JPS58162697A - Water-soluble oil composition for temper rolling - Google Patents

Abstract

PURPOSE:A water-soluble oil composition for temper rolling, having improved corrosion prevention properties, stain resistance properties, solubility in acid, safety and hygienic properties, containing a dicarboxylic acid partial ester salt of an oxyalkylated amine and an alkanolamine. CONSTITUTION:The desired water-soluble oil composition for temper rolling containing (A) a dicarboxylic acid partial ester of an oxyalkylated amine shown by the formulaI R1 is >=4C organic group; R2 is H or a hydrocarbon group- containing organic group, etc.; R'1 is dicarboxylic acid; A1 is 2-4C alkylene; M1 is alkali(earth)metal, ammonium, etc.; n1 is >=1; m is 1 or 2 , etc. and (B) an alkanolamine shown by the formula II (R3 and R4 are H, hydrocarbon, etc.; n3>=3; A3 is 2-4C alkylene) usually in a weight ratio of (99.5:0.5)-(50:50).

Description

[Detailed description of the invention] The present invention relates to a temper rolling oil composition.

More specifically, the present invention relates to a water-soluble temper rolling oil composition that has excellent rust prevention properties, stainless steel resistance, acid dissolution properties, safety and hygiene properties, and the like.

In temper rolling of a cold rolled steel sheet after an annealing step, a liquid generally called temper rolling oil is used to perform a good rolling operation, clean the surface of the steel sheet, and impart intermediate rust prevention properties. There are two types of temper rolling oil: oil-based temper rolling oil whose main component is light maroon oil and water-soluble temper rolling oil. Generally, water-soluble (chemical solution) type temper rolling oil is preferred. For this reason, water-soluble temper rolling oil containing sodium nitrite and alkanolamine as its main ingredients has come to be used. Temper rolling oil containing sodium nitrite and alkanolamine has excellent rust prevention properties and is suitable for the purpose of temper rolling oil.However, when nitrite reacts with amines, some of the It has been pointed out that trosamines are formed, and temper-rolling oil containing nitrites has the disadvantage that when a steel plate is coated, the coating film tends to peel off.

For this reason, water-soluble organic temper rolling oils that do not contain nitrites have recently been developed, including carboxylic acid salts with 10 carbon atoms or less, salts of carboxylic acids with amines with 10 carbon atoms or less, or nitro-rolling oils of benzoic acid. Although compounds containing groups or amino group-substituted compounds have been proposed, these compounds have drawbacks such as poor solubility in acids such as hydrochloric acid and poor anti-corrosion properties, making them impractical for practical use. Many problems arise with this process.

Under these circumstances, the present inventors conducted intensive research on a water-soluble temper rolling oil composition that does not contain nitrites, dissolves in acids, and has excellent antirust properties, and as a result, the present invention was achieved. That is, the present invention is a water-soluble temper rolling oil composition characterized by containing a dicarboxylic acid partial ester salt of an oxyalkylated amine (A) and an alkanolamine (or the like).

In the present invention, the dicarboxylic acid partial ester salt (A) of an oxyalkylated amine has the general formula %) [wherein ■, is an organic group having a C4 or higher hydrocarbon group;
- is an organic group having H, I hydrocarbon group or (-A20
) nH, and R3 and R2 combine to form -CH2CH,
001I.

CH□-matoko may be +0H2-)5 to form a ring. A1*A2 is a C2-C4 alkylene group; fluorine is a dicarboxylic acid residue; M is an alkali metal, alkaline earth metal, ammonium, or amine cation. Examples include compounds represented by nI + "2 is an integer of 1 or more; m is 1 or 2."

Tomo is an organic group having a C6 or higher hydrocarbon group.

Examples include organic groups having a hydrocarbon group of 04 or more and a hydrocarbon group of C4 or more. The hydrocarbon group of 04 or more is 04 to □, preferably an alkyl group or alkenyl group of 'Q+-qe (butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group).

stearyl group, oleyl group, etc.); cycloalkyl group (
cycloalkyl group, etc.) and aromatic hydrocarbon groups (aryl groups such as phenyl group and naphthyl group; aralkyl group such as benzyl group; and alkaryl group such as butylphenyl group).

