JPS5817510B2 - SuiseihifukuyousoSabutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous coating composition that dries at room temperature.

Specifically, although it is an aqueous system, it exhibits the same viscosity in terms of solid content as the organic solvent vehicle used in organic solvent-based coating compositions, and also has a similar acid value. , and relates to an aqueous coating composition using a vehicle in which the pigment can be directly kneaded in the pigment dispersion process, and the mechanical properties, chemical properties, durability F+, etc. of the coating film obtained from the composition. The various properties of the coating are far superior to those of coatings obtained from known water-based coating compositions, and are equivalent to those of coatings obtained from organic solvent-based coating compositions. Or something that shows better performance.

Water-based coating compositions have been desired for reasons such as cost reduction, fire prevention, and hygienic issues for manufacturing workers and painters. The need is increasing due to the problem of scarcity of and key resources.

However, at present, no aqueous coating composition has appeared that can meet these demands.

Conventional room-temperature drying coating compositions: 1. Polymerized oils and alkyd resins whose main components are natural or synthetic drying oils or semi-drying oils, and those formed by oxidative polymerization or cellulose. The mainstream is to use a thermoplastic polymer compound such as a derivative, natural resin or its derivative, thermoplastic condensation type or polymer type polymer dissolved in an organic solvent as a vehicle, and then dry it by evaporation.
In these coating compositions, it is essential to use an organic solvent in order to maintain an appropriate solids content, provide an appropriate viscosity, and form a uniform and beautiful coating film during production and coating.

In addition to the above-mentioned organic solvent-based coating compositions, a few aqueous-based coating compositions are in practical use.

One of them is a water-soluble coating composition that uses polymers that have been made soluble in water by aging the vehicle main component and introducing a large amount of hydrophilic groups; For materials, the viscosity of the system is maintained within an appropriate range for handling (
7. In order to maintain the solid content of the vehicle within a range that allows sufficient coating performance, it is necessary to further compare the molecular weight of the polymer that is the main component of the vehicle with that of an organic solvent-based coating composition. In addition, a large amount of an organic solvent that is compatible with water must be added as a cosolvent.

Therefore, the organic solvent content cannot be significantly reduced.

In addition, as the hydrophilic group introduced in large quantities into the polymer, carboxyl groups, which have a large water-solubility effect, are usually used.
As a result, the acid value becomes very high, which limits the types of pigments that can be added in the production of coating compositions.Furthermore, due to the high acid value and abrasive molecular weight, coatings obtained from coating compositions are The film has serious drawbacks such as poor water resistance, chemical resistance, and durability, and poor flexibility.

Another typical example is an aqueous coating composition using a polymer latex as the main vehicle component, but the polymer latex is a high molecular weight, low viscosity system and does not require a high acid value. However, since latex is a mechanically unstable system, it cannot be used as a vehicle for pigment kneading.

Therefore, coating compositions are usually produced by kneading pigments with hydrophilic pigment dispersion aids, etc., and then adding and mixing them with latex. The water resistance, chemical resistance, and durability of the coating film decrease due to the addition, and since the pigment is not directly wetted by the polymer, which is the main component of the clay, a pigment reinforcing effect cannot be expected, and the performance of the polymer is reduced. It has serious drawbacks such as the inability to demonstrate

The present inventors have developed a water-based vehicle that exhibits similar behavior to the vehicles used in organic solvent-based coating compositions, such as those with a vehicle viscosity of 100 poise or less at a solids content of 40% to 60%. The molecular weight of the polymer that is the vehicle and the main component of the vehicle is comparable to that of a latex polymer, and the vehicle and polymer itself are stable.
By obtaining an aqueous vehicle that can be used directly as a vehicle for mixing pigments, it is possible to create an aqueous coating composition that exhibits behavior and properties n1 that are at least as good as organic solvent-based coating compositions and the coatings obtained therefrom. The present invention was arrived at as a result of repeated research aimed at perfecting the system.

The aqueous coating composition of the present invention has the following general formula: represents an aliphatic hydrocarbon group, aromatic hydrocarbon group, alicyclic hydrocarbon group, or a halide or heterocyclic compound of these groups.

