JPS58127760A - Aqueous crosslinkable resin dispersion containing asphalt - Google Patents

Abstract

PURPOSE:To provide the titled aq. dispersion which gives a coating film having well-balanced properties between flexibility and strength or heat resistance, by dispersing a carbonyl group-contg. copolymer, a hydrazine derivative and asphalt in water. CONSTITUTION:70-99.6wt% vinyl monomer such as methyl methacrylate, 0.1- 20wt% carbonyl group-contg. monomer contg. at least one aldehyde or Keto group and one polymerizable double bond per molecule, such as vinyl methyl ketone, and 0.5-10wt% amide of a 3-5C mono-and/or dicarboxylic acid and/or N-(1-4C alkyl)-and/or N-alkylol-substd. derivative of said acid, such as acrylamide, are emulsion-polymerized to obtain a carbonyl group-contg. copolymer (A) having a glass transition temp. of 30 deg.C or below. 100pts.wt. component A, 0.02-1mol (per mol of carbonyl group of component A) of a hydrazine derivative contg. at least two hydrazine residue, and 2-560pts.wt. asphalt are dispersed in water.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous dispersion of an asphalt-containing carbonyl group-containing copolymer that provides a coating film with a good balance of flexibility, strength, and heat resistance.

The dispersion of the present invention is used for floor coating materials, steel pipes, anticorrosive paints for ships, waterproof materials for construction such as roofs and walls, paving base materials for tennis courts and playgrounds, adhesives for tiles, soundproofing materials, and underbodies of vehicles. It is useful as a coating material, waterproofing material for shipping containers, anti-vibration material, filler, etc.

It is known to use inexpensive asphalt as a waterproofing material and a rustproofing material. However, asphalt is preferable because it needs to be heated and melted during construction such as coating and paving. Furthermore, this material has poor heat resistance and becomes brittle at low temperatures, and still has poor crack followability.

In order to omit the heating and melting step during the above-mentioned construction, an asphalt emulsion has been proposed in which asphalt is heated and melted or dissolved in a solvent and then dispersed in water using a surfactant. Although this product has the advantage of being able to be applied at room temperature, it takes several days to dry and does not improve heat resistance, low-temperature embrittlement, or crack followability.

Asphalt emulsions containing latexes such as SBR, SNR, MBR, etc. have been proposed to improve the drawbacks of asphalt emulsions. However, this material is difficult to dilute with water, and it is difficult to apply with a brush.
Roll painting is not possible, = 5- Construction is limited to spray painting.

It has also been proposed to mix an asphalt emulsion with an aqueous emulsion such as polyvinyl acetate or acrylic resin for the purpose of improving the workability of the asphalt emulsion and the flexibility of the resulting cured product (JP-A-56 -95958), it is difficult to obtain a cured product with a balance of flexibility, low-temperature brittleness, heat resistance, and creep resistance as well as tar-epoxy paints and tar-urethane paints. If it is improved, there is a drawback that heat resistance and creep resistance decrease.

The present inventors investigated various resins for the purpose of improving the drawbacks of asphalt/resin aqueous emulsions, and found that asphalt/resin aqueous dispersions using specific crosslinkable resins can be applied by brushing, rolling, or spray painting. We have discovered that it is possible to form a coating film at room temperature that can be applied by any of the following methods and has excellent corrosion resistance, low-temperature brittleness resistance, water resistance, heat resistance, crack followability, and chemical resistance, and has thus arrived at the present invention. did.

That is, the present invention provides the following: 6- (4) Component carbonyl group-containing copolymer having a glass transition temperature of 30° C. or lower ■) Component: Hydrazine derivative having at least two hydrazine residues C) Component Niasphalt (4) An aqueous dispersion containing component (0), in which the hydrazine derivative as component (g) is in a proportion of 0.02 to 1 mole per mole of carbonyl group of the copolymer as component (4); An aqueous dispersion of a crosslinkable carbonyl group-containing copolymer containing asphalt, characterized in that the component asphalt is blended in a ratio of 2 to 560 parts by weight per 100 parts by weight of the component (4) copolymer. It provides:

In the present invention, the carbonyl group-containing copolymer having a glass transition temperature of 30°C or lower, preferably -85°C to +8°C as a carrier component, has at least one aldo group or one keto group in the molecule and one polymerizable copolymer. Monomer with crab heavy bond 0.1~
It is obtained by copolymerizing 10% by weight with other polymerizable monomers (JP-A-54-110248, JP-A No. 54-1)
Publication No. 44432, Japanese Patent Application No. 55-77190, No. 55
-77191).

