JPH09151229A - Novel phenolic, aqueous resin composition and intermediate and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a phenolic, aq. resin compsn. having excellent water resistance, chemical resistance, adhesion and storage stability by subjecting a phenolic comps. with a particular N-substd. (meth)acrylamide deriv. and an arom. aminosulfonic acid to condensation reaction in the presence of formaldahyde. SOLUTION: This phenolic, aq. resin compsn. comprises a condensate, having an average mol.wt. of 500 to 500000, prepd. by subjecting, to condensation reaction, 1mol of a phenolic compd. with 1 to 0.1mol of N-substd. acrylamide deriv. or N-substd. methacrylamide deriv. represented by the formula (X represents H-C-H, CH3 -C-CH3 , O=S=O, or O; and R represents CH3 or H) and 1 to 0.05mol of an arom. aminosulfonic acid in the presence of 5 to 0.5mol of formaldehyde. Pref., 5 to 200 pts.wt. aq. crosslinkable component having in its molecule two or more functional groups reactive with amino, methylol, hydroxyl and/or other groups is incorporated into 100 pts.wt. aq. resin comps.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phenolic aqueous resin composition, an intermediate thereof and a method for producing the same, for example, a coating film-forming material such as paint, ink, coating agent, sealing agent, adhesive agent and the like. It can be used in fields such as binders.

[0002]

2. Description of the Related Art In recent years, it has been desired to reduce the amount of organic solvents emitted into the atmosphere from the viewpoint of environmental protection. Paint, ink,
Attempts to reduce the amount of organic solvents used have also been tried in the adhesives industry. Among them, phenol-based aqueous resins provide well-balanced paints and adhesives with excellent chemical resistance, corrosion resistance, and adhesion. However, the cured product containing the phenol resin has a drawback that flexibility is insufficient and cracks and cracks are likely to occur due to impact.

Conventional aqueous phenolic resins have a phenolic hydroxyl group in the aromatic nucleus, and a water-soluble resol resin obtained by condensing phenols with formaldehyde under alkaline conditions is used in adhesives, paints and paper phenolic laminates. It is used. However, the aqueous resin used here is colored from reddish brown to light brown, and the cured product and cured film formed using them are similarly hard and colored. Therefore, conventional water-based phenolic resin is a dark color chemical-resistant special paint, adhesive for structural plywood,
It was limited to fields where the color of the resin such as paper phenolic laminate did not matter.

On the other hand, the present inventors have developed an aqueous phenolic resin which is already colorless and transparent and which forms a film having good water resistance, chemical resistance and adhesion to a metal surface (Japanese Patent Application No. 305926), since it is a water-soluble resol resin, there is a problem in storage stability because the condensation reaction proceeds when it is stored at room temperature.

On the other hand, with respect to N-methylolacrylamide, various derivatives have been applied in a wide range of fields, as in the review article (Takeshi Endo supervised: New development of reactive polymers, P.32, CMC). . Examples of the reaction product with phenols include a dihydroxybenzophenone derivative (POLYMER LETTERS EDITION, Vol.15,675 (1977)) and a cosmetic composition containing a photopolymer (Japanese Patent Publication No. 59-29562). There are no reports on phenolic resins, especially the aqueous phenolic resin composition of the present invention.

[0006]

Therefore, as a result of studies to solve the above problems, the present inventors have found that phenols and an N-substituted acrylamide derivative or an N-substituted methacrylamide derivative (hereinafter referred to as "N-substituted (meth ) "Acrylamido derivative") and aromatic amino sulfonic acid are condensed with formaldehyde, the amount of aromatic amino sulfonic acid and formaldehyde used is appropriate for phenols or bisphenols and N-substituted (meth) acrylamide derivatives. When the amount of the phenolic water-based resin is within the above range, it is possible to reduce the coloring property without impairing the water solubility and water dispersibility of the condensate, to impart a film-forming ability, and to have excellent storage stability. The inventors have found that a composition can be obtained and reached the present invention.

Therefore, the main object of the present invention is to provide a novel phenolic aqueous resin which forms a colorless and transparent film excellent in water resistance, chemical resistance, adhesion and storage stability without using any organic solvent. To provide a composition.