W is O or an integer of 1, and is a divalent to tetravalent organic group represented by C (R12-0←-+R13-0 piece R14), or M, R12 to R14 is R
", M represents a divalent to tetravalent metal ion such as tin, zinc, magnesium, calcium, barium, aluminum, etc., and h y 1 + J + k r
l+In.

n and p are O or an integer of 1 to 4, l+-m+n+
p=2-4, h≦l, i≦m1, J≦11 and ≦p, x+y and 2 are O or an integer of 1, and q and r are O or an integer of 1-100.

However, if All is M, h=j ” l = n
= 0, i = m = integer from 2 to 4, k2p =
An integer from 2 to 4, i + k≦4.

tnW is (A.

In this case, h is O or an integer from 1 to 2, 1°3, and k
is an integer of 0 or 1, l + m + n + p
= 2, h≦1. l≦rn + J≦n + k≦p, and if any one of i, j, is not O, the other three are always O.

However, h = i = j = k = n = p
= O and when l and m are 1, R2 and R5 may form a bond with each other to form a cyclic compound.

] Polymerizable monomers having at least two ethylenically unsaturated double bonds (excluding butadiene and substituted butadiene).

Hereinafter, they will be referred to as L and A monomers.

) (B) General formula % Formula % [In the formula, Rb is a group represented by -R15c double R16- or, and RI 5 and R16 are a hydrogen atom or a methyl group.

Ro is a hydrogen atom, -COOH, or a group represented by 1000R17, and R17 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or R
19-0(-R"O+, R18-,
R18 is an aliphatic hydrocarbon group having 2 to 3 carbon atoms;
9 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

S is O or an integer from 1 to 3.

] A polymerizable monomer having one ethylenically unsaturated double bond and at least one carboxyl group (hereinafter referred to as
B monomer notation.

) and (D): Polymerizable monomers other than those mentioned above (hereinafter referred to as FD monomers).

), the ratio of each polymerizable monomer is 0.5 to 3 A monomers per 100 parts by weight of the mixture.
In an amount ranging from 2 parts by weight, the B monomer increases the acid number of the mixture from 4 to 2 parts by weight.
A mixture of polymerizable monomers in an amount corresponding to the range of 40 and the remainder being the D monomer is subjected to emulsion polymerization to prepare a true copolymer latex, and then a basic compound is added to the latex to adjust the pH. It is characterized by the fact that the aqueous copolymer dispersion obtained by adjusting the amount of copolymer to 6 or more can be used as a vehicle.

The A monomer used to prepare the aqueous copolymer latex of the present invention includes cyclopentadiene, methylcyclopentadiene, dicyclopentadiene, xadiene, cyclohexadiene, ofcudiene, cyclooctadiene, cyclododeca Aliphatic polyunsaturated hydrocarbons such as trieno and their halogen substituted products, polyunsaturated aromatic hydrocarbons such as divinylbenzene, diisopropenylbenzene, divinyltoluene, divinylxylene, etc. Ethylene glycol, diethylene glycol , triethylene glycol, tetraethylene glycol, polyethylene glycol, flobile/glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymer, ■, 3- Butylene glycol, 1,4-
Butilev ReIJ Cole, ■, 4-pencundiol,
Lucky glycols such as hexylene glycol, neopentyl glycol, and hydrogenated bisphenol A (meth)
Diester stones with acrylic acid or crotonic acid and diethers and divinyl ethers with (meth)allylic alcohol or croton alcohol, glycerol, trimethylolethane, trimethylolpropane, pentae IJ S IJ to-/L/, dipene erythritol,
Polyesters of lucky polyhydric alcohols such as hexahydro-8-triazine and trihydroxyethyl isocyanurate with (meth)acrylic acid or crotonoic acid, polyethers and polyvinyl ethers with (meth)allylic alcohol or croton alcohol, tin, zinc,
Metal salts of magnesium, calcium, barium or aluminum with (meth)acrylic acid or crotonic acid; esters and vinyl esters of (meth)acrylic acid or crotonic acid with (meth)allylic alcohol or crotonic alcohol; ) Allyl or croton alcohols Ethers or vinyl ethers with (meth)allyl or croton alcohols, fumaric acid, isophthalic acid, terefumaric acid, oxalic acid, malonic acid, succinic acid, curcuric acid, adipic acid, pimelic acid, subetic acid Dibasic acids such as , azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, polybasic acids such as allyl alcohol or croton alcohol tonodiesters and divinyl esters, trimellitic acid, pyromellitic acid, etc. Polyesters and polyvinyl esters of acid and (meth)allylic alcohol or croton alcohol, tin, zinc, magnesium, calcium or aluminum salts of vinyl sulfonic acid or styrene-P-sulfonic acid may be mentioned; At least one type of monomer selected from the group of monomers can be effectively used.

