtures thereof. Approximately 0.01 of the ingredients selected from
~40% by weight cans. Suitable ingredients also include methyl, ethyl or butylthiourea, acacia, mangrove or chestnut tannins, oak fivefold tannin J3 and valonia acorn extract.

The treatment solution of this invention is applied to metal surfaces by conventional methods. The metal surface to be treated is preferably one that has been treated with a chemical conversion coating, but it is also effective on untreated metal surfaces, and can improve the corrosion resistance and paint adhesion of the (untreated) metal surface. . Treatment of the metal surface with the treatment solution may include, for example, spray coating,
This is done by roller coating, electrocoating or dip coating. The temperature of the solution in J3 in such solution treatment ranges over a wide range, but preferably ranges from about 21°C (70°) to about 71°C (160°).
[). The metal surface coated with the treatment solution in the manner described above is then rinsed (with water), although good results may be obtained without rinsing. However, depending on the final coating process, for example, when performing electrostatic coating, it is better to perform rinsing with water.

The metal surface treated as described above is dried by a drying process such as circulating air drying or oven drying.

The drying temperature may be room temperature, but the temperature may be raised to shorten the drying time.

After drying, paint is applied to the treated metal surface. The metal surface is suitable for being coated by standard coating techniques such as spray coating, electrostatic coating, dipping, roller coating, electrocoating, etc. As a result of the treatment according to the present invention, the corrosion resistance and adhesion properties of the chemically coated metal surface are extremely good.

(Tomotane ■-yu) 3 equipped with turbine blades, nitrogen blowing pipe, condenser, etc.
95% in 78 liter steel reactor
Add about 45 klJ (100 bonds) of ethanol solvent and gently raise the temperature to 50°C to dissolve the molecule 1Q.
5000 ml of poly-4-vinylphenol 18kQ was slowly added to the solvent with stirring.

After all of this polymer had been added, the reactor was closed and heated to 80°C to dissolve the remaining polymer. The reactor was then cooled to 406C and 23K (1 (50 lb)) of N-methylamine ethanol and 45 kg (100 Ib) of deionized water were added, maintaining the temperature at 40 °C ± 2 °C. 25 kg of 37% formaldehyde solution (54°1 bond) was added over a period of 1 hour.
°C and diluted with 10% nitric acid 143k (315 min) to obtain a stable aqueous solution of the compound of this invention.

(kL mouse-2) Condenser, nitrogen blowing pipe, overhead lj2 J″4′
- Into a 1000ml reaction flask equipped with a thermometer, thermometer, etc.
Add 801 m of poly-4-vinylphenol (500 g m
and 100 gm of deionized water and heated to 50'C to react. 108g of 37% formaldehyde solution
Add m for at least 1 hour and leave to rest for another 3 hours at 50°C.
The mixture was then heated at a temperature of 806C for 3 hours.

The reaction was cooled and 65 Q nl of 75% phosphoric acid was added followed by 227 gm of deionized water resulting in a stable aqueous solution of the compound of this invention.

(Hui Masu-K) 24-gauge cold-rolled steel panels coated with oil to prevent corrosion during shipping are cleaned with mineral spirits and then treated with a strong alkaline cleaner (marketed under the trademark PARCO). ) using an aqueous solution of iron phosphate conversion coating treatment solution (trademark BONDERTTE), followed by a 60 second wash at a solution temperature of approximately 66°C, followed by a 60 second wash at a temperature of 43°C. After coating (commercially available) and this chemical conversion coating treatment,
The treated panel was washed with cold water for 30 seconds and then
．． The 5% solution was sprayed at a temperature of 43° C. for 130 seconds. The panel was then rinsed and dried in an oven at 177°C for 5 minutes.

These panels are commercially available from PPG.
U R A C R O N J (TM) Paint CWi”tfi and standard salt spray method (AST
MB-117-61). 504
After the lapse of time, the panels treated according to Example 1 as described above yielded results comparable to the standard glue 1] treated comparison panels.

(Backyard■-A> After adding about 25 kg (54,1 lb) of 37% formaldehyde solution, the reaction was heated at 80 °C for 3 hours,
1 = Results ,
1 fathom of a stable aqueous solution of the lip compound of this invention
child .

(Back check-1) A cold rolled steel panel was cleaned with a strong alkaline cleaner, and the cleaned metal surface was rinsed with warm water. An iron phosphate conversion coating solution (commercially available under the trademark BONDERITE) was then sprayed at a temperature of approximately 71°C (IGOo') and the panels were rinsed with cold water before post-treatment. Poly-4-vinyl from Example 4 A dilute solution of the phenol derivative was mixed with hexyliflu A[1 tannic acid to give approximately 496C (1
It was applied to metal that had been subjected to phosphate conversion treatment at 20°1). Poly-4-.