Another object of the present invention is to provide an intermediate for producing a novel phenolic aqueous resin composition and a method for producing the same.

[0009]

The above object of the present invention is to provide 1 mol of a phenol, 1 to 0.1 mol of an N-substituted (meth) acrylamide derivative represented by the following general formula (1) and 1 to 1 of an aromatic aminosulfonic acid. An average molecular weight of 5 obtained by condensing 0.05 mol with 5 to 0.5 mol of formaldehyde.
An aqueous resin composition comprising a condensate of 00 to 500,000 and 1 mol of a bisphenol represented by the following general formula (2) in acetic acid in the presence of an acid catalyst, to N-methylol acrylamide or N-methylol methacrylamide ( "N
-Methylol (meth) acrylamide ")
N characterized by reacting at a ratio of 0.2 to 0.7 mol
-Achieved by a method of making substituted (meth) acrylamide derivatives. Hereinafter, the present invention will be described in detail.

The term "phenols" used in the present invention means a mononuclear or polynuclear aromatic compound having a phenolic hydroxyl group, and examples thereof include phenol, para-cresol and its isomers, resorcinol and its isomers, lower alkoxyphenols, and lower alkoxyphenols. Alkylphenols may be mentioned. In addition, bisphenols are included in a part of the phenols here, but specifically, 4,4′-dihydroxydiphenylsulfone and 2,2-bis (4) represented by the following general formula (2). -Hydroxyphenyl) propane, 4,4'-dihydroxybenzophenone, 4,4 '-(perfluoroisopropylidene) diphenol, 4,4'-dihydroxydiphenylmethane, 2,2-bis (4-hydroxyphenyl) butane, 4 ,Four'
-Dihydroxy diphenyl ether, 4,4'-dihydroxy diphenyl sulfite, 4,4'-dihydroxy biphenyl, and isomers thereof.

The N-substituted (meth) acrylamide derivative used in the present invention is a product represented by the following general formula (1) obtained by the reaction of the above bisphenols and N-methylol (meth) acrylamide. Means

The N-substituted (meth) acrylamide derivative is preferably in a ratio of 1 mol of an acrylamidemethyl group or a methacrylamidemethyl group (hereinafter referred to as "(meth) acrylamidomethyl group") to 1 mol of bisphenols. Introduced is desirable, for example 2-
(3-acrylamidomethyl-4-hydroxyphenyl) -2
'-(4-Hydroxyphenyl) propane, 1- (3-acrylamidomethyl-4-hydroxyphenyl) -1'-(4-hydroxyphenyl) sulfone, 1- (3-acrylamidomethyl-4-hydroxyphenyl) -1 '-(4-Hydroxyphenyl) methane, 1- (3-acrylamidomethyl-4-hydroxyphenyl) -1'-(4-hydroxyphenyl) ether, 2- (3-methacrylamidomethyl-4-hydroxyphenyl)- 2 '-(4-hydroxyphenyl) propane, 1- (3-
Methacrylamidomethyl-4-hydroxyphenyl) -1'-
(4-hydroxyphenyl) sulfone, 1- (3-methacrylamidomethyl-4-hydroxyphenyl) -1 '-(4-hydroxyphenyl) methane, 1- (3-methacrylamidomethyl)
-4-hydroxyphenyl) -1 '-(4-hydroxyphenyl) ether and the like.

Further, examples of the aromatic aminosulfonic acid used in the present invention include 4-aminobenzenesulfonic acid and its isomers, naphthylaminesulfonic acid and its isomers, and 2-amino-5-methylbenzenesulfonic acid. Those having a methyl group such as can also be used.

Formaldehyde is used as an aqueous solution.

These phenols, N-substituted (meth)
For the acrylamide derivative and formaldehyde, a condensation reaction is carried out in the presence of formaldehyde of 5 to 0.5 mol with 1 mol of a phenol, 1 to 0.1 mol of an N-substituted (meth) acrylamide derivative and 1 to 0.05 mol of an aromatic aminosulfonic acid.

The condensation reaction is preferably carried out in the presence of a basic substance, and as the basic substance used at that time, metal hydroxides such as sodium hydroxide, calcium hydroxide and potassium hydroxide, ammonia and its aqueous solution. Etc. are preferred.