Monomer B of the present invention includes unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; Methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2n
d-jf alcohol, tert-butyl alcohol,
amyl alcohol, inoamyl alcohol, cyclohexyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, tecyl alcohol, dotecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, phenyl alcohol, benzyl alcohol, etc. When monovalent alcohol gourd or glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, fluoropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, methyl alcohol, L-methyl alcohol, Examples include monoethers with monohydric alcohols such as butyl alcohol, and monoesters with unsaturated dibasic acids such as maleinoic acid, fumaric acid, itaconic acid, and citraconic acid. At least one selected type can be used effectively.

D monomers of the present invention include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, decyl alcohol, isobutyl alcohol,
nd-j-y-l alcohol, tert-decyl alcohol, amyl alcohol, isoamyl alcohol, hexyl alcohol, cyclohexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol,
Monohydric alcohols such as dotesyl alcohol, myristyl alcohol, cetyl alcohol, allyl alcohol, phenyl alcohol, benzyl alcohol, or ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol , monoethers of glycols such as tetrapropylene/glycol and monohydric alcohols such as methyl alcohol, ethyl alcohol, and decyl alcohol, and esters of (meth)acrylic acid or crotonic acid, or maleinoic acid, fumaric acid, itaconic acid, and citraconic acid. Diesters with unsaturated dibasic acids such as ethylene, propylene, butylene, imbutylene, amidino, hexylene,
Lefin hydrocarbons such as cyclohexeno, octyne, inoctene/, teseno, dodecene, methyl/,
Chlorstyrene, P-tert-j thyrstyrene, α-
Aromatic vinyl compounds such as methylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, etc., old vinyl halides such as vinyl fluoride, vinyl chloride, vinyl bromide, vinyl iodide, vinylidene fluoride, vinylidene chloride, odor vinylidene halides such as vinylidene chloride, vinylidene iodide, (meth)acrylonitrile, crotonitrile, 3-amino-crotonitrile, isopropylcyanoacrylate, 2-cyano-3-(dimethylamino)ethyl acrylate, methyleneglutaronitrile, 2 - Unsaturated cyanide compounds such as cyanoethyl acrylate, 2-chloroacrylonitrile, vinylidene cyanide, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid , benzoic acid, P
-tert-butylbenzoic acid, persatic acid (VE
Vinyl esters of monocarboxylic acids such as R8ATTCACID) or unsaturated alcohol esters such as esters with (meth)allyl alcohol or croton alcohol, methyl alcohol, ethyl alcohol, furoyl alcohol, decyl alcohol, isobutyl alcohol, 2nd 7thyl alcohol , tert-butyl alcohol, amyl alcohol, isoamyl alcohol,
Hexyl alcohol, cyclohexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, phenyl alcohol, benzyl alcohol or ethylene glycol,
Glycols consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol with 1 carbon number
These include vinyl ethers of monohydric alcohols consisting of monoethers with to four aliphatic monohydric alcohols, and unsaturated alcohol ethers consisting of ethers with (meth)allyl alcohol or croton alcohol.

In preparing the aqueous copolymer latex, a monomer mixture containing the A monomer in an amount ranging from 0.5 to 32% by weight in the total monomer mixture is used; The viscosity of the aqueous copolymer latex contained in the aqueous coating composition of the present invention becomes extremely high, making it extremely difficult to manufacture and apply the coating composition. The aqueous copolymer latex becomes unstable, making it difficult to directly knead pigments in the production of coating compositions, and even if kneading is possible, the resulting aqueous coating compositions using such latexes The coating film has low gloss and poor physical properties such as flexibility and impact resistance.