Specifically, (→, methyl methacrylate, vinyl aromatic compounds, tertiary butyl acrylate, vinyl halides, ethylene, acrylonitrile, methacrylonitrile, acrylic or methacrylic acid of alcohols having 2 to 8 carbon atoms) esters, methyl acrylate, vinyl esters, 1
,3-diene selected monomer 70～
99.6% by weight (b) 6 0.1-20% by weight, preferably 1 carbonyl group-containing monomer having at least one aldo or keto group and one polymerizable double bond in the molecule ~10% by weight (c)
, mono- or/and dicarboxylic acids having 3 to 5 carbon atoms or/and amides of these acids substituted at the nitrogen atom by an alkyl group having 1 to 4 carbon atoms or/and an alkylol group. 5 to 10% by weight, preferably 1 to 5% by weight, of at least the above monomers (a) to (C) obtained by emulsion polymerization and having a glass transition temperature of 30°C or less has flexibility, strength,
This is preferred because it provides a coating film with well-balanced heat resistance.

In particular, (a), methyl methacrylate, tertiary butyl acrylate, vinyl aromatic compounds, vinyl halides, ethylene,
Monomers selected from methacrylnitrile, acrylonitrile, esters of acrylic or methacrylic acid of alcohols having 2 to 8 carbon atoms, methyl acrylate, vinyl esters, i,3-dienes 70~
99.5% by weight, and (b) 0-20% by weight, preferably 1% of a carbonyl group-containing monomer having at least one aldo or keto group and one polymerizable double bond in the molecule. ~10 heavy view% and (c)
, a monocarboxylic acid having 3 to 5 carbon atoms or/and an alkyl group having 1 to 4 carbon atoms in the nitrogen atom or/
and 0.5 to 10% by weight, preferably 1 to 5% by weight, of an amide of these acids substituted with an alkylol group. Further, 5 to 250 parts by weight of the monomers (a) to (C) above mixed in the following proportions are added and emulsion polymerized to form a shell of a different copolymer on the outside of the core. Carbonyl group-containing copolymer (+1) having a multi-layered structure and a glass transition temperature of 165°C to +15°C Monomer of particles (a): 70 to 99.6% by weight, preferably 88 to 96% by weight (b) Academic body o, i ~ 20% by weight, preferably 3
7% by weight of monomer (C) 0.5 to 10% by weight, preferably 1 to 5% by weight, is particularly preferred because it provides a coating film with an excellent balance of the above-mentioned coating film performance requirements. For an example of the production of this carbonyl group-containing copolymer having a multilayer structure, please refer to JP-A-57-385010-.

Further, a mixture of carbonyl group-containing copolymers having glass transition temperatures different by 10 DEG C. (see JP-A-57-3857) also provides a coating film similar to that of the carbonyl group-containing copolymer having a multilayer structure.

Examples of the vinyl monomer of component (a) include methyl methacrylate, vinyl aromatic compounds (e.g. styrene), tertiary butyl acrylate, acrylonitrile, methacrylonitrile, vinyl halides (e.g. vinyl chloride, vinylidene chloride), and ethylene. etc. (group 1) and alcohols having 2 to 8 carbon atoms such as ethanol, impropanol, n-propanol, n-butanol, imbutanol or 2-ethylhexanol and acrylic acid and/or methacrylic acid. Esterified products from acids, methyl acrylate, vinyl acetate and vinyl propionate,
Examples include methacrylamide propane sulfonic acid, 1-3 dienes, especially butadiene (group 1), and the like.

