JPS6262853A - Self-crosslinking type copolymer composition - Google Patents

Abstract

PURPOSE:A composition forming a film having corrosion prevention and water resistance, obtained by blending a solution of a carbonyl group-containing copoly mer in an organic solvent with an aqueous solution of a specific hydrazine derivative. CONSTITUTION:(A) A solution of a carbonyl group-containing copolymer in an organic solvent is blended with (B) an aqueous solution of a hydrazine derivative containing two or more -NH.NH2 groups is such a way that the amount of the carbonyl group of the copolymer of the component A is 0.2-20 equivalents based on 1 equivalent of -NH.NH2 group. A copolymer obtained by subjecting 0-75wt% (vinyl halide, ethylene, etc.,), 95-25wt% (vinyl ester, 1,3-diene, etc.,), 0.5-80wt% (carbonyl group-containing monomer polymerizable with aldo group or keto group), 0-10wt% (acid amide) and 0-40wt% (acrylonitrile, etc.,) to radical polymerization is used as the component A. An aliphatic polybasic acid dihydrazide is used as the component B.

Description

[Detailed Description of the Invention] [Industrial Application Field] The self-crosslinking copolymer composition of the present invention can be used as a coating material for wood, metal, paper, resin molded products, etc., as an emulsion for adhesives and polymer cements. Useful.

[Prior art] Room-temperature crosslinkable aqueous dispersions of carbonyl group-containing copolymers containing hydrazine derivatives are known ← JP-A-54-
No. 110248, No. 54-144432, No. 55-1
No. 47562, No. 57-3857, No. 58-9664
No. 3, see Publication No. 60-38468). This aqueous dispersion forms a film at a film forming temperature of 5 to 25°C. Moreover,
It is noteworthy that it provides a coating with strong adhesion to adherends such as cloth and metal.

For example, JP-A-54-144432 discloses that (a) an aqueous dispersion of a carbonyl group-containing copolymer having a glass transition temperature of 0 to 50°C, (b) a water-soluble aliphatic dihydrazine derivative, and (c) A paint binder containing water-soluble zinc salts, manganese salts, cobalt salts or iron salts is applied to a cotton cloth tape to form a film, which is measured using a roll stripping device according to DIN 53-289. kg7
It is stated that a cotton cloth tape having an adhesion strength of 3.5 cm was obtained.

The aqueous resin dispersion composition described in the above publications is a composition in which an aqueous dispersion of a copolymer having a carbonyl group is blended with an aqueous solution of a hydrazine derivative of adipic acid dihydrazide or a polymer having two or more -NHφNHz groups. Then, upon drying, the hydrazine derivative undergoes a crosslinking reaction with the carbonyl group of the copolymer to form a film. This film has excellent hardness, elongation, and chemical resistance.

[Problems with conventional technology]

When the above-mentioned aqueous dispersion composition is used as a coating agent for metal, it is desired to further improve the water resistance of the resulting film from the viewpoint of rust prevention.

[Specific measures to solve the problem]

In the present invention, a film excellent in rust prevention and water resistance is obtained by using a non-crosslinking organic solvent solution of a carbonyl group-containing copolymer instead of an aqueous dispersion of the carbonyl group-containing copolymer.

(Structure of the Invention) The present invention provides: (4) Component: An organic solvent solution of a carbonyl group-containing copolymer. Component: An aqueous solution of a hydrazine derivative having two or more -NH-NH2 groups. -NH-NH2 group 1
The carbonyl group (>
The present invention provides a self-crosslinking copolymer composition characterized in that C=O) is blended in an amount of 0.2 to 20 equivalents, preferably 0.5 to 10 equivalents.

Solid component: The organic solvent solution of the carbonyl group-containing copolymer of component (4) contains a mixed monomer of 0.1 to 80% by weight of a polymerizable monomer having a carbonyl group and other polymerizable monomers. In the presence of a polymerization initiator such as benzoyl peroxide, t-butyl perbenzoate, azobisin butyronitrile, etc., in an organic solvent such as butyl selon, tetrahydrofuran, ethyl selon, chlorobenzene, toluene, or tetralin,
It is obtained by radical polymerization at a temperature of 60 to 150°C. The number average molecular weight of this copolymer is 1,500 to 2
00,000.

A preferred composition of the mixed monomers is as follows.