In this way, in the production of the aqueous copolymer dispersion of the present invention, A
The use of monomers seems to play a major role in improving coating film performance.

That is, since the A monomer is used, the aqueous copolymer dispersion of the present invention and the pigment can be directly kneaded as described above, so that the water-soluble dispersion aid normally used for dispersing the pigment can be used. There is no need to use a dispersing agent, and it is thought that there will be no deterioration in performance such as water resistance and chemical resistance due to water-soluble dispersing agents. It is thought that the coating film performance is improved because it is appropriately crosslinked.

In addition, when preparing the aqueous copolymer latex, a monomer mixture containing polymerizable B monomers and having an acid value of 4 to 40 as a whole monomer mixture is used. If it is less than 4, the dispersed particles of the obtained aqueous copolymer dispersion are insufficiently solubilized in water and become unstable, making it impossible to directly knead the pigment, and the acid value exceeds 40. in case of,
The aqueous copolymer dispersion is added to the vehicle and the pigment is kneaded.
When preparing a coating composition, for example, if a basic pigment is used, the resulting coating composition may thicken or gel during storage. Moreover, since the coating film obtained from such a coating composition is highly hydrophilic, water resistance, chemical resistance, etc. are reduced.

Manufacture of aqueous copolymer latex (a specific range of the amount of A monomer in the total monomer mixture used, a specific range of acid value as the total monomer mixture, and i), essential requirements in the present invention This determines whether or not the aqueous coating composition of the present invention can be produced and the quality of the coating film obtained from it, and only by strictly following it can the intended purpose be achieved. .

For example, according to British Patent No. 985,276, it is obtained by emulsion polymerization of a mixture of a polyester of a polyhydric alcohol and (meth)acrylic acid, (meth)acrylic acid, and other polymerizable monomers. It is stated that a copolymer emulsion neutralized by adding a base can be used as a pigment dispersant by directly kneading pigments, but the acid value of the copolymer described in the specification is about 300. As mentioned above, this is just a continuation of the concept of making the composition water-soluble by introducing a large amount of hydrophilic groups, as in the case of known water-soluble coating compositions, but in the case of a high acid value like this, Although the stability of the aqueous dispersion is naturally good, as stated in the specification, the viscosity becomes extremely high, so 10%
It is difficult to handle unless the non-volatile content is as follows.
When used as a vehicle for coating compositions rather than as a pigment dispersant, there are restrictions on the pigments that can be used.
Moreover, the performance of the coating film obtained therefrom is of no value at all as a coating.

The aqueous copolymer latex of the present invention can be prepared in an inert atmosphere and under autogenous pressure F or under artificially induced pressure, in a closed container or under atmospheric reflux, in an open container in the presence of a polymerization catalyst or in the absence of a polymerization catalyst. It can be produced by emulsion polymerization of the above-mentioned polymerizable monomer mixture in the presence or absence of an emulsifier and/or a protective colloid.

The solid content of the aqueous copolymer latex is 30 to 70% by weight.
It is preferable to rub it.

In addition, the polymerization reaction temperature does not need to be particularly specified, but it is 0°C.
The temperature is from 100°C to 100°C, preferably from 30 to 90°C, and the pH
Preferably, the value ranges from 2 to 10.

After the polymerization reaction is completed, an inorganic and/or organic base is added to the obtained aqueous copolymer latex to neutralize at least some of the carboxyl groups of the copolymer, thereby producing an aqueous copolymer dispersion. The pH value of the aqueous copolymer dispersion is preferably 6 or more.

When the pH value is 6 or less, the copolymer is insufficiently solubilized in water, the stability of the aqueous copolymer dispersion decreases, and agglomeration may occur during pigment kneading.

For the emulsion polymerization reaction, any known method can be used, such as a monomer dropping method, a pre-emulsion method, or a combination of these methods.

Furthermore, the entire monomer mixture may be divided into two or more parts and a multi-stage polymerization method may be performed, and the monomer compositions of each divided set may be the same or different.

The characteristics of the composition of the present invention may be better exhibited by using such a multi-stage polymerization method using division.