In these assembly reactions, it is preferable to use 1.0 to 2.0 molar equivalents of the basic substance with respect to 1 mol of the aromatic aminosulfonic acid. If these molar ratios and molar equivalent ratios deviate from the ranges, the amount of unreacted aromatic aminosulfonic acid increases, unreacted phenols increase, and unreacted N
-The substituted (meth) acrylamide derivative is likely to increase.

With these charged molar ratios, the concentration is usually 20 to 50% under an aqueous condition, the reaction temperature is 60 to 110 ° C., and the reaction time is 3 to.
The phenolic aqueous resin composition of the present invention can be obtained in 20 hours.

The formaldehyde condensate of the phenols, the N-substituted (meth) acrylamide derivative and the aromatic aminosulfonic acid obtained by the above reaction preferably has an average molecular weight of 500 or more and 500,000 or less, more preferably The range is 1,000 to 100,000. If the molecular weight is less than 500, the chemical resistance, corrosion resistance, flexibility and adhesiveness of the coating will be insufficient, and if it is greater than this range, the viscosity will increase excessively and handling will become difficult. The average molecular weight is measured by the GPC method using sodium polystyrene sulfonate as a standard sample.

N-substituted (meth) used in the above condensation reaction
Acrylamide derivatives can be prepared in acetic acid in the presence of acid catalysts,
0.2 mol of N-methylol (meth) acrylamide is used per 1 mol of the bisphenol represented by the general formula (2).
It can be obtained by reacting 0.7 mol, more preferably 0.4 to 0.55 mol.

In this case, if N-methylol (meth) acrylamide is added in an amount of more than 0.7 mol with respect to 1 mol of the bisphenol, the (meth) acrylamide methyl group is introduced in a ratio of 2 mol or more with respect to 1 mol of the bisphenol. It is not preferable because a large amount of the above components are produced.

Examples of the acid catalyst used in these reactions include sulfuric acid, hydrochloric acid, nitric acid and paratoluenesulfonic acid, and the reaction proceeds in acetic acid in the presence thereof. For example, regarding the ratio of acetic acid to sulfuric acid,
1 to 8 ml of 97% sulfuric acid is mixed with 100 ml and used. In this case, if the amount of sulfuric acid used as a catalyst is 1 ml or less, the reaction efficiency is low and unreacted substances are likely to remain. Further, if the amount of 97% sulfuric acid is more than 8 ml, it is difficult to control the reaction, and a large amount of neutralizing agent is required for the post-treatment after completion of the reaction.

The reaction temperature is 5 to 90 ° C. and the reaction time is 1
~ 36 hours. After the reaction was completed, the reaction solution was added to cold water,
The precipitate generated there is filtered and dissolved in an organic solvent such as ethyl acetate.

Further, after neutralizing the obtained solution and removing inorganic salts by washing with water, the solvent can be removed by distillation under reduced pressure to obtain a reaction product. Examples of the method for purifying the reaction product include a purification method based on silica gel column chromatography.

Even if a mixture of unreacted bisphenol and a component in which 1 mol of (meth) acrylamidomethyl group is introduced to 1 mol of bisphenol, a condensation component of formaldehyde for synthesizing the above aqueous resin is obtained. There is no problem in using it in the reaction.

However, when there are many components in which 2 mol or more of (meth) acrylamidomethyl group is introduced to 1 mol of bisphenols, it tends to remain unreacted when used in the condensation reaction of formaldehyde.

The phenolic aqueous resin composition of the present invention comprises
Since it has a phenolic hydroxyl group, amino group, methylol group, secondary amine, acrylamide group or methacrylamide group (hereinafter referred to as "(meth) acrylamide group") in its structure, it should react with those functional groups. The physical properties can be further improved by blending a crosslinking component capable of forming such as an aqueous epoxy resin, an aqueous melamine resin, an aqueous blocked isocyanate, and an aqueous reactive urethane resin.

At this time, the amount of the aqueous crosslinking component to be added is preferably 5 to 200 parts (by weight). If the amount of the aqueous crosslinking component to be added is 5 parts or less, the effect of adding the crosslinking component is difficult to appear. When 200 parts or more are blended, the transparency, colorlessness or lightness of the coating, storage stability, etc., which are features of the aqueous resin composition of the present invention, may be impaired.

