JPS6262851A - Self-crosslinking type resin composition - Google Patents

Abstract

PURPOSE:A composition forming a film of coating having extremely improved water resistance, chemical resistance, corrosion prevention properties, etc., obtained by adding a high polymer hydrazine derivative to a solution of a copolymer containing an aldehyde group or ketone group in an organic solvent. CONSTITUTION:(A) A solution of a copolymer containing an aldehyde group or ketone group in an organic solvent is blended with (B) a slightly water-soluble high polymer hydrazine derivative containing at least two carboxylic acid hydrazido groups in one molecule in a ratio to give 0.02-10mols carboxylic acid hydrazido groups based on total amounts of aldehyde group and ketone group. A copolymer having 1,500-200,000 number-average molecular weight is used as the component A. A high polymer hydrazide derivative having 1,000-500,000, preferably 3,000-200,000 number-average molecular weight is used as the component B.

Description

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

[Conventional technology]

An aqueous copolymer dispersion containing a water-soluble low molecular weight hydrazine derivative in an aqueous dispersion of a carbonyl group-containing copolymer has already been proposed (Japanese Patent Application Laid-open No. 110248/1983,
(Japanese Unexamined Patent Publication No. 54-144432). Such a copolymer dispersion easily forms a coating film at a film-forming temperature of 5 to 25°C, and provides a coating film with excellent adhesion to adherends such as cloth and metal, but the water resistance of the coating film is , chemical resistance, blocking resistance, and adhesive strength to various adherends were insufficient.

The present inventors first obtained a coating film by incorporating a water-soluble polymer hydrazine conductor having at least two carboxylic acid hydrazide groups in the molecule into an aqueous dispersion of a carbonyl group-containing copolymer. (Japanese Unexamined Patent Publication No. 58-96643). However, even those containing such a water-soluble polymeric hydrazine conductor still have the drawback of insufficient water resistance, chemical resistance, rust prevention, etc.

[Problem that the invention seeks to solve]

The present invention aims to provide a solvent-type copolymer resin composition that provides a coating film with extremely excellent water resistance, chemical resistance, rust prevention, etc.

[Structure of the invention]

(Means for Solving the Problems) As a result of various studies to solve the above-mentioned problems, the present inventors have found that, in an organic solvent solution of a copolymer containing a healdehyde group or a ketone group, This objective could be easily achieved by incorporating a polymeric hydrazine derivative that is poorly soluble in water.

That is, the self-crosslinking co-electronic body fluid composition of the present invention contains a highly water-poorly water-soluble copolymer having at least two carboxylic acid hydrazide groups per molecule in an organic solvent solution of a copolymer containing an aldehyde group or a ketone group. Molecular hydrazine derivative,
The carboxylic acid hydrazide group is contained in a proportion of 0.02 to 10 moles based on the total amount of aldehyde groups and ketone groups.

(5) Component: The copolymer solution containing an aldehyde group or a ketone group used in the present invention contains a polymerizable monomer having an aldehyde group or a ketone group and another polymerizable monomer. diluted with an organic solvent, and diluted with 60-150% in the presence of a polymerization initiator.
Obtained by radical polymerization at a temperature of °C.

The polymerizable monomers include (a) n-alkyl esters of acrylic acid having 1 to 8 carbon atoms, n-alkyl esters of methacrylic acid having 2 to 8 carbon atoms, vinyl esters of saturated carboxylic acids, .99.4 to 25% by weight of a monomer selected from the group consisting of 3-dienes; (b) a polymerizable carbonyl group-containing monomer having at least one aldehyde group or ketone group in the molecule; 0.5 to 80 wt% of the body, (
c) Monoolefinically unsaturated carboxylic acids having 3 to 5 carbon atoms, unsaturated carboxylic amides, N-alkyl and/or N-alkylol derivatives of unsaturated carboxylic amides, monoolefinically unsaturated A monomer selected from the group consisting of carboxylic acids, 0 to 10% by weight, and (d
) 0 to 74. It is preferable to use a monomer mixture containing more than 4% by weight.

As the monomer (b), a carbonyl group-containing monomer having at least one aldehyde group or ketone group and one polymerizable double bond in the molecule is used. Then, ester bond (-C-0-) and carboxyl group (-C-O
Compounds having only H) are not included in this monomer (b). Specific examples of monomer (b) include acrolein,
Diacetone acrylamide, formylstyrene, 4~
Vinyl alkyl ketones having 7 carbon atoms (e.g. vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), with the general formula: 1e represents an alkyl group having 1 to 3 carbon atoms, and R4 represents an alkyl group having 1 to 4 carbon atoms, respectively. ,
diacetone acrylate, diacetone methacrylate,
Acetonitrile acrylate, 2-hydroxypropyl acrylate-acetylacetate, butanediol-
Examples include 1,4-acrylate-acetylacetate. Particularly preferred are diacetone acrylamide,
Acrolein and vinyl methyl ketone.