The concentrations of vinylphenol derivatives and hexafluorotanninate contin 1~ are 0.05~02% and 000%, respectively.
It was changed from 6 to 0.03%. All panels were oven baked at approximately 177°C (50'F) for 5 minutes. f'PARcOLENEJ™ standard thickness comparison panels were used.

Said treated panels were coated with a cathodic electrostatic coating agent "P".
powercron 300j' (trademark), voltage 120-140 pol 1 ~, temperature approximately 27°C (80'
F) Acrylic electrocoating (PP0 company) under conditions of time 60 to 90 seconds, with uniform film appearance and film thickness 0.95 to 1
The aim was to obtain 0 mils (24-25 microns).

The coating cured in 20 minutes when the metal temperature reached a maximum of 113°C (325°). The panels were subjected to a standard salt spray test according to ASTM B17 = 61 and compared to RI[1 mate treated and deionized water rinsed comparison panels. The results were similar to those of the PARCOI ENE 60j™ activated chromium comparison panel!
Nine compounds containing 1% poly-4-vinylphenol were obtained.

(Practical 1-1) Cold-rolled steel panels were cleaned, and a phosphate chemical conversion coating was formed on the panel surfaces. A tempered rolled galvanizing steel panel (TRG) was cleaned and a conversion coating of either zinc phosphate or composite oxide type was formed. Four of these panels were given a final rinse of 10 seconds using one of the following final tin treatments:

Final rinse No. 1 Modified chromic acid (rPARcOLEN '62 manufactured by Occidental Chemical Corporation)
J) Final rinsing No. 2 Deionized water final rinsing No. 3 0.25% aqueous solution of acid salt of poly-4-vinylphenol derivative with pH 6.0 of Example 4 Final rinsing No. 34 Number 3 or higher and 0 .01!4ffi% titanium ions were added as l-12TiF6 at pH 6.1 in a 0.2% aqueous solution of the acid salt of a poly-4-vinylphenol derivative, and then the panels were painted by one-coat and two-coat paint systems. Painted 1=.

Paint 1 ~ 1 Glizden 71308 PolyLure 2000 White Polyester Paint 2 H&T Black Vinyl Paint 3 Midland White Polyester Paint 1 4 Midland - DekuMeta 9x165 Epoxy Brimer Midland - DekuMeta 5x121 Crystal 1'Dexstar J Why 1 ~ Polyester Trap Coat The above panels are , then scribed, 8STHD37
Standard AST described in 94-64■, HB-1
17-61 5% salt spray test, 8 STH2247-6
4T wet water test and 180° mold bending test.

The results are shown in Table 1 attached to the last page entitled "5% Salt Spray Results."

The table shows the creep back from the scribe, the degree of blistering, and the degree of red rust. A final rinse containing polymer will remove less rust from the scribe (creepback) than a deionized water final rinse. In the case of titanium addition, the rust from the scribe (marked line) is removed by polymer rinsing (creep back) in N04 except for 6 cases.
Less than comb acid rinse.

Wet test results for iron phosphate conversion coated panels rinsed as per the table above were substantially equivalent. Adhesion to the polymer-containing rinse by 180° bending test is at least equivalent to that with a chromic acid rinse;
It was excellent.

<Child 15-J) Panels were processed in the same manner as in Example 6, except that the processing time was shortened by 5 seconds. Superior results were obtained on zinc phosphate and composite metal oxide chemical conversion coatings compared to chromic acid post-treatment. However, the poly-4 prepared in Example 4
- Vinylphenol derivative solution to 0.02% in a pH 5.1 treatment bath with kizafluorotitanic acid to a concentration of 0.1%
The results for iron phosphate used under these conditions were not very good. Corrosion resistance could be improved by doubling the concentration of the poly-4-vinylphenol derivative, hexafluoroditanic acid and the treatment bath with the above composition plus 0.2% thiourea and 0.05% tannic acid.

(Support-1) The cleaned aluminum panel was treated with a chromium-free conversion coating solution (commercially available under the trademark BONDERITF 787). After rinsing with cold water, rinse one set of these panels with a chromium-free rinse solution (trademark 1).
'PARcOLENE 88J), and another Cera 1- was rinsed with the post-treatment solution prepared in Example 4.

After rinsing, the panels were passed through a squeeze roll to remove excess solution. Treatment liquid and final rinse liquid (trademark rPARcO) marketed under the trademark IBONDERITE 722J.
A chromium standard comparison panel was prepared using a chromium standard comparison panel (commercially available as LENE10J). After such rinsing, the panels were again passed through squeeze rolls.

The treated panels were painted with a two-single coat system.

1. Haunchi Paint Hirakory Brown Polyester XR829D 2. DuPont Paint White Acrylic 884-50
Lucite 2100 series painted panels were subjected to a 504 hour acetate water spray test. Peel off the tape from the marked lines after each 168 hours,
Paint loss, general blistering, edge rust, etc. were evaluated. The evaluation after 504 hours is as follows.