An aqueous resin composition containing an aqueous melamine resin as a crosslinkable component with respect to the aqueous resin composition is particularly excellent in transparency of the coating film, and an aqueous resin composition containing an aqueous epoxy resin is also particularly resistant to chemicals. Excellent in adhesiveness and adhesion to metal surface, the coating using the aqueous resin composition containing the aqueous reactive urethane resin is also excellent in flexibility, and the aqueous resin composition containing the aqueous blocked isocyanate similarly has hardness. Is high and has excellent storage stability.

The rate of film formation can be controlled by adding various known catalysts to the aqueous resin composition of the present invention. Examples of the catalyst used at that time include known aqueous phenol resin catalysts, aqueous epoxy resin catalysts, aqueous blocked isocyanate catalysts and aqueous melamine resin catalysts.

Particularly when a crosslinking component is blended,
The addition of catalyst is even more effective. In the addition of these catalysts, the kinds and amounts thereof are set depending on the actual use conditions required for the product containing the phenolic aqueous resin composition of the present invention. Depending on the required conditions, it can be added at the time of preparing the aqueous resin composition, but a catalyst may be added immediately before the film forming step.

The aqueous crosslinked resin composition of the present invention thus obtained is particularly excellent in adhesion to the metal surface,
Not only is it excellent as a primer for painting and adhesion, but it can also be applied as a vehicle resin for water-based paints and a binder resin for water-based inks.

Other than the above film-forming materials, water-based adhesives for plywood, water-based adhesives for various plastics,
It is also useful as a binder for fibrous substances such as pulp and glass fibers and particulate substances such as wood powder, cellulose powder and ceramics.

Further, the aqueous resin composition of the present invention may be used in combination with other non-reactive aqueous resin.
In this case, water-based urethane, water-based polyester, various latexes, water-based acrylic, etc. are exemplified as the non-reactive water-based resin having no reactivity.

The aqueous crosslinked resin composition of the present invention is used by adding 0.01 to 15 parts (by weight) of a drying promoting component such as alcohol in order to improve the evaporation rate of water during drying, if necessary.

In addition, pigments such as rust preventive pigments, coloring pigments, extender pigments, thixotropic agents, viscosity modifiers, flow aids, surface modifiers, primary rust preventives, defoamers, antiseptics, fungicides, etc. The various additives of (1) are added and mixed in the required amounts.

Since the N-methylol (meth) acrylamide derivative of the present invention has a radical-polymerizable double bond in the molecule, it can be copolymerized with other radical-polymerizable monomers.

In other words, it is a useful substance that can be widely used in various ways as a novel acrylic monomer having a phenolic hydroxyl group.

The aqueous resin composition of the present invention has good flexibility, good adhesive strength, chemical resistance, acid resistance, alkali resistance,
Shows water resistance and has excellent storage stability.

Since an aqueous resol resin, which is a general aqueous phenol resin, makes itself aqueous, it has 1 mole or more of methylol groups per 1 mole of phenol nucleus, whereas the novel phenol resin of the present invention has an aromatic The amount of the methylol group can be controlled appropriately by making the resin hydrophilic by the group aminosulfonic acid.

This makes it possible to freely control the density of crosslinks in the film formed during drying and baking, and to impart flexibility to the film by lowering the crosslink density.

The (meth) acrylamidomethyl group introduced into the bisphenol suppresses the condensation reaction of the methylol group due to its steric hindrance, but the molecular weight of the condensate can be freely adjusted by controlling the reaction temperature and reaction time. You can control. Rather, the steric hindrance of the (meth) acrylamidomethyl group works effectively during storage at room temperature and can suppress the condensation reaction of the methylol group during storage at room temperature.

Furthermore, since the use of bisphenols can suppress the formation of a quinone structure which is a chromophore, the color number of the condensate can be further reduced.

Further, by reducing the compounding ratio of the aromatic amino sulfonic acid, it is possible to further suppress the formation of chromophore and increase the water resistance of the coating film.