For example, in a two-stage polymerization method, all monomers having functional groups such as carboxyl groups and hydroxyl groups are present only in the divided second-stage polymerizable monomer mixture, so that aqueous copolymerization is possible. The relatively close to the outer layer of the dispersed particles of the coalesced latex allows for the distribution of functional groups, which results in better solubilization of the dispersed particles in the aqueous dispersion, and therefore greater stability, and the presence of functional groups inside the particles. As a result, the water resistance, chemical resistance, etc. of the coating film obtained from the aqueous coating composition can be improved.

Furthermore, the aqueous copolymer dispersion used in the aqueous coating composition of the present invention is obtained from a copolymer composition that has a relatively high secondary transition point, unlike ordinary latex polymers. One of its characteristics is that it tends to form a film easily at room temperature, but this is because the solubilized molecular chains of the outer layer are formed in a film formation process similar to the film formation process from a chain polymer solution. It is thought that this is the time to take.

Therefore, by the multi-stage polymerization method, the amount of the polymerizable monomer mixture in the final stage set is made relatively large compared to the amount of the total polymerizable monomer mixture, and the polymerizable monomers indicated by The content of the group should be much less than that of other groups, or in some cases, it should be included.

It is also possible to raise the conversion temperature of the coating film and form the film at a lower temperature by, for example, not increasing the conversion temperature.

The polymerization catalyst used in the emulsion polymerization step includes inorganic or organic peroxides, such as ammonium, sodium, and potassium persulfates or perborates, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide,
Di-tert-butyl peroxide, diisoglopylbenzene hydroperoxide, peracetic acid, and azo compounds such as: 2,2'-azobisisobutyronitrile, 4,4-azobis-(4-cyanopentanoic) Known radical-forming polymerization initiators such as acids or alkali metal salts thereof can be used, and their usage amount (1
o, oi relative to the total weight of all monomer mixtures.

It is appropriate to use it in the range of 3 to 3% by weight, preferably 0.1 to 1.0% by weight.

In addition, when a peroxide is used, reducing agents such as ascorbic acid and soluble sulfites are used when it is necessary to increase the polymerization rate or lower the polymerization reaction temperature.

Hydrosulfide, sulfone oxalate, thiosulfate,
It can be used as a redox system in combination with a metal monomer or a compound thereof that generates heavy metal ions in water, such as ferrous sulfate.

Emulsifiers used in the emulsion polymerization step include anionic surfactants, such as alkali metal or ammonium alkyl sulfates, such as sodium, potassium or ammonium dodecyl sulfate, sodium dodecyl polyglycol ether salnoate, sodium sulforisinoate, alkyl sulfonates. ,
For example alkali metal or ammonium salts of sulfonated paraffins, fatty acid salts such as sodium laurate,
triethanolamine oleate or abietate,
Alkylaryl sulfonates, such as sodium dodecylbenzene sulfonate or alkali metal sulfates of alkylphenol hydroxyethylene, high alkylnaphthalene sulfonates, naphthalene sulfonic acid formalin condensates, dialkyl sulfosuccinates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylaryl sulfates , nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, sorbitan fatty acid esters, polyoxyethylene sorbicun fatty acid esters, fatty acid monoglycerides such as glycerol monolaurate, polyoxyethylene oxypropylene polymers, etc. Condensation products of ethylene oxide with fatty acid amines, amides or acids, polymeric emulsifiers such as polyvinyl alcohol, sodium poly(meth)acrylate, potassium or ammonium, polyhydroxyethyl(meth)acrylate, polyhydroxypropyl(meth)acrylate, ) Use of acrylate, or a copolymer of two or more types of polymerizable monomers that are the constituent units of these polymers, or a mixture of one or more types of copolymers with other monomers. The amount added is usually 0 to 50 weight, preferably 10 weight or less, based on the total weight of the entire monomer mixture.

As the protective colloid used in the emulsion polymerization step, one or more protective colloids selected from anionic protective colloids such as sodium alginate and ε and nonionic protective colloids such as hydroxyethyl cellulose are suitable.