(a), methyl methacrylate, vinyl aromatic compound, (
meth) tertiary butyl acrylate, vinyl chloride,
0 to 80% by weight of electric wood selected from ethylene (b), esters of acrylic or methacrylic acid of alkanols having 2 to 8 carbon atoms, vinyl esters, methyl acrylate, 1,3-diene Selected monomers 95-2ON amount % (c), carbonyl group-containing monomers having at least one aldo or keto group and one polymerizable double bond in the molecule 0
．． 5 to 80% by weight (d) of mono- or/and dicarboxylic acids having 3 to 5 carbon atoms or/and substituted at the nitrogen atom by alkyl groups or/and alkylol groups having 1 to 4 carbon atoms; Amides of these acids 0-10% by weight (e), acrylonitrile, methacrylonitrile, 0-40% by weight
.

The vinyl monomers of component (a), namely methyl methacrylate, vinyl aromatic compounds such as styrene, tertiary butyl (meth)acrylate, halogenated vinyl esters such as vinyl chloride and/or vinylidene chloride, and ethylene are 0 to 80% by weight in the polymer, preferably 20 to 50% by weight
% amount.

(b) 1 minute vinyl monomers include, for example, alcohols having 2 to 8 carbon atoms such as ethanol, isopropanol, n-7' lovanol, n-butanol, imbutanol or 2-ethylhexanol and acrylics. Examples include esters of acids and/or methacrylic acids, methyl acrylate, vinyl acetate, vinyl propionate, and 1,3-dienes (eg, butadiene). Among these, 2-ethylhexyl acrylate, n
-Butyl acrylate and ethyl acrylate are preferred. These component (b) monomers are 95 to 20 in the copolymer.
It is used in an amount of 80 to 50% by weight, preferably 80 to 50% by weight.

In addition, as the carbonyl group-containing monomer of component (c),
A monomer having at least one carbonyl group (aldo group or keto group) and one polymerizable double bond in the molecule,
That is, in particular polymerizable monoolefinically unsaturated aldo and keto compounds, which include esters M(-CO
O-), and compounds having only carboxyl groups (-COOH) are excluded.

Specifically, acrolein, diacetone acrylamide,
Formylstyrene, preferably vinyl alkyl ketones having 4 to 7 carbon atoms, such as in particular vinyl methyl ketone, vinyl ethyl ketone and vinyl isobutyl ketone and/or in which R1 is H or CHa, R2 is H
or an alkyl group having 1 to 3 carbon atoms R3 is 1
an alkyl group having ~3 carbon atoms, and R4 is 1
acrylic (methacrylic) oxyalkylpropanal, diacetone acrylate, acetonyl acrylate, diacetone acrylate, diacetone methacrylate, 2-hydroxyglobyl acrylate acetyl (meaning an alkyl group having ~4 carbon atoms) Acetate and butanediol-1,4-acrylate-acetylacetate are used.

Among these, acrolein, diacetone acrylamide, and vinyl methyl ketone are preferred.

The carbonyl group-containing monomer as component (c) is used in an amount of 0.5 to 80% by weight, preferably 2 to 30% by weight, in the copolymer.

Furthermore, monoolefinically unsaturated heptano and/or dicarboxylic acids having 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid and maleic acid, and/or amides thereof, can be used as monomers for component (d). for example acrylamide, methacrylamide and/or their N-alkyl or N-alkylol derivatives, such as N-methylacrylamide, N-isobutylacrylamide, N-methylmethacrylamide, N-methylolacrylamide,
Mention may be made of N-methylolmethacrylamide, N-ethoxymethylacrylamide, N-n-butoxymethylacrylamide or N-impropoxymethacrylamide.

These vinyl monomers as component (d) may be used in an amount of 10% by weight or less in the copolymer, if necessary.

If necessary, in addition to these vinyl monomers (a) to (d), 0 to 40% by weight of acrylonitrile or methacrylonitrile or/and 10% by weight or less of monoolefinically unsaturated sulfonic acid are added in total, The type and amount of each vinyl monomer are determined so that the copolymer obtained by copolymerization has a glass transition temperature of 185°C to 60°C.

Component (E): Water-soluble hydrazine derivatives having two or more -NH-NH2 groups in the molecule include dihydrazide of polybasic acid;
For example, aliphatic dihydrazide having 12 to 4 carbon atoms such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide and/or itaconic acid dihydrazide. Water-soluble dihydrazines, such as ethylene-1,2-
Dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, etc.: Water-soluble polymers obtained by reacting polyacrylamide and hydrazine hydrate, etc. can be used.

(Composition) The blending ratio of component (1) and component (F) is (1 equivalent of -NH-NH2 group of the hydrazine derivative of component (2) to carbonyl group of the copolymer of component CA) <>C=O) is 0.2~
It is used at a ratio of 20 equivalents.