Among these components (a), the vinyl monomers of the first group act to impart flexibility to the coating film, whereas the vinyl monomers of the component (a) of the eighth group act to impart flexibility to the coating film. It functions to impart heat resistance to the film. Therefore, either the first group and the eighth group are used in combination, or the component (a) of the part constituting the nucleus is replaced with the component (a) of the part constituting the shell. Preferably, they are used from one group or vice versa. Among these, when 2-ethylhexyl acrylate is used, the glass transition temperature can be lowered to -85°C.

Next, as the carbonyl group-containing monomer of component (b),
Monomers with at least one aldo group or one keto group and one polymerizable double bond in the molecule, i.e. in particular polymerizable monoolefinically unsaturated aldo and keto compounds, which contain ester bonds ( -COO-), compounds having only carboxyl group C-C0OH) are excluded. In particular acrolein, diacetone acrylamide, formylstyrene, vinyl alkyl ketones preferably having 4 to 7 carbon atoms, such as in particular vinyl methyl ketone, vinyl ethyl ketone and vinylisobutyl ketone and/or R1 is H or CH3, R2 is H or an alkyl group having 1 to 3 carbon atoms, R3 is an alkyl group having 1 to 3 carbon atoms, and R4 is an alkyl group having 1 to 4 carbon atoms. acrylic (methacrylic)oxyalkylpropanal, diacetone acrylate, acetonyl acrylate, diacetone acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate-acetylacetate and butanediol-1,4-acrylate represented by -acetylacetate is used.

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

Component (C) monomers include monoolefinically unsaturated mono- and/or dicarboxylic acids having 3 to 5 carbon atoms, such as acrylic acid, 13-methacrylic acid and maleic acid, and/or The amides may be, for example, acrylamide, methacrylamide, and/or their N-alkyl or N-alkylol derivatives, such as N-methylacrylamide, N-isobutylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide. ,
Examples include N-ethoxymethylacrylamide M, N-butoxymethylacrylamide or N-isopropoxymethacrylamide, among which acrylic acid,
Preferred are methacrylic acid, itaconic acid and maleic acid.

The type and amount of these monomers are determined so that the resulting carbonyl group-containing copolymer has a glass transition temperature (Tg) of 30°C or less, preferably -65°C to +15°C. If Tg exceeds 30° C., the coating film formation properties at room temperature are impaired and the low temperature brittleness resistance of the coating film is also reduced.

The above-mentioned emulsion of carbonyl group-containing copolymer particles having a multilayer structure can be easily produced using a conventional emulsion polymerization method as described in JP-A-57-3850-14-.

For example, first stage emulsion polymerization is performed in a system of the monomers that form the core portion of the polymer particles, an emulsifier, a polymerization initiator, and water, and after the polymerization is substantially completed, the monomers that form the core portion of the polymer particles are A polymer and a polymerization initiator are added to perform second stage emulsion polymerization. At this time, in order to make the synthetic resin particles produced have a two-layer structure, no emulsifier is added in the second stage emulsion polymerization, or even if added, the amount is limited to such an extent that new particles are not formed. Advantageously, care is taken to ensure that polymerization substantially proceeds in the polymer particles formed.

The structure of this copolymer particle does not necessarily have to be a two-layer structure, and the monomer composition can be changed as necessary to carry out the third stage polymerization.
Alternatively, it is also possible to carry out further polymerization to obtain a three-layer or more structure.

The emulsifier and polymerization initiator used in this emulsion polymerization are not particularly limited, but they should be selected according to the monomer system so that the polymerization can be carried out smoothly. Examples of emulsifiers include higher alcohol sulfate ester salts, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts,
Anionic surfactants such as polyoxyethylene alkyl phenol ether sulfate salts, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, ethylene oxide block copolymers, lobilene oxide block copolymers, and sorbitan derivatives are suitable. Polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, pensoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxa, and water-soluble redox type initiators. It is preferable that 50% by weight or less of the solid content of the carbonyl group copolymer emulsion of component (4) of the present invention is other SBR latex,
It is also possible to replace it with polyvinyl acetate emulsion, acrylic resin emulsion, polyvinylidene chloride emulsion, etc.