The resulting copolymer contained in the copolymer solution obtained by copolymerizing the monomer mixture consisting of the monomers (aL (b), (C) and (d)) described above is Monomer (
The copolymer is composed of substantially the same proportions as each of a) to (d).

To explain the effects of each of these monomer units (a) to (d), monomer unit (a) imparts flexibility to the coating film of the composition of the present invention. The monomer unit (1) reacts with the carboxylic acid hydrazide group of the polymeric hydrazine derivative to provide a crosslinked structure and improve the physical properties of the coating film. The monomer unit (C) is used, if necessary, to improve the adhesion of the coating film to the base material, etc., and to improve the physical properties of the coating film using a functional group. Monomer unit (d)
has the effect of adjusting the coating hardness.

Examples of organic solvents for diluting vinyl monomers include toluene,
Xylene, chlorobenzene, ethyl cellosolve, butyl cellosolve, tetrahydrofuran, tetralin, mineral spirit, etc. can be used.

As the polymerization initiator, peroxides such as benzoyl peroxide, cumene hydroperoxide, and tertiary butyl hydroperoxide, azobisisobutyronitrile, and the like are used.

The number average molecular weight of this copolymer containing a keto group or an aldehyde group is 1,5 Q O to 200,000.

Component ('B): In the present invention, a poorly water-soluble polymeric hydrazide having at least two n8 benic acid hydrazide groups in the molecule is added to an organic solvent solution of the copolymer containing an aldehyde group or a ketone group. In this case, "slightly water-soluble" means that the solubility of the polymeric hydrazine derivative in water is 5.5% at room temperature. Of/100m (water) or less. The molecular weight of such poorly water-soluble polymeric hydrazine derivatives is usually t, o o o in terms of number average molecular weight.
~500.000. Preferably 3,000 to 200,0
It is 00.

Such poorly water-soluble polymeric hydrazine derivatives used in the present invention can be easily produced, for example, by reacting a polymer having a carboxylic acid ester group with hydrazine or hydrazine hydrate (i.e., hydrazi/Hittlead) (Japanese Patent Publication No. 52 (Refer to Publication No.-22878).

The above polymer having a carboxylic acid ester group is produced by copolymerizing an ester of an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, or itaconic acid with a lower alcohol and an unsaturated monomer such as styrene, divinylbenzene, or inftylene. By doing so, you can get better results.

(Composition) In the present invention, the blending ratio of <A) the organic solvent solution of the copolymer containing an aldehyde group or a ketone group and the (poor water-insoluble polymeric hydrazine derivative) is the same as that contained in the copolymer solution. Total amount of aldehyde groups or ketone groups in the copolymer 1
The carboxylic acid hydrazide group of the polymeric hydrazine derivative is 0.02 to 10 moles per mole, preferably 0.1 to 2 moles.
This is the ratio of moles.

Various methods can be used for blending the copolymer solution and the polymeric hydrazine derivative in the present invention. A typical blending method is to add a solvent solution of a polymer hydrazine derivative in which a polymer hydrazine hydrate is dissolved in an appropriate solvent (such as isopropyl alcohol) to an organic solvent solution of the copolymer and mix. There are two methods: a method in which a high molecular weight hydrazine derivative is dissolved in the monomer mixture during the production of a four-component copolymer.

The self-crosslinking resin composition of the present invention comprises either the copolymer solution or a poorly water-soluble polymeric hydrazine derivative,
Alternatively, there is no problem in preparing both in combination of two or more types.゛The self-curing ma8 fat composition of the present invention is
In some cases, in addition to the poorly water-soluble polymeric hydrazine derivative, other hydrazine derivatives, such as water-soluble polymeric hydrazine derivatives having two or more carboxylic acid hydrazide groups in one molecule, or low-molecular-weight hydrazine derivatives (e.g. It is also possible to disperse and blend adipic acid hydrazide, sebacic acid hydrazide, etc.). However, it is desirable that such other hydrazine derivatives be used in a relatively small amount, which would impair the effects of the present invention.

Furthermore, the self-crosslinking resin composition of the present invention may contain other acrylic or acrylic-styrenic copolymer aqueous dispersions, alkyd resins, pigments commonly known in paint formulation technology, calcium carbonate, talc, clay, mica powder,
It is possible to incorporate extender pigments such as perlite.

The self-crosslinking resin composition of the present invention can be obtained by applying the self-crosslinking resin composition to a suitable base material and drying it to obtain the following: (1) aldehyde or ketone group in the copolymer and (13)
'fQ=5. Because the hydrazide groups easily react with each other to form a crosslinked structure, the coating film has excellent properties such as water resistance, solubility resistance, durability, blocking resistance, and yellowing resistance. Good adhesion to vinyl resins, alkyd resins, etc.