The following crosslinking reaction occurs by drying the organic solvent and water, resulting in a tough film.

The blending of component (4) and component (B) is as follows: (If the organic solvent for A and ri is a water-miscible solvent such as butyl cellosolve or tetrahydrofuran, the two are mixed as is, but when mixed with water such as toluene, If they are not miscible, add water and emulsifier to the solid ingredients in advance and use oil-in-water (
It is preferable to prepare a dispersion liquid and then add and blend the component (B).

The composition of the present invention may further contain other aqueous dispersions of resins, inorganic fillers, pigments, cement, solvents, viscosity modifiers, and the like.

The composition of the present invention is useful as mastic materials, general paints, floor or roof coating materials, waterproofing materials for paper and fibers, adhesives, and the like.

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the examples are based on weight unless otherwise specified.

Water-based molecules 1!1. Example of liquid production Example 1 Temperature controller, anchor stirrer, reflux condenser, supply container,
The following raw materials were charged into a reaction vessel equipped with a thermometer and a nitrogen inlet tube.

water 180
Part 3570 aqueous solution of the sodium salt of the ester in sulfuric acid of p-nonylphenol (anionic emulsifier) reacted with 20 moles of ethylene oxide; 20 copies.

Separately, the following mixtures and aqueous solutions were prepared as feed I and feed ①.

Feed I Water 200 parts The above anionic emulsifier aqueous solution (35% aqueous solution) 25 parts Styrene
242 parts n-butyl acrylate
215 parts acrolein 1
1 part Acrylic acid 10 parts Acrylamide 10 parts Feed ■ Water 85 parts Potassium persulfate 2.5 parts.

1/101 of Feed I was charged into the reaction vessel into which the raw materials were charged and heated to 90°C, and then 1/10 of Feed I was charged. Next, the remaining feed (1) and feed (2) were simultaneously fed into the reaction vessel in small increments over 3 to 3.5 hours.

After the supply was completed, the reaction was continued at 90° C. for 1.5 hours. The reaction vessel was then cooled to room temperature, and aqueous ammonia was added to adjust the pH of the reaction product to 7-8. The concentration, total amount of copolymer, and monomer composition of the copolymer of the obtained aqueous copolymer dispersion are as shown in Table 1 below, and the monomer composition ratio of the copolymer is as follows: The monomer ratio was almost completely consistent with the calculated monomer ratio.

Rows 2 to 3 The copolymerization composition of Example 1 was changed to the ratio shown in Table 1, and the same polymerization operation as in Row 1 was performed to obtain an aqueous dispersion.

■Production example of components: Example 4 Butyl cellosolve 2
002 was introduced and the temperature was maintained at 85° C. while introducing nitrogen gas.

The following feeds 1 and 2 were uniformly added into this reaction vessel over a period of 2 hours, and after the addition was completed, the temperature was kept at 85°C for 1 hour to complete the reaction and to obtain the desired water-soluble carbonyl group. A butyl cellosolve solution (solid content: 36% by weight) of the containing copolymer was obtained.

This carbonyl group-containing polymer has 100% water? The solubility in the polymer was 0.11, and the number average molecular weight of this polymer was about 15,000.

Example 5 Using the same reaction apparatus as in Production Example 4, 200ml of toluene was placed in the reaction vessel. The temperature was maintained at 80° C. while introducing nitrogen gas. Add the following feed 1 and feed 2 into this reaction vessel.
The mixture was added uniformly over a period of time, and after the addition was completed, the temperature was raised to 85° C. and the reaction was continued for an additional hour to obtain a poorly water-soluble carbonyl group-containing oligomer solution (solid content concentration: 35% by weight).

The solubility of this oligomer in 100f of water is 0.32
The number average molecular weight of the oligomer was approximately 4.000.

Example 6 Using the same reaction apparatus as in Production Example 4, 3 liters of water was added to the reaction vessel.
009 was added, and the temperature was maintained at 90° C. while introducing nitrogen gas. The following Feed 1 and Feed 2 were uniformly added into this reaction vessel over a period of 3 hours, and after the addition was completed, the reaction was further carried out at 90°C for 1 hour. %) was obtained.

This polymer water 100? The solubility in the polymer was 352 or more, and the number average molecular weight of the polymer was about 25.000.

Table 1 shows the resin raw materials used in the production of the copolymers of Production Examples 1 to 6 and the properties of the obtained polymers or oligomers.