Examples of the organic group having a hydrocarbon group of 04 or more include the following groups.

l) Amino group-containing hydrocarbon group 2) Amide group-containing hydrocarbon group R,, CON→A, /← (2')3
) Ester group-containing hydrocarbon group n; coo云A2I← (8')4)
Ether group-containing hydrocarbon group R, lO→A2I+-(4') [wherein, is O, or more hydrocarbon group;
6 alkylene group i A'2 is a 6-C4 aJ alkylene group; X is I-1, →A'20+T-■ or 1+A
', 0jo■tv2-ccx: It's a seagull. ] General formula (r) ~ (/r) Nioite A'z i is A
1. ! :iL! ′! Yokawa'i is striped and jn3*"4 is nl
s ''2;<This is the same group as the above hydrocarbon group.

A and / are C8 to C6 alkylene groups, and include ethylene, propylene and hexamethylene groups.

A' is a C2-q alkylene group and is the same group as +AI. Among these, preferred are C4 or higher hydrocarbon groups, and particularly preferred are alkyl groups.

- is ■, an organic group having a hydrocarbon group or (-A, O)
nH. As an organic group having this hydrocarbon group, q
As mentioned above, preferably a 01 to C2 degree hydrocarbon group or an organic group having this hydrocarbon group is mentioned. These are the towns;
You can cite the statement exactly 5 times, except that 04 or more was changed to q or more in . R1 and 4 are bonded to -CH,OH
,0OH2CH2- or +0H2-)-5 to form a ring (such as a morpholine ring).

A, , A, is C! ~C4 fullkylene group, including ethylene group, propylene group, butylene group and ethylene.

Examples include propylene combination groups (random, block). Preferred are ethylene group, propylene group, and combinations thereof (random, block).

"l is a dicarboxylic acid residue (a group obtained by removing two carboxyl groups from a dicarboxylic acid), and the dicarboxylic acids constituting the residue include aliphatic dicarboxylic acids [succinic acid, adipic acid, azelaic acid, Saturated dicarboxylic acids such as sebacic acid; maleic acid, alkenylsuccinic acid, dimer acid (
unsaturated dicarboxylic acids such as sulfate, fatty acid dimer), etc.
and aromatic dicarboxylic acids (phthalic acid, isophthalic acid,
terephthalic acid, etc.), S- or O-containing dicarboxylic acids (thiodiacetic acid, thiodipropionic acid, oxydiacetic acid, etc.). Preferred are phthalic acid and maleic acid.

Ml is an alkali metal, alkaline earth gold, ammonium or amine cation. Examples of alkali metals include Li, Na, Ni, etc.; examples of alkaline earth metals include Oa, Mg, 8R, Ba, etc.; examples of amine cations include alkyl or alkenyl amines (methylamine, dimethylamine, ethylamine);

diethylamine, propylamine, amine, etc.); alkanolamines [the alkanolamines include the alkanolamines mentioned below. ] and other amine cations. Preferred among Ml are alkanolamines.

"Ie" 2 is an integer of 1 or more, preferably an integer of 1 to 20. The total number of n (total number of moles of alkylene oxide added, n1+n2+, etc.) is usually 1 or more, preferably 1 to 20. Particularly preferably 1 to 10.

When the total number of n is more than 20, the rust prevention property tends to deteriorate.

Specific examples of dicarboxylic acid partial ester salts of oxyalkylated amines are as follows.

In the following description, MA is maleic acid, PA is phthalic acid, D8A is dodecenylsuccinic acid, 8A is succinic acid, dieta is jetanolamine, monoeta is monoethanolamine, EO is ethylene oxide, PO is propylene oxide, (PO ) 6 each represents a PO6 molar adduct.

(1) Oxyalkylated aliphatic amine dicarboxylic acid partial ester salt octylamine (PO) 2MA half ester jeta salt, octylamine (EO), FA half ester monoester salt, laurylamine (EO) 2 P A /λ -Fester Na salt, laurylamine (EO) 6P A/S
-Festerzita salt, laurylamine (PO) 2
M A /S = feedster dieta salt, laurylamine (
PO) 6MA half ester dieter salt, laurylamine (PO) 6(EO) 4PA half ester dieter salt, lauryl afz-(PO fist) 68A ha7-phester dieter salt, lauryl amine (PO) sMA half ester monoeta salt.

N-methyl laurylamine (EO) 6PA half ester dieta salt, stearylamine (EO), PA iz
- Phester Na salt, stearylamine (PO) 6M
Aha.

-Fester monoetha salt, stearylamine (EO),
.