In addition, known chain transfer agents are used in emulsion polymerization, such as ter
Alkyl mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, carbon tetrachloride, chloroform or triphenylmethane, etc. may be used. In addition to the aqueous copolymer latex, aqueous copolymers Bases used to form the dispersion include ammonia,
Ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, butylamine, dibutylamine, tributylamine, isobutylamine, tert-butylamine, ethanolamine, jetanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, morpholine Inorganic or organic bases such as
One or more types selected from these groups are used.

The amount used may be such that the pH of the aqueous copolymer dispersion is 6 or higher, and it can be added according to a usual addition procedure.

The aqueous copolymer dispersion contained in the aqueous coating composition of the present invention produced as described above has a pH of 6 or more and is treated in the same manner as the vehicle in the known organic solvent-based coating composition, and colored or Clear enamel can be easily prepared.

In the preparation of colored enamel, a coating composition is obtained by directly kneading various inorganic and/or organic pigments.Pigment kneading equipment includes roll mills, pebble mills,
All known equipment can be used, such as whole mills, speed line mills, sand mills, vibratory mills, high speed impeller dispersers, etc.

Most known pigments can be used, and dyes and the like can also be added freely.

For example, white pigments such as zinc white, antimony white, lead white, titanium white, calcium leadate, and lithopone, black pigments such as carbon black, graphite, iron black, and aniline black, gray pigments such as zinc powder, and zinc oxide, Cuprous oxide, red lead, cadmium red, cadmium mercury light, chromium vermilion, red pepper, alisarin lake, indanthrene brilliant orange GK, indanthrene brilliant orange RK, thioindigo red, thioindigo red, toluidine maroon, Permanent Orange, Permanent Orange Ni 2R, Permanent Red F2R, Permanent Red F 5 R, Perlane/Tread 4R, Vermilion Red, Para Red, Pigmet Scarlet 3B,
Villazo Amane Red, Fire Red, Brilliant Carmine 6B, Helio Bordeaux BL.

Benzidine Orange, Bordeaux 5B, Bordeaux 10B1
Red pigments such as Bon Maroon Light, Hon Maroon Medium, Resole Red, Lake Red C1 Lake Red D, Rhodamine Lake Y, brown pigments such as amber, iron oxide powder, yellow lead, yellow ocher, cadmium yellow, litharge, zinc yellow, titanium yellow. , lead cyanamide, green gold,
Yellow pigments such as Hansa yellow and benzidine yellow, zinc wire, emerald green, chrome green, cobalt green, chromium oxide, viridian, pigment green B1, green pigments such as phthalocyanine green, blue pigments such as ultramarine blue, navy blue, and phthalocyanine blue, cobalt purple, Purple pigments such as Mars purple, manganese purple, dioxazine violet, and methyl violet lake, metal powder pigments such as aluminum powder and brass powder, zinc sulfide, zinc cadmium sulfide, calcium sulfide, strontium calcium sulfide, uranine,
Fluorescent pigments such as Thioflavin T10-Damine B, asbestos board, alumina white, clay, diatomaceous earth, chalk, slaked lime,
Gypsum, talc, barium carbonate, precipitated calcium carbonate,
Extender pigments such as precipitated magnesium carbonate, precipitated barium sulfate, abrasive powder, chalk, pallite, bentonite, and white carbon can be used.

It is also free to add other additives known in emulsion polymerization technology or coating composition manufacturing technology, such as chelating agents, buffering agents, salts of mineral or organic acids, solvents, pH regulating aids, etc. .

The aqueous coating composition of the present invention can be applied by known coating methods such as brushing, spraying, airless spraying, electrostatic spraying,
It can be applied using methods such as dipping, electrodeposition, roll coating, and flow coating.

The aqueous coating composition of the present invention can exhibit excellent coating film performance by drying at room temperature or under heated conditions.

The coating composition of the present invention can be applied to various base materials such as wood, metal, stone, concrete, asbestos boards, and plastics.

The aqueous coating composition of the present invention has excellent characteristics as described above, and will be explained more specifically using Examples.

Hereinafter, all parts and units are by weight, respectively.

Example 2 In a flask equipped with a dropping funnel, a stirrer, an inert gas inlet tube, a thermometer, and a reflux condenser, 105 parts of water, 05 parts of ammonium persulfate as a polymerization catalyst, 5 parts of sodium dodecylbenzenesulfonate as an emulsifier, and protection were added. 0.1 part of sodium alginate was added as a colloid, heated to 70° C. while slowly blowing nitrogen gas, and stirred to form a homogeneous solution.