Furthermore, by mixing the aqueous resin composition of the present invention with a crosslinkable component such as an aqueous epoxy resin, an aqueous melamine resin, an aqueous blocked isocyanate, an aqueous reactive urethane resin, the metal adhesion of the coating, chemical resistance, water resistant,
The weather resistance can be further improved.

Embodiments of the present invention will be described below with reference to examples, but the present invention is not limited thereto. In addition, all "parts" indicating the blending amount indicate "parts by weight".

[0047]

【Example】

Embodiment 1 FIG. A reactor equipped with a stirrer, a reflux device, a thermometer, and a formaldehyde aqueous solution dropping device was added to the reactor with ion-exchanged water
Parts, 43.3 parts of 4-aminobenzenesulfonic acid and 11 parts of sodium hydroxide are added and dissolved by stirring. Phenol in this aqueous solution
169.4 parts, 2- (3-acrylamidomethyl-4-hydroxyphenyl) -2 '-(4-hydroxyphenyl) propane 31.1
Parts were added. The resulting reaction solution was heated to a temperature of 80 ° C, 113.6 parts of a 37% aqueous formaldehyde solution was added dropwise over 1 hour with stirring, and the mixture was further reacted at a temperature of 80 ° C for 9 hours, and water was added to bring the solid content to 30%. It was adjusted. The aqueous condensate obtained has a viscosity of 38.
cps (solid content 30% aqueous solution, 25 ° C), and the weight average molecular weight was 27,000.

Embodiment 2 FIG. In a reactor similar to that of Example 1, 705.1 parts of ion-exchanged water and 43.3 of 4-aminobenzenesulfonic acid were added.
And 11 parts of sodium hydroxide are added and dissolved by stirring. 2,2-bis (4-hydroxyphenyl) propane 20
5.5 parts and 2- (3-acrylamidomethyl-4-hydroxyphenyl) -2 '-(4-hydroxyphenyl) propane 31.1 parts were added. The obtained reaction solution was heated to a temperature of 80 ° C., 113.6 parts of a 37% aqueous formaldehyde solution was added dropwise over 1 hour with stirring, and the reaction was continued at a temperature of 80 ° C. for 9 hours. After the reaction was completed, water was added to adjust the solid content to 30%. The obtained aqueous condensate had a viscosity of 65 cps (solid content 30% aqueous solution, 25 ° C.) and had a weight average molecular weight of 36,000.

Embodiment 3 FIG. In the same reactor as in Example 1, 748.4 parts of ion-exchanged water and 43.28 of 4-aminobenzenesulfonic acid were added.
And 11 parts of sodium hydroxide are added and dissolved by stirring. 2,2-bis (4-hydroxyphenyl) sulfone 22
5.3 parts and 2- (3-acrylamidomethyl-4-hydroxyphenyl) -2 '-(4-hydroxyphenyl) propane 31.1 parts were added. The obtained reaction solution was heated to a temperature of 80 ° C., 113.6 parts of a 37% aqueous formaldehyde solution was added dropwise over 1 hour with stirring, and the reaction was continued at a temperature of 80 ° C. for 9 hours. After the reaction was completed, water was added to adjust the solid content to 30%. The obtained aqueous condensate had a viscosity of 65 cps (solid content 30% aqueous solution, 25 ° C.), and had a weight average molecular weight of 37,500.

Embodiment 4 FIG. In the same reactor as in Example 1, 710.3 parts of ion-exchanged water and 43.3 of 4-aminobenzenesulfonic acid were added.
And 11 parts of sodium hydroxide are added and dissolved by stirring. 2,2-bis (4-hydroxyphenyl) propane 20
5.5 parts and 1- (3-acrylamidomethyl-4-hydroxyphenyl) -1 '-(4-hydroxyphenyl) sulfone 33.3 parts were added. The obtained reaction solution was heated to a temperature of 80 ° C., 113.6 parts of a 37% aqueous formaldehyde solution was added dropwise over 1 hour with stirring, and the reaction was continued at a temperature of 80 ° C. for 9 hours. After the reaction was completed, water was added to adjust the solid content to 30%. The obtained aqueous condensate had a viscosity of 65 cps (solid content 30% aqueous solution, 25 ° C.) and had a weight average molecular weight of 37,000.