PA Ha, - feedester Na salt, stearyl propylene diamine (EO), oDSA half ester dieta salt, sulfuric acid partial ester salt aniline (PO) 4MA half ester Na salt, Anili: / (EO) 6PA half ester dieta salt, pencil urea i:/ (PO) 4MA half ester dieta salt O) Dicarboxylic acid partial ester salt of oxyalkylated heterocyclic amine Morpholine (EO) 1PA half ester dieta salt etc. Partial ester salts in the present invention are produced by known methods. can do. For example, a catalyst (Na O
The terminal hydroxyl group is converted into an amineoxyalkylene ether by adding alkylene oxide such as ethylene oxide or propylene oxide singly or in combination of two or more at 50 to 200°C, usually in the presence of H, KOH, etc. Esterify with dicarboxylic acid (or acid anhydride) so that at least one carboxyl group remains.

In this case, when using a dicarboxylic anhydride such as maleic anhydride, conolilic anhydride, or phthalic anhydride, the acid anhydride can be formed by heating to 100 to 200°C without using a catalyst. It opens the ring and reacts easily. When dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid are used, they can be esterified by dehydration using an alkali or acid catalyst, usually at 100 to 20[sigma]C. After esterification, the carboxyl group of Hafestel is converted into an alkaline substance (alkali metal hydroxide,
The salt can be removed by neutralization using a known method (carbonate; alkaline earth metal hydroxide; ammonia; amine).

The alkanolamines (b) used in the present invention have the general formula % formula % (3) (wherein 'R, f, R3 are ■, a hydrocarbon group or +A4
0). 4 days are 1 and +'3t"4 is an integer greater than or equal to 1, A
3. Examples include compounds represented by the formula -CIT2CH20 (J2CH, , - or +CH2+ may be formed by bonding to form a ring).

In general formula (3), ~, the hydrocarbon group of R3 is 0
1-C22 alkyl group (methyl, ethyl, propyl.

butyl, octyl, lauryl, stearyl, oleyl, etc.) and cycloalkyl groups (cyclohexyl, etc.). A3. Examples of the (1') alkylene group of A4 to C4 include ethylene, 'propylene and butylene groups. n3. n is an integer of 1 or more, preferably 1-6.

Alkanolamines (b) include alkanolamines (monoethanolamine, jetanolamine, triethanolamine, isopropanolamine, butanolamine, etc.), alicyclic amine alkylene oxide side adducts (cyclohexylamino ethanol, cyclohexylamine alkylene oxide adducts, etc.), aliphatic amine alkylene oxide adducts (octylamine,
laurylamine, palmitylamine, stearylamine.

alkylene oxide adducts such as diethylaminoethanol) and heterocyclic amine alkylene oxide adducts (such as morpholine alkylene oxide adducts)
can be given. Preferred among these are monoethanolamine, jetanolamine, triethanolamine and cyclohexylaminoethanol.

The weight ratio of (A) and (to) is usually 99.5: 05
-50:■ Preferably 95:5-70-80. (
If the amount of B) is less than 0.5, the effect of adding B) will be particularly low, and if the amount of B) is more than 50, the antirust property will deteriorate.

The method of mixing (A) and (B) is not particularly limited; for example, after dissolving υ) in water, adding (A) and mixing; stirring (A) and (B) in water; An example of this method is to add the ingredients and mix and stir. The former is preferred.

The mixture may be mixed at room temperature or heated. In addition, if the cation used for neutralizing (A) is an alkanolamine, an excess amount of the alkanolamine is added during neutralization to form a mixture of the neutralized salt (A) and the alkanolamine (b). Good too.

The water-soluble temper rolling oil composition of the present invention contains component (μ) and component (to), but if necessary, antifoaming agents, surfactants, etc. may be added to the extent that the effects are not diminished. can. Inorganic phosphates, borates, nitrobenzoic acid, nitrosalicylic acid, aliphatic amine N-oxide compounds, etc. described in Japanese Patent Application No. 56-86888 can also be added.

In principle, the water-soluble temper rolling oil composition of the present invention is used as an aqueous solution. Its concentration is usually 1 to 20% by weight,
Preferably it is 1 to 10% by weight.

The material to which the water-soluble temper rolling oil composition is applied is cold rolled steel strip after batch or continuous annealing. The method of use thereof is to perform light rolling using the part of the present invention in the temper rolling process after the annealing process.

The water-soluble temper rolling oil composition of the present invention has excellent solubility in acids such as hydrochloric acid and sulfuric acid, and even when pickling is performed as a pretreatment of steel sheets by customers, the water-soluble temper rolling oil composition has excellent solubility in acids such as hydrochloric acid and sulfuric acid. There are no disadvantages such as floating substances re-adhering to the steel plate and staining it. It also has excellent rust prevention properties.