A polymerizable monomer mixture having an acid value of 20.3, consisting of 15 parts of ethylene glycol dimethacrylate, 26 parts of acrylic acid, 55 parts of styrene, and 27.4 parts of dibutyl itaconate prepared in advance through a dropping funnel, was added over a period of 2 hours. and dripped it.

Thereafter, the temperature was maintained at 70° C. and stirring was continued for 2 hours, then cooled to 30° C., and 22 parts of 28% ammonia water was added to obtain an aqueous copolymer dispersion.

The pH of this aqueous copolymer dispersion was 81, and the solid content was 49.
8%, viscosity 1350□cps (B type viscometer, 6r, p,
The same holds true for all examples where the temperature is 25°C or lower.

)Met. Examples 3 to 5 The same reactor as in Example 2 was used, using various monomer mixtures, polymerization catalysts, emulsifiers, and neutralizing agents shown in Table I, and varying their amounts and polymerization conditions. , an aqueous copolymer dispersion was produced by the same reaction procedure.

The results were as shown in Table 1.

Example 6 80 parts of water, 5 parts of polyoxyethylene nonylphenol ether (HLB=15) as an emulsifier, and a polymerization catalyst were placed in a flask equipped with two dropping funnels, a stirrer, an inert gas inlet tube, a thermometer, and a reflux condenser. 0.5 part of ammonium persulfate was added thereto, and the mixture was stirred and heated to 50° C. while slowly blowing nitrogen gas to form a homogeneous solution.

Then, from one dropping funnel, 70 parts of diallyl phthalate, 39 parts of acrylic acid, and 25.0 parts of styrene were added.
A polymerized monomer mixture with an acid value of 30.4, consisting of 20.0 parts of methyl methacrylate and 44.1 parts of ethyl acrylate, was added to 20 parts of water with 0.2 parts of sodium bisulfite from the other dropping funnel. Each dissolved aqueous solution was added dropwise over a period of 2 hours.

Thereafter, stirring was continued for 2 hours while the temperature was still maintained at 50°C, then cooled to 30°C, and 5.6 parts of triethylamine was added to obtain an aqueous copolymer dispersion.

The pH of this aqueous copolymer dispersion was 86, and the solid content was 51.
1%, and the viscosity was 3.230 cps.

Examples 7 and 8 According to the same reaction procedure as in Example 6, various polymerizable monomer mixtures, polymerization catalysts, emulsifiers, and neutralizers shown in Table 2 were used, and their amounts and polymerization conditions were changed to produce aqueous A copolymer dispersion was produced.

The results were as shown in Table 2.

Example 11 A flask similar to Example 6 was charged with 60 parts of water, 2 parts of polyoxyethylene nonylphenol ether (HLB-215) as an emulsifier, and 0.5 part of cumene hydroperoxide as a polymerization catalyst, and nitrogen was gently blown into the flask. While stirring, the mixture was heated to 50° C. and stirred to obtain a homogeneous solution.

After that, 10 ml of diallyl chloride was added from one dropping funnel.
parts, 3.6 parts of methacrylic acid, 45 parts of tributyl ether
．． A pre-emulsion prepared in advance by thoroughly stirring 20 parts of a used polymerizable monomer mixture with an acid value of 23.5 and 3 parts of polyoxyethylene nonylphenol ether (HLB = 15) consisting of 0 parts and 414 parts of styrene was added. A water bath solution prepared by dissolving 0.5 parts of ferrous sulfate in 20 parts of water was added dropwise from one of the dropping funnels over a period of 2 hours.

Thereafter, stirring was continued for 2 hours while the temperature was still maintained at 50°C, and then the mixture was cooled to 30°C, and 26 parts of 28% aqueous ammonia was added to obtain an aqueous copolymer dispersion.

The pH of this product was 8.0, the solid content Gj was 50.1%, and the viscosity was 2,050 cps.