Next, hydrazine derivatives having at least two hydrazine residues of the (Bl component) will be described.

Examples of the hydrazine derivatives include the following dicarboxylic acid dihydrazides containing 2 to 10 carbon atoms, particularly 4 to 6 carbon atoms. Oxalic acid hydrazide, malonic acid hydrazide, succinic acid hydrazide, glutaric acid hydrazide, adipic acid hydrazide, sebacic acid hydrazide, maleic acid hydrazide, fumaric acid hydrazide and/or itaconic acid hydrazide, aqueous aliphatic acids having 2 to 4 carbon atoms Examples include ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, and water-soluble acid hydrazide polymers represented by the following formulas.

■ 17- [In the formula, X is a hydrogen atom or a carboxyl group, Y is a hydrogen atom or a methyl group, and A is each unit of acrylamide, methacrylamide, acrylic ester, methacrylic ester, or maleic anhydride. , B are acrylamide, methacrylamide, acrylic ester, methacrylic ester or other monomer units copolymerizable with maleic anhydride. In addition, tlm and n indicate numbers that satisfy each of the following formulas (2).

The water-soluble acid hydrazide polymer having at least two hydrazide groups in the molecule represented by this general formula is described in detail in, for example, JP-A-55-6535, so a detailed explanation of the polymer will be omitted. do.

Among these, adipic acid dihydrazide, isopolytalic acid dihydrazide, and sepacic acid hydrazide are preferred.

18- These hydrazine derivatives are blended in an amount of 0.02 to 1 mole, preferably 0.4 to 0.6 mole, per mole of carbonyl group of the copolymer of component (4).

When the water in the aqueous dispersion dries, the hydrazine group of this hydrazine derivative undergoes a crosslinking reaction with the carbonyl group of the copolymer of component (4), resulting in a three-dimensional structure with excellent heat resistance, creep resistance, and chemical resistance. Provides a coating film with a network structure. During the formation of this coating film, the asphalt is confined within the crosslinked network structure, resulting in a coating film with excellent heat resistance, low-temperature brittleness resistance, and crack followability.

In addition, the crosslinked coating film has excellent repeatability and stretch recovery properties.

Next, as the asphalt of component (C), natural asphalt such as V-chia asphalt and rock asphalt such as Trinidad Ebure, Giltonite, and Pyrobituminous asphalt, cutback asphalt thereof, and straight asphalt produced from the petroleum refining process are used. Petroleum asphalt and petroleum pitch such as asphalt and blown asphalt, their cutback asphalt, mixed bituminous materials such as pitch pitumen and astar, heavy oil catalytic cracking cycle oil, light oil catalytic cracking cycle oil, lubricating oil and The oil may be a petroleum process oil obtained by extraction, refining, hydrogenation, etc. of these fractions or other fractions, and may also be a mixture of the above substances.

These asphalts are copolymers of component (4) (solid content)
2 to 560 parts by weight, preferably 2 to 100 parts by weight
It is blended in a proportion of 5 to 400 parts by weight, more preferably 35 to 150 parts by weight. If the amount is less than 2 parts by weight, no further improvement in water resistance can be expected. On the other hand, if the amount exceeds 560 parts by weight, the effect of improving the heat resistance, low-temperature embrittlement resistance, and creep resistance of the coating film will be insufficient.

Furthermore, when 25 parts by weight or more is used, an increase in weight can be expected and thick coating can be achieved.

It is best to mix an aqueous dispersion of the two components.As is already known, an aqueous dispersion of asphalt can be prepared by heating and melting the asphalt, or by mixing toluene, xylene, mineral spirits, coal, etc. It can be obtained by dissolving it with tar or the like, mixing it into water containing a nonionic or anionic surfactant, and stirring it mechanically.