In particular, in the present invention, since a poorly water-soluble polymeric hydrazine derivative is blended, water resistance, chemical resistance (for example, efflorescence resistance), and rust prevention properties are improved compared to when a water-soluble hydrazine derivative is blended. An excellent coating film can be obtained.

17 Therefore, the self-crosslinking resin composition of the present invention is excellent as a coating material for gloss paints, mastic top coat materials, soft mastic top coat materials, slate materials, and the like. It is also useful as a repair agent for old paint films.

(Examples, etc.) The following will be further described in detail by giving copolymer production examples, polymer hydrazine derivative production examples, examples, and comparative examples.

Parts and sections in these examples are by weight unless otherwise specified.

Copolymer aqueous separation 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 parts 35% aqueous solution of p-nonylphenol sulfuric acid half ester reacted with 20 moles of ethylene oxide) 35% aqueous solution of 11um salt (anionic emulsifier) 5 parts p-nonylphenol (nonionic emulsifier) reacted with 25 moles of ethylene oxide 20 parts of 20% solution.

The following mixture was used as feed 1.

Water 200 parts 35% solution of the above anionic emulsifier 25 parts Styrene 242 parts Acrylic acid n
-Butyl 215 parts acrylic acid
Part 10 Acrolein
11 parts acrylamide
10 Parts As Feed 1, a solution of 2.5 parts of potassium persulfate in 85 parts of water was prepared.

After replacing the inside of the reactor with nitrogen gas, feed 1 is added to the charge.
was added and the mixture was heated to 90°C. Then 10% of Feed 0 was injected into the reactor and then the remaining Feeds 1 and 1 were fed into the reactor uniformly in parallel over a period of 3 to 3.5 hours. After the supply, the mixture was kept at 90° C. for 1.5 hours to perform emulsion polymerization, and then aqueous ammonia (28%) was added to adjust the pH to 8 to obtain an aqueous dispersion of the copolymer.

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

Example 4 Preparation of co-polymer solution that is sparingly soluble in water In a reaction vessel equipped with a temperature controller, anchor type stirrer, reflux condenser, thermometer and nitrogen inlet tube, butyl cellosolve 2.
002 was introduced and the temperature was maintained at 85° C. while introducing nitrogen gas.

Into this reaction vessel, the following feed 1 and feed 2 were uniformly added over a period of 2 hours, and after the addition was completed, the reaction was further maintained at 85°C for 1 hour to complete the reaction and produce the target poorly water-soluble carbonyl group-containing polymer. A butyl cellosolve solution (solid content: 36% by weight) was obtained.

The solubility of this carbonyl group-containing polymer in 100 r of water was 0.12, 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, 200 f of toluene was placed in the reaction vessel and maintained at 80° C. while introducing nitrogen gas. The following feed 1 and feed 2 were uniformly added into this reaction vessel over a period of 2 hours, and after the addition was completed, the temperature was raised to 85°C and the reaction was continued for another 1 hour. A polymer solution (solid content concentration: 35% by weight) was obtained.

The solubility of this copolymer in water is 0.3 F.
The number average molecular weight of the copolymer was approximately 4,000.

Production Example 6 of Water-Soluble Copolymer Using the same reaction apparatus as in Production Example 4, 3 mL of water was added to the reaction vessel.
00r was introduced, nitrogen gas was introduced, and the temperature was maintained at 90°C. 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, an additional 1
The reaction was carried out for a period of time to obtain an aqueous solution (solid content: 27% by weight) of a carbonyl group-containing polymer.

This polymer water 100? The solubility in the polymer was 352 or more, and the number average molecular weight of the polymer was about 2.5000.

Table 1 shows the resin raw materials used for producing the copolymers of Production Examples 1 to 6 and the properties of the obtained copolymers.

In addition, the abbreviations in the table are as follows.

SM: Styrene A-nB n-butyl acrylate ACL
: Acroreini/ 8A Niacrylic acid A-R Niacrylamide 2-EHA : 2-Ethylhexyl acrylate EA : Ethyl acrylate MMA : Methyl methacrylate r) A -AA
m i d Nidiacetone Acrylamide Child Hydrazine Derivative Production Example 7 This example is a production example of a poorly water-soluble polymeric hydrazine derivative.

1 methyl acrylate, 8
67, benzoyl peroxide 0.24? , dioxane 20
0? was added, and the polymerization reaction was carried out at 80° C. for 4 hours while pressing forward.

Next, add hydrazine hydroxide (80% aqueous solution) to this.
50? In addition, a homogeneous liquid phase was obtained, and the reaction was carried out at 80°C for 2 hours. 3. The obtained homogeneous liquid phase reaction product was poured into hexane, and the formed precipitate was separated from house to house to obtain a poorly water-soluble polymeric hydrazine derivative. Ta. This derivative had a hydrazidation rate (ratio of formed carboxylic acid hydrazide groups to the total amount of carboxylic acid ester groups before reaction. The same applies to the following examples) of 30%. Further, this derivative had a solubility in water of 0.3 f/100d (water) and a number average molecular weight of about 20,000.