The rust prevention performance when the steel plates are stacked is also good over a long period of time. It also has the performance of having a high coefficient of friction (for example, 0.2 or more, in a 1-2% aqueous solution), which is necessary for a temper rolling oil composition.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Rolling Oil Composition of the Present Invention Various performances of the rolling oil compositions (ak) of the present invention and comparative rolling oil compositions (1-p) below were evaluated. Display the results -
Shown in 1.

Comparative rolling oil composition 1: Nitrous acid-amine-based tempered rolling oil m: Benzoic acid/jeta salt n Nioleic acid/jeta salt 0: Lauric acid alkanolamide P Nilaurylamine (EO) 6 Table 1 Note) o : Those that show no abnormality in the relevant test △: 〃
Items exhibiting very slight abnormalities ×: Items exhibiting abnormalities Various performances were evaluated using the following test methods. The test piece used for the test was steel plate 8PC-1 (200X 100X
Q, (imm) was immersed in a test solution of a 5% aqueous solution of the oil of the present invention, squeezed with a rubber roll, and air-dried to adjust the adhesion amount of the test solution to 150 to 200 mg/m'.

(1) 10 g of the rolling oil composition of the present invention in 10 g/hydrochloric acid having an acid solubility of 12 wt.
g/ and whether the solid content settles out or becomes a suspension.
We also observed its solubility, including whether it dissolved in a transparent state.

(2) Wet test (A) Steel plate coated with test liquid (size, 1100t x 2)
00ff) After dropping 9.2 cc of C ion-exchanged water and stacking five steel plates in sequence, they were wrapped in kraft paper and the four corners were tightened with port. This is i degrees 9596 or more, temperature 5
Leave it in a humid box at 0'C for 3 days.

The state of rust in the overlapped portion of the steel plates was observed.

(3) Wet test (B) After stacking five test liquid-treated steel plates, they were wrapped in kraft paper and the four corners were tightened with bolts. This was left in a humid box at a humidity of 95% or higher and a temperature of 50° C. for 10 days, and the state of rust at the overlapped portion of the steel plates was observed.

(4)　Bacrotest The test liquid treated steel plate was left in a box for 5 days.

The state of rust was observed.

(5) Paint Repellent Superac E-42 (trade name, acrylic paint) was applied to the test liquid treated steel plate using a roll.

The repellency of the paint was observed.

(6) Paint adhesion Steel plate coated with Superlac E-42 (coating thickness 15-2
0μ) was immersed in warm water at 40°C for 24 hours, then cross-cut, applied with Erichsen (7 mW), and observed for adhesion using cellophane tape.

Claims (1)

[Scope of Claims] 1. A water-soluble temper rolling oil composition comprising: (A) a dicarboxylic acid partial ester salt of an oxyalkylated amine; and an alkanolamine. 2. The weight ratio of (A) and (B) is 99. ': 0.
The composition according to claim 1, wherein 1 (A) has the general formula %) [wherein R1 is an organic group having a C4 or higher hydrocarbon group; R2゛H2 carbon seven carbon hydrogen group or +A2
0) n2IT, R1 and Ru combine to form 10H2CH
2αEH,, CH, - or +CH21 may form a ring. A, , A is a C2-C4 alkylene group, l< is a dicarboxylic acid residue M, is an alkali metal,
It is an alkaline earth metal, ammonium or amine cation. "Is" 2 is an integer greater than or equal to 1. im is 1 or 2. ] The composition according to claim 1 or 2, which is a compound represented by: 4, (A) is a general formula [wherein R1 is an organic group having a hydrocarbon group of 04 or more;
A1. A2 is a C2 to C4 alkylene group; R1' is a dicarboxylic acid residue; Ml is an alkali metal, alkaline earth metal,
Ammonium or amine cation. n1sn
2 is an integer greater than or equal to 1. ] The composition according to claim 8, which is a compound represented by: 5, (Bl is the general formula [wherein, - is a H1 hydrocarbon group, or +A, 0+n
H and e ``3 m'' 4 is an integer greater than or equal to 1 s A3+
A4 is a C2-C4 alkylene group. ChitoR3 is combined with +C112+-, or -CH2CH20CH2
It may become CH2- to form a ring. ] The composition according to any one of claims 1 to 4, which is a compound represented by the following. 6. The composition according to claim 5, wherein the compound represented by general formula (3) is monoethanolamine, jetanolamine, triethanolamine and/or cyclohexylaminoethanol.