In addition to these components (4) to (0), the aqueous dispersion composition of the present invention may optionally contain water-soluble heavy metal salts such as zinc sulfate, manganese sulfate, cobalt sulfate, zinc acetate, manganese acetate, cobalt acetate, A small amount of lead acetate, zinc nitrate, manganese nitrate, cobalt nitrate, lead nitrate, zinc nitrite, lead nitrite, etc. can be blended.

In addition, the aqueous dispersion of the present invention includes pigments commonly known in the paint formulation art, extender pigments such as calcium carbonate, talc, clay, mica powder, pallite, potassium hexametaphosphoric acid, potassium condensed phosphate, sodium or ammonium salts, sodium or ammonium salts of polyacrylic acid, customary anionic or nonionic surfactants, dispersants such as methylcellulose, ethylcellulose, flobylcellulose, carboxymethylcellulose, polyvinyl alcohol, thickeners, Solvents such as toluene, xylene, mineral spirits, and coal tar, plasticizers such as DOP and DBP, inorganic aggregates such as agarite and silica sand, and resin particle aggregates such as rubber powder, foamed polystyrene, foamed polyethylene, and foamed polypropylene. , glass fibers, reinforcing fibers such as pulp fibers, etc. can be blended.

The aqueous dispersion of the present invention is generally prepared by blending the hydrazine derivative of the component (B) and an asphalt emulsion into the aqueous dispersion of the carbonyl group-containing copolymer of the component (4) produced by emulsion polymerization. easily done.

When the aqueous dispersion of the present invention is applied and dried, the aldo group or keto group in the copolymer of component (2) easily reacts with the hydrazide group in the hydrazine derivative of component (6) to form a crosslinked structure. Therefore, the coating film has excellent solvent resistance, durability, blocking resistance, heat resistance, and creep resistance. In addition, since the asphalt particles are held in the network formed by this crosslinked material, the coating film is freed from asphalt stickiness and low-temperature embrittlement.The present invention will be explained in more detail with reference to Examples-22= do. Parts and percentages in these examples are by weight unless otherwise stated.

Polyacrylamide aqueous solution 3001 (molecular weight 30,000-40,0
00.20% aqueous solution) Hydrazine Hitlerde aqueous solution
600? (80% aqueous solution) was added, and the mixture was reacted at 70° C. for about 10 hours with constant stirring.

Thereafter, the above reaction product was slowly added to 101 methanol with stirring. The resulting precipitate was purified by reprecipitation to obtain a water-soluble acid hydrazide polymer. This polymer had a hydrazide group content of 75 mol % as measured by iodometric titration.

) Production Example 1 of Copolymer Particles of Component - Temperature regulator, anchor-shaped 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 200
Part: 20 moles of ethylene oxide; 5 parts of a 35% aqueous solution of the sodium salt of the sulfuric acid half ester of p-nonylphenol (anionic emulsifier); 5 parts; 25 moles of ethylene oxide; 20 parts of a 20% solution of p-nonylphenol (nonionic emulsifier):

Next, after purging the inside of the reaction vessel with nitrogen gas, 10% of the feed I shown below was added, and the mixture was heated to 90°C.

Feed ■ Water 200 parts 35% aqueous solution of the above anionic emulsifier 25 parts Styrene 223 parts 2-ethylhexyl aqueous lJt/-4155 parts acrolein
6 parts acrylic acid 8 parts acrylamide 8 parts.

Furthermore, after charging 10% of 2.5 parts of potassium persulfate dissolved in 85 parts of water (Feed ■) into the container, all of the remaining Feed ■ and 40% of Feed ■ The mixture was fed into the container over a period of 5 hours, and after the feeding was completed, the feed I was kept at the same temperature for 2 hours to polymerize, thereby obtaining a core copolymer.

Into this reaction vessel, the following feed (2) was fed over 1 hour, and the remaining feed (2) was further fed over 0.5 hour,
Then, the reaction was carried out at 90° C. for 1.5 hours to complete polymerization, and the reaction vessel was cooled to room temperature to obtain an aqueous dispersion.