Embodiment 5 FIG. In a reactor similar to that of Example 1, 698.6 parts of ion-exchanged water and 43.3 of 4-aminobenzenesulfonic acid were added.
And 11 parts of sodium hydroxide are added and dissolved by stirring. 2,2-bis (4-hydroxyphenyl) propane 20
5.5 parts and 1- (3-acrylamidomethyl-4-hydroxyphenyl) -1 '-(4-hydroxyphenyl) methane 28.3 parts were added. The obtained reaction solution was heated to a temperature of 80 ° C., 113.6 parts of a 37% aqueous formaldehyde solution was added dropwise over 1 hour with stirring, and the reaction was continued at a temperature of 80 ° C. for 9 hours. After the reaction was completed, water was added to adjust the solid content to 30%. The obtained aqueous condensate had a viscosity of 65 cps (solid content 30% aqueous solution, 25 ° C.) and had a weight average molecular weight of 36,000.

Embodiment 6 FIG. In the same reactor as in Example 1, 708.4 parts of ion-exchanged water and 43.3 of 4-aminobenzenesulfonic acid were added.
And 11 parts of sodium hydroxide are added and dissolved by stirring. 2,2-bis (4-hydroxyphenyl) propane 20
5.5 parts and 2- (3-methacrylamidomethyl-4-hydroxyphenyl) -2 '-(4-hydroxyphenyl) propane 32.5 parts were added. The obtained reaction solution was heated to a temperature of 80 ° C., 113.6 parts of a 37% aqueous formaldehyde solution was added dropwise over 1 hour with stirring, and the reaction was continued at a temperature of 80 ° C. for 9 hours. After the reaction was completed, water was added to adjust the solid content to 30%. The obtained aqueous condensate had a viscosity of 65 cps (solid content 30% aqueous solution, 25 ° C.) and had a weight average molecular weight of 37,000.

Embodiment 7 FIG. In the same reactor as in Example 1, 699.1 parts of ion-exchanged water and 43.3 of 4-aminobenzenesulfonic acid were added.
And 11 parts of sodium hydroxide are added and dissolved by stirring. 2,2-bis (4-hydroxyphenyl) propane 20
5.5 parts and 18.5- (3-acrylamidomethyl-4-hydroxyphenyl) -1 '-(4-hydroxyphenyl) ether 28.5 parts were added. The obtained reaction solution was heated to a temperature of 80 ° C., 113.6 parts of a 37% aqueous formaldehyde solution was added dropwise over 1 hour with stirring, and the reaction was continued at a temperature of 80 ° C. for 9 hours. After the reaction was completed, water was added to adjust the solid content to 30%. The obtained aqueous condensate had a viscosity of 65 cps (solid content 30% aqueous solution, 25 ° C.) and had a weight average molecular weight of 36,000.

Examples 8 to 16 Using the condensates synthesized in Examples 1, 2 and 3, the crosslinkable components were blended at the blending ratio (solid content weight ratio) shown in Table 1, and the solid content was 30%. Adjusted to. However, the parts by weight indicate the weight of the solid content.

Comparative Example 1 To the same reactor as in Example 1, 593 parts of ion-exchanged water, 43 parts of 4-aminobenzenesulfonic acid and 11 parts of sodium hydroxide were added and dissolved by stirring. In this aqueous solution
228 parts of 2,2-bis (4-hydroxyphenyl) propane was added. The resulting reaction solution was heated to a temperature of 80 ° C, 162 parts of a 37% aqueous formaldehyde solution was added dropwise over 1 hour, and the temperature was further changed to 80 ° C.
Was reacted for 2 hours. After the reaction was completed, water was added to bring the solid content to 30.
%. The resulting aqueous condensate has a color number of 2 and a viscosity of 70c.
ps (30% solid content aqueous solution, 25 ° C), weight average molecular weight
It was 55,000.

Comparative Examples 2 to 4 Aqueous resins of Comparative Examples 2 to 4 were prepared according to the resin blending ratios shown in Table 1.