Treatment of B787 Example 4 8787 Polyvinyl-4-878
7+PLN88 Phenol +PLN10
Derivative haunch E D6.08 EO-13, D9
EO-1” Paint S 7-10.D6 S O
-2, D9 SO-2”5%PD8 0-I
F9 0-ISF9 Decobon Paint E D6 E HO2, D9
EO-2S-3s 5o-25o-1”, HO25o-2S3%P, 0
6 1% 89 1%, V 90-2”
0-1” 3%P, 06
3%, V 9+9 [-Edge evaluation (rating) S-Screen evaluation (rating) The salt spray results measured by rust blisters from the groove lines are based on the chemical conversion coating treatment solution (trademark r BONDE).

commercially available as RIT E 787-j) and polyvinyl-
Aluminum panels treated with 4-phenol derivative (from Example 4) were coated with the chemical conversion coating treatment solution (trademark rBON).
(commercially available as DE RI TE 722J) gave better or better results than b with the above-mentioned [PARCOLENElo].

(Once in the Branch) Each panel was treated as in Example 5, except that each panel was given a final rinse with one of the solutions in Appendix 2.

Each panel was painted and tested as per Appendix 2. The result of Rinse No. 2 is Rinse No. 011
of the chromic acid control compared to or equivalent to that of the chromic acid control. The results obtained with Rinse No. 3 were comparable to those obtained with Rinse No. 2.

The embodiments and descriptions described above are not intended to limit the invention, which is defined by the following claims.

Claims (1)

[Scope of Claims] In the formula, R-R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms; Y is hydrogen, Z, CR4R50R6, CH2Cl, or an argyl or aryl group having 1 to 18 carbon atoms; . R4"10 hydrogen or an alkyl, aryl, hydroxyalkyl, aminoalkyl, mercaptoalkyl, or phospho)norgyl moiety, and R4 to R1o are carbons of a chain length or less such that the compound is insoluble or non-dispersible. consisting of a polymer of chain length, where n is from 2 to a number such that this polymer is insoluble or non-dispersible, and a number less than or equal to this, an acid salt of this polymer, and mixtures thereof. A method of treating a metal surface with an aqueous solution comprising: treating a metal surface with an aqueous solution comprising an effective amount of a soluble or dispersible compound selected from the group consisting of:
2. The method according to claim 1, wherein the ratio is 0 to 200%. 3. The method of claim 2, wherein the mole percent of 7 per monomer is about 50-150%. (4) The method according to claim 2, wherein the pH is about 0.5 to about 12. (1・
(5) The method according to claim 4, wherein pI-I is about 2.0 to about 8.0. 6. The method of claim 1, wherein said compound is present in an amount of about 0.018% to about 514%. (7) The compound has an amount of about 0.025 to about 1 tllxff
7. A method according to claim 6, wherein the i% is present in an amount of i%. (8) The method according to claim 5, wherein Z has the following structural formula. (9) The method according to claim 5, wherein Z has the following structural formula. (10) The method according to claim 1, wherein the compound is a reaction product of poly-4-vinylphenol formaldehyde and a secondary amine. -5 alkyl group: Y is hydrogen, Z, CR4R50R, CH2Cl, or an alkyl or aryl group having 1 to 18 carbon atoms: Z is R4 to R1o are hydrogen or alkyl, aryl, hydroxyalkyl, aminoalkyl, mercaptoalkyl or /J\sulfoalkyl moieties, and R4 to RIO are
The carbon chain length is less than or equal to the chain length at which the compound becomes insoluble or non-dispersible, and n is between 2 and a number at or below such that the polymer becomes insoluble or non-dispersible. an aqueous solution for treating metal surfaces, comprising a polymer as shown in Table 1, a soluble or dispersible compound selected from the group consisting of acid salts of the polymer and mixtures thereof. 12) The aqueous solution according to claim 11, to which a pigment is added. (13) Claim 1, wherein the solution is paint.
Aqueous solution according to item 1. (14) Claim 1, wherein the solution is an aqueous solution.
Aqueous solution according to item 1. (15) Mole% GΔ of 7 parts per 7 units ~ 50% ~
12. The aqueous solution according to claim 11, which has a concentration of 150%. (16) The aqueous solution according to claim 16, wherein 1))-1 of the aqueous solution is about 0.5 to about 12. (17) The aqueous solution according to claim 15, wherein the aqueous solution has a pH of about 2.0 to about 8.0. 18. The aqueous solution of claim 11, wherein said compound is present in said aqueous solution in an amount of about 0.01 to about 5% by weight. (19) The aqueous solution of claim 18, wherein the compound is present in the aqueous solution at a concentration of about 0.025% to about 11%. (20) Claim 1 in which Z is the following structural formula:
Aqueous solution according to item 1. (21) Claim 1 in which Z is the following structural formula:
Aqueous solution according to item 1. (22) The aqueous solution according to claim t411, wherein the compound is a reaction product of poly-4-vinylphenol formaldehyde and a secondary amine.