Feed III Methyl methacrylate 65.2 parts 2-ethylhexyl acrylate 25.8 parts acrolein
5 parts acrylic acid
2 parts acrylamide 2
The pH of the aqueous dispersion thus obtained was adjusted to 7 to 8 with aqueous ammonia to obtain an aqueous carbonyl group-containing copolymer dispersion (1) having a solid mass of 48%.

25- Production example 2 of copolymer of prison component 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.

200 parts of water 35% aqueous solution of the sodium salt of the sulfuric acid half ester of p-nonylphenol (anionic emulsifier) reacted with 20 moles of ethylene oxide 5 parts 20% solution of p-nonylphenol (nonionic emulsifier) reacted with 25 moles of ethylene oxide 20 parts The following mixture was used as Feed 1.

Water 200 parts 35% solution of the above anionic emulsifier 25 parts Styrene
240 parts acrylic acid 2-ethylhexyl ester 215 parts acrylic acid 10 parts 26-acrolein 25 parts acrylamide 10 parts Water as feed 8
A solution of 2.5 parts of potassium persulfate in 5 parts was prepared.

After purging the inside of the reactor with nitrogen gas, feed I was added to the charge.
was added and the mixture was heated to 90°C. Then 10% of feed (1) was injected into the reactor, and then the remaining feeds (1) and (2) were fed into the reactor uniformly and in parallel over a period of 3 to 3.5 hours. After being held at 90° C. for another 1.5 hours after the feed, the reactor was cooled to room temperature. The pH of the dispersion was adjusted to 7 to 8 with aqueous ammonia to obtain an aqueous fraction (TI) with a solid content of approximately 48%.

of Ta.

(Margin below) Table 1 St: Styrene MMA: Methyl methacrylate 2-EHA: 2-ethylhexyl acrylate AlIr
Niacrolein 8A Niacrylic acid A/Am1d Niacrylamide composition ■ Asphalt emulsion “ASEM-2” (trade name) manufactured by Yatomi Shokai Asphalt with a softening point of approximately 75°C 62% by weight xylene
15 〃 Nonionic surfactant 2 〃 Water 21 〃 Composition “Straight asphalt with a softening point of about 75°C 60% by weight
Nonionic surfactant 1.5 Carboxymethylcellulose 0.5 Water
38 〃29- Composition■ Strayed asphalt 1-s21i mass% clay with a softening point of about 70°C 3 Sodium nitrite o, 5 Water
44.5//Example 1 Adipic acid dihydrazide, asphalt emulsion composition I, and dibutyl phthalate as a plasticizer were added to the aqueous dispersion (I) of a carbonyl group-containing copolymer having a solid content of approximately 48% obtained in Production Example 1. were blended in the proportions shown in Table 2 and stirred at room temperature to prepare an aqueous dispersion of a carbonyl group-containing copolymer containing asphalt.

This aqueous dispersion was coated on a glass plate with a mold using a roll coater.
The coating was applied to a thickness of 1.5 times using a 100% polyester resin, and dried at room temperature for 7 days and at 40° C. for 2 days to obtain a black coating film.

This coating film was evaluated as follows.

(1) Tensile strength and tensile elongation 18 test specimens were punched out using a No. 2 dumbbell, and 8 specimens each were treated under the following conditions. Elongation was measured.

b) Normal strength elongation Store in a constant temperature room at 20℃ for 1 day.

(mouth), low temperature strength and elongation Low 1) Stored in a constant temperature room at +5℃ for 1 hour, Low temperature 2) -10
Stored in a constant temperature room at ℃ for 1 hour and measured at the same temperature as the storage temperature.

(2), 80℃ heat resistance Punch out the coating film into a size of 20mm x 100+m, store it in a constant temperature room at 20℃ for 1 day, fix the upper end 30m, and
After hanging for 7 hours in a constant temperature room at 20° C., the length e was measured in a room at 20° C., and calculated using the following formula.

0 (3), punch out the coating film into a size of 20 creep width x 100 nun width,
After storing it at 20℃ for 1 day, mark the center with 40 gauge marks and stretch it to 80+cm. It was stored in a constant temperature room for 4 days. Next, the fixation at both ends was released, and the residual strain/N was measured after 3 days, and the residual strain was calculated from the following formula.