[0057]

[Table 1]

The following components were used as the compounding crosslinkable components in Table 1. Water-based melamine resin; Watersol S-695 (manufactured by Dainippon Ink & Chemicals, Inc.) Water-based epoxy resin: Aquatoto 8535 (manufactured by Toto Kasei) and Epicurure 3255 (manufactured by Yuka Shell) were used in a 1: 1 mixture. Aqueous blocked isocyanate; Elastron BN-69 (Daiichi Kogyo Seiyaku) Aqueous urethane resin: Superflex E-2000 (Daiichi Kogyo Seiyaku) Aqueous resol resin; Aqueous resol resin A: BRL-105 (Showa High Polymer) Aqueous Resol resin B: DM-465 (manufactured by Oshika Shinko)

Embodiment 17 FIG. With respect to the aqueous resins of Examples 1, 2, 3 and Comparative Example 1, changes in viscosity with time when stored at room temperature are shown in FIG. From the results of FIG. 1, it can be seen that the aqueous resin of the present invention exhibits good storage stability.

Example 18. 100 ml of acetic acid and 22.8 parts of 2,2-bis (4-hydroxyphenyl) propane were added to a reactor equipped with a stirrer and stirred until 2,2-bis (4-hydroxyphenyl) propane was dissolved. While cooling the reactor with ice water, 5 ml of 97% sulfuric acid was added, and further 5.05 parts of N-methylol acrylamide was added. After stirring the reaction solution at room temperature for 20 hours, the reaction solution was added to 1 liter of ice water while stirring. Thereafter, the precipitate was collected by filtration and dissolved in 1 liter of ethyl acetate. The ethyl acetate solution was washed with saturated brine and 10% aqueous sodium carbonate solution, and the ethyl acetate solution was concentrated.
The reaction product was separated by silica gel chromatography (solvent: ethyl acetate) to obtain 2- (3-acrylamidomethyl-4-hydroxyphenyl) -2 '-(4-hydroxyphenyl) propane (18.6 parts, yield 60%). . The structure of 2- (3-acrylamidomethyl-4-hydroxyphenyl) -2 '-(4-hydroxyphenyl) propane was confirmed by ¹ H-NMR. Assignment of ¹ H-NMR is shown in FIG. 2.

(Test Method) Examples 1 to 16 and Comparative Examples 1 to 1
The water-soluble resin composition prepared in 4 was diluted with water to a solid content of 10%, spray-coated on a base material (polished mild steel plate or glass plate), and a wettability test was performed, followed by preliminary drying at room temperature or 60 ° C. And baked at 180 ° C. for 20 minutes. Film thickness is 10-15μ
m. The following pencil hardness test, adhesion test, impact resistance test, acid resistance test, alkali resistance test, color number measurement and color tone evaluation of the coating film were performed on the obtained coated plate. The results of the tests shown below are shown in Table 2.

(Wettability Test) On a degreased polished mild steel sheet (based on JIS-G3141), a 10% diluted aqueous resin is spray-coated to see if the coating material spreads uniformly or unevenly on the steel sheet. Was visually evaluated.

The following tests were conducted using a test plate having a coating formed on a polished mild steel plate.

(Pencil hardness test) According to the JIS K5400 standard pencil scratch test method. Pencil (Mitsubishi Uni, made by Mitsubishi Pencil,
Only the wood part of the product name) was scraped off, and the core was rubbed against the coated steel plate surface at an angle of 45 degrees to indicate the pencil hardness just before the coated surface was scratched.

(Adhesion Test) A test was conducted based on the JIS K5400 standard eye-eye test method. Make a cut on the painted surface with a cutter to make 100 cuts at intervals of 2 mm, attach cellophane adhesive tape on it and peel off 5 times in the 180 degree direction, and count the number of remaining cuts .

(Impact resistance test) A test was conducted based on the DuPont test method specified by JIS K5400. 50g of 50g
The changes that occur in the coating when dropped from a height of cm were evaluated.

(Acid resistance test) A test was conducted based on the acid resistance test specified in JIS K5400. After soaking in a 5% sulfuric acid aqueous solution for 24 hours, gently washing with running water, shaking off the water, and visually observing the state of the coating film. Furthermore, the test piece was left in the standard state for 2 hours, and the state of the coating film was examined again.