The abbreviations in the table are as follows.

SM Nistyrene A-nB n-butyl acrylate ACL
Niacrolein AA Niacrylic acid A"Am1d Niacrylamide 2-EHA: 2-Ethylhexyl acrylate EA: Ethyl acrylate MMA: Methyl acrylate DA・n%@id Nidiacetonoacrylamide Example 7 Temperature controller, anchor type stirrer, reflux cooling A polyacrylamide aqueous solution 300 F (molecular weight 30,000 to 40,0
00.20% aqueous solution) Hydrazine hydrate aqueous solution
6002 (80% aqueous solution) was added and reacted at 70°C for about 10 hours with stirring.

Thereafter, the above reaction product was slowly added to 10 tons of methanol while stirring. The resulting precipitate was purified by a reprecipitation method to obtain a water-soluble acid hydrazide polymer. This polymer had a hydrazide group content of 75 mol % as measured by iodometric titration.

(Leaving space below) Example 1 200 parts of the butyl cellosolve solution of the carbonyl group-containing polymer obtained in Production Example 4 was added to 41 parts by weight of a 36% aqueous solution of sebacic acid dihydrazide, and the mixture was stirred and mixed to obtain a copolymer aqueous dispersion composition. Ta.

This composition was used as a paint and evaluated by the following method.

The results are shown in Table 2.

(11 Water resistance test paint is specified in JIS A-5403 (asbestos slate) A coating film with a thickness of 50μ is obtained on a flexible board (length 7.5c!n, width 15 strokes, thickness 0.5crn) A test piece was prepared by applying the coating as described above and drying it at 20°C for one week.

This test piece was immersed in water at 40°C, and the appearance of the coating film and the presence or absence of blisters were evaluated after 2 days and 1 week.

(2) Rust prevention test The paint was applied to a mild steel plate to form a coating film with a thickness of 50 μm, and was dried at 20° C. for one week to prepare a test piece.

This test piece was immersed in a 3% saline solution, and the occurrence of rust was evaluated visually after 1 and 2 days.

(3) Adhesion test A coating material was applied onto the alkyd resin coating film to obtain a coating film with a thickness of 50 μm, and dried at 20° C. for one week. The resulting coating film was subjected to a peeling test using an adhesive tape (cellophane tape (Product 1) manufactured by Nichiban ■), and the adhesive strength at that time was evaluated.

(4) Evaluation criteria Evaluation was based on the following criteria. Tsu: Rida.

Examples 2 to 6, Comparative Examples 1 to 4 Paints having the composition ratios shown in Table 2 were prepared and used in Example 1.
It was evaluated in the same manner.

The results are shown in Table 2.

Claims (1)

[Scope of Claims] 1), Component (A): An organic solvent solution of a carbonyl group-containing copolymer (B) Component: An aqueous solution of a hydrazine derivative having two or more -NH/NH_2 groups; -NH・NH_2 of hydrazine derivative
A self-crosslinking copolymer composition characterized in that the carbonyl group (>C=O) of the copolymer of component (A) is blended at a ratio of 0.2 to 20 equivalents per equivalent of the group. . 2) The self-crosslinking copolymer composition according to claim 1, wherein the hydrazine derivative of component (B) is an aliphatic polybasic acid dihydrazide. 3), the carbonyl group copolymer of component (A) is (a),
0 to 75% by weight of a monomer selected from methyl methacrylate, vinyl aromatic compound, tertiary butyl acrylate, tertiary butyl methacrylate, vinyl halide, and ethylene (b), 2 to 8 carbon atoms 95 to 25% by weight of a monomer selected from esters of acrylic acid or methacrylic acid of alkanols having atoms, vinyl esters, methyl acrylate, and 1,3-dienes (c), at least one aldo in the molecule 0.5-80% by weight of monomers containing carbonyl groups or keto groups and one polymerizable double bond (d) mono- and/or dicarboxylic acids having 3-5 carbon atoms or/ and 0 to 10% by weight of amides of these acids substituted at the nitrogen atom by alkyl groups and/or alkylol groups having 1 to 4 carbon atoms (e), acrylonitrile, methacrylonitrile 0 to 4
0% by weight Self-crosslinking according to claim 1, which is obtained by radical polymerizing the vinyl monomers (a) to (e) above in the above ratio in an organic solvent. type copolymer composition. 4) The self-crosslinking copolymer composition according to claim 1, wherein the hydrazine derivative of component (B) is a water-soluble polymer obtained by reacting polyacrylamide and hydrazine hydrate. thing.