Example 8 This example is also an example of the production of a poorly water-soluble polymeric hydrazine derivative.

In a reaction vessel similar to Production Example 1, methyl methacrylate 5
02, Butyl methacrylate 40? , t-butylbenzoyl peroxide 0.4? , and D ethyl cellosolve 3
002 was added, and a polymerization reaction was carried out at 90° C. for 6 hours while stirring.

Next, add 20? In addition, a homogeneous liquid phase was obtained, and the mixture was reacted at 85° C. for 4 hours. The obtained homogeneous liquid-phase reactant was treated as in Production Example 1 (7) to obtain a slightly water-soluble polymeric hydrazine derivative. The hydrazidation rate of this derivative was 30, and the solubility in water was 0. 1?/100■ (water), and the number average molecular weight is approximately 1';, r+o.

Met.

Example 9 This example is also an example of the production of a poorly water-soluble polymeric hydrazine derivative.

In a reaction vessel similar to Production Example 7, acrylamide 202
, butyl acrylate 100S', azobisisobutyronitrile 31, and ethyl cellosolve 300f were subjected to a polymerization reaction at 70° C. for 3 hours while stirring with an X-ray machine.

Next, add 4 hydrazine hydrogen chloride (100%) to this.
0y was added to form a homogeneous liquid phase, and the reaction was carried out at 90°C for 5 hours.

The obtained homogeneous liquid phase reactant was treated as in Production Example 1,
A poorly water-soluble polymeric hydrazine derivative was obtained. The hydrazidation rate of this derivative was 15, the solubility in water was 0.6 r/100 (water), and the number average molecular weight was about 10,000.

Example 10 This example is an example of the production of a water-soluble polymeric hydrazine derivative.

In the same reaction vessel as in Production Example 7, an aqueous solution of polyacrylic acid amide was added. (Molecular weight 30,000
~40,000°20% aqueous solution) Hydrazine Hitlerd 3002 (80%
Aqueous solution) was added and reacted at 70°C for about 10 hours with stirring.

The reaction product was poured into methanol, and the resulting mixture was distributed door to door to obtain a water-soluble polymeric hydrazine derivative. This hydrazine derivative had a hydrazidation rate of 70% and a solubility in water of 409/100 ml (water).

Example 1 To 1.0007 μL of the butyl cellosolve solution of the acrylic copolymer having an aldehyde group obtained in Production Example 4, 200 parts of a 40% isopropyl alcohol solution of the poorly water-soluble polymeric hydrazine derivative obtained in Production Example 7 was added. The mixture was added and stirred for 1 hour to obtain the desired self-4 self-crosslinking resin composition.

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

The results are shown in Table 2.

Paint film physical property test method: (1) Water resistance test paint was prepared using a flexible board (7,5 (771X 15αX thickness 0
．． 5C1n) to a thickness of 50μ,
A test piece was prepared by drying at 0°C for one week. This test piece was immersed in water at 40°C for one week, and the appearance of the coating film and the presence or absence of blistering were evaluated.

(2) IT efflorescence test The paint was applied to a thickness of 50 μm on the same flexible board as in (1) above, and dried at 20° C. for one week to prepare a test piece. This test piece was immersed diagonally in water at 40°C, half immersed in the water, and left for one week. ) The elution status was evaluated visually.

(3) Apply the rust prevention test coating to a thickness of 50μ on a mild steel plate, and
The test pieces prepared by drying at 0° C. for one week were immersed in a 3% saline solution for two days, and the occurrence of rust was visually evaluated.

(4) Adhesiveness test The paint was applied to the alkyd resin coating film and the vinyl chloride resin coating film to a thickness of 50 μm, and dried at 20° C. for one week. The resulting coating film was subjected to a peel test using adhesive tape manufactured by Nichiban (trade name) and cellophane tape (trade name), and the adhesive strength at that time was evaluated.

(5) Evaluation criteria The evaluation was based on the following criteria.

A: Very good B: Good C: Average D: Poor Examples 2 to 8, Comparative Examples 1 to 6 A paint having the composition shown in Table 2 was prepared, and this paint was used in Example 1. The obtained coating film was evaluated in the same manner as above.

The results are shown in the same table.

Claims (1)

[Claims] 1) A poorly water-soluble polymeric hydrazine derivative having at least two carboxylic acid hydrazide groups per molecule is added to an organic solvent solution of a copolymer containing an aldehyde group or a ketone group. A self-crosslinking resin composition containing ketone groups in a proportion of 0.02 to 10 moles based on the total amount.