Example 12 In a stirred autoclave equipped with an inert gas inlet tube, a thermometer, and a polymerizable monomer inlet tube, 95 parts of water, 0.5 parts of potassium persulfate as a polymerization catalyst, and 4 parts of sodium dodecylbenzenesulfonate as an emulsifier were added. 0.2 parts of sodium phosphate was added as a buffer, and the mixture was flushed three times with nitrogen gas.

After that, reduce the pressure in the autoclave and add 8 parts of vinyl chloride.
12 parts of vinylidene chloride was charged from the polymerizable monomer inlet tube.

Thereafter, a polymerizable monomer mixture consisting of 5.0 parts of divinylbenzene, 3.9 parts of acrylic acid, 20 parts of methyl acrylate, and 51.1 parts of styrene, which had been prepared in advance by heating and stirring at 50°C, was added for 20 hours. It was so big.

Thereafter, stirring was continued for 4 hours while the temperature was still maintained at 50°C, and then the mixture was cooled to 30°C, and 33 parts of 28% aqueous ammonia was added to obtain an aqueous copolymer dispersion.

The pH of this dispersion was 8.0, the solids content was 50.0%, and the viscosity was 2.630 cps.

Example 16 In a flask equipped with a dropping funnel, a stirrer, an inert gas inlet tube, a thermometer, and a reflux condenser, 110 parts of water, 0.5 part of potassium persulfate as a polymerization catalyst, and polyoxyethylene nonylphenol ether (HLB2) as an emulsifier were added. 15)5
70℃ while slowly blowing in nitrogen gas.
The mixture was heated and stirred to form a homogeneous solution.

Thereafter, a fourth polymerizable monomer mixture consisting of 25 parts of styrene and 25 parts of ethyl acrylate prepared in advance was added dropwise from the dropping funnel over a period of 45 minutes. A second polymerizable monomer mixture consisting of 77 parts of ethyl maleate, 253 parts of styrene, and 12 parts of ethoxyethyl allyl ether was added dropwise over 45 minutes.

Thereafter, the temperature was maintained at 70° C. and stirring was continued for 2 hours, then cooled to 30° C., and 3.5 parts of 28% aqueous ammonia was added to obtain an aqueous copolymer dispersion.

The pH of this aqueous copolymer dispersion was 8.5, and the solid content Gj
47.5%, and the viscosity was 3620 cps.

Examples 17 and 20 Example 11 - Similar operations were carried out with polymerizable monomer mixture compositions:
The experiment was conducted by changing the emulsifier, polymerization catalyst, neutralizing agent, and solid content.

The results were as shown in Table 3.

Example 24 A flask equipped with two dropping funnels, a stirrer, an inert gas inlet tube, a thermometer, and a reflux condenser was charged with 105 parts of water, 2 parts of sodium dodecylbenzenesulfonate, and 0.5 part of ammonium persulfate, and slowly stirred. The solution was heated to 50° C. and stirred while blowing nitrogen gas into it to obtain a homogeneous solution.

Thereafter, a first polymerizable monomer mixture consisting of 20 parts of methyl nucleate and 30 parts of ethyl acrylate, 20 parts of water, and 3 parts of polyoxyethylene nonylphenol ether (HI, B=15) were thoroughly stirred and prepared in advance. The prepared pre-emulsion was added dropwise over a period of 45 minutes.

After the dropping, a second polymerizable monomer mixture consisting of 15 parts of 1,3-butylene glycol dimethacrylate, 3.1 parts of methacrylic acid, 20 parts of styrene and 11.9 parts of allyl butyl ether prepared in advance was added for 45 minutes. In short, drops■
did.

The aqueous solution in which 0.2 parts of sodium bisulfite was dissolved in 20 parts of water was started to be added dropwise at the same time as the first polymerizable monomer mixture pre-emulsion was started, and was added dropwise over a period of 2 hours.

After the dropwise addition was completed, the temperature was maintained at 50° C. and stirring was continued for 2 hours, then cooled to 30° C., and 3.2 parts of dimethylethanolamine was added to obtain an aqueous copolymer dispersion.

The solid content of this aqueous copolymer dispersion was 40.7%, the pH was 79, and the viscosity was 2,530 cps.

Comparative Examples 1 to 5 Aqueous copolymer dispersions were prepared according to the same procedure as in Example 2, except that the amounts of ethylene glycol