0 (4) 1 Workability (a), 20°C drying time The wall thickness is 1.5. The aqueous dispersion was applied to obtain a coating film of
The coating was stored and dried in a constant temperature room of H, and a part of the coating film was cut out every day and immersed in water to investigate the number of days without re-emulsification.

(r mouth), roll coating, brush coating suitable for aqueous dispersion diluted with water to 3000 cps or less at 25°C, mortar mK 3 times reciprocating coating using a general painting tool and a brush. The presence or absence of polymer aggregates was investigated when

These results are shown in Table 2.

Examples 2 to 12, Comparative Examples 1 to 5 Aqueous dispersions having the compositions shown in Table 2 were prepared, and evaluated in the same manner as in Example 1 using these.

The results are shown in the same table.

In addition, ADH in the table refers to adipic acid dihydrazide, and CD
H represents sepacic acid dihydrazide, DBP represents dibutyl phthalate, and KS-1000 represents calcium bicarbonate powder (trade name) manufactured by Kaneko Mining Co., Ltd.

(Margin below) 33-

Claims (1)

[Scope of Claims] 1) "A carbonyl group-containing copolymer having a glass transition temperature of 30° C. or less (Component (G)) A hydrazine derivative component C having at least two hydrazine residues asphalt above (4)" An aqueous dispersion containing component (0), in which the hydrazine derivative as component (B) is present at a ratio of 0.02 to 1 mole per mole of carbonyl group of the copolymer component, and component C). The asphalt is a copolymer of component (4) 10
1. A crosslinkable resin aqueous dispersion containing asphalt, characterized in that it is blended in a ratio of 2 to 560 parts by weight to 0 parts by weight. 2) A patent claim characterized in that the carbonyl group-containing copolymer of component (A) is obtained by emulsion polymerization of at least the following vinyl monomers (a) to (c). Aqueous dispersion (a) according to scope 1, methyl methacrylate, vinyl aromatic compound, tert-butyl acrylate,...vinyl rogenide, ethylene, acrylonitrile, methacrylonitrile, 2 to 8 carbon atoms a monomer selected from esters of acrylic acid or methacrylic acid of alcohols, methyl anlylate, vinyl esters, 1,3-dienes, 70 to 99.6% by weight (b),
0.1 to 20% by weight of carbonyl group-containing monomer having at least one aldo or keto group and one polymerizable double bond in the molecule (c), having 3 to 5 carbon atoms 1 to 4 in mono or/and dicarboxylic acid or/and nitrogen atom
0.5 to 10% by weight of amides of these acids substituted with alkyl groups and/or alkylol groups having 3) carbon atoms;
), methyl methacrylate, tertiary butyl acrylate, vinyl aromatics, vinyl rogenide, ethylene, acrylonitrile, methacrylonitrile, esters of acrylic and methacrylic acids of alcohols having 2 to 8 carbon atoms , methyl acrylate, vinyl ester, 1
．． 3-Diene, carefully selected monomer 70-99
．． 5% by weight; (b) 0-20% by weight of a carbonyl group-containing monomer having at least one aldo or keto group and one polymerizable double bond in the molecule; and (c) 3-20% by weight. Mono- or/and dicarboxylic acids having 5 carbon atoms or/and 1 to 4 at nitrogen atoms
A copolymer [I] obtained by emulsion polymerization of 0.5 to 10% by weight of an amide of these acids substituted with an alkyl group or/and an alkylol group having To this, 5 to 250 parts by weight of the monomers (a) to (C) above mixed in the following proportions are added and emulsion polymerized to form a copolymer shell on the outside of the monomers. 70 to 99.4% by weight of the monomer of the aqueous dispersion (a) according to claim 1, which is a carbonyl group-containing copolymer (I+) particle formed with a multilayer structure. Monomer (b) 0.1-20% by weight (C) monomer
0.5-10% by weight.