(Alkali resistance test) The test was carried out based on the alkali resistance test of JIS K5400. After soaking in 5% sodium carbonate solution for 24 hours, wash gently with running water,
After shaking off the water, the state of the coating film is visually inspected.
Furthermore, the test piece was left in the standard state for 2 hours, and the state of the coating film was examined again.

(Measurement of Color Number) The color number of a 30% aqueous solution of the prepared aqueous resin and compounded composition was measured by the Gardner method.

(Evaluation of color tone of coating film) An aqueous resin was cast on a 2 mm thick glass plate, preliminarily dried at room temperature or 60 ° C., and then baked at 180 ° C. for 20 minutes to form a 20 μm film. It was This was visually evaluated.

From the results shown in Table 2, the aqueous resin composition of the present invention not only forms a coating film having low colorability but also exhibits excellent physical properties in pencil hardness, adhesion, impact resistance, acid resistance and alkali resistance. I understand.

[0072]

[Table 2]

[0073]

When phenols, N-substituted (meth) acrylamide derivatives and aromatic aminosulfonic acids are condensed with formaldehyde, phenols or bisphenols and aromatic aminosulfones for N-substituted (meth) acrylamide derivatives are condensed. By keeping the amounts of acid and formaldehyde used in appropriate ranges, it is possible to reduce the colorability without impairing the water solubility and water dispersibility of those condensates, and to impart not only film-forming ability but also storage. It was possible to obtain a phenolic aqueous resin composition having excellent stability.

The film not only forms a film of high hardness as compared with the conventional aqueous phenol, but is also excellent in flexibility, and has the same water resistance, chemical resistance and adhesion to the metal surface as the conventional phenol. Showed sex.

By adding a crosslinking component to the aqueous phenolic resin, a more colorless coating can be formed, and a coating with improved water resistance and chemical resistance can be formed.

Further, by using the phenolic water-soluble resin composition of the present invention, the organic solvent content is low, the coloring property is low, and the chemical resistance, corrosion resistance, flexibility, adhesion and storage stability are excellent. It is possible to provide coatings, inks, film-forming products such as coating agents, sealing agents, adhesives, and binders for fibers.

[Brief description of the drawings]

FIG. 1 is a diagram showing changes with time in viscosity of aqueous resins of Examples and Comparative Examples when stored at room temperature.

FIG. 2 is an explanatory diagram showing NMR assignments confirming the structure of the N-substituted acrylamide derivative of the present invention.

Claims (7)

[Claims] 1. 1 mol of phenols and the following general formula (1):
1-0.1 mol of an N-substituted acrylamide derivative or N-substituted methacrylamide derivative represented by and 1-0.05 mol of an aromatic aminosulfonic acid, formaldehyde 5-0.5
Average molecular weight obtained by condensation in the presence of moles 500 to 50
A phenolic aqueous resin composition comprising a condensate having an amount of 0.00000. 2. The aqueous resin composition according to claim 1, wherein the phenol is a bisphenol represented by the following general formula (2). 3. An N-substituted acrylamide derivative or N-substituted methacrylamide derivative represented by the following general formula (1). 4. In an acetic acid in the presence of an acid catalyst, N-based on 1 mol of a bisphenol represented by the following general formula (2).
A process for producing an N-substituted acrylamide derivative or an N-substituted methacrylamide derivative, which comprises reacting methylol acrylamide or N-methylol methacrylamide at a ratio of 0.2 to 0.7 mol. 5. The aqueous resin composition according to claim 1 or 2.
With respect to 00 parts by weight, amino group, methylol group, hydroxyl group,
Characterized by compounding 5 to 200 parts by weight of an aqueous crosslinkable component having two or more functional groups in a molecule which react with one or more of a secondary amine, an acrylamide group or a methacrylamide group. Aqueous resin composition. 6. The aqueous crosslinkable component is an aqueous melamine resin,
The aqueous resin composition according to claim 5, which is one of an aqueous epoxy resin, an aqueous reactive urethane resin and an aqueous blocked isocyanate. 7. A film forming agent, a sealing agent, an adhesive or an aqueous binder, which comprises the aqueous resin composition according to any one of claims 1, 2, 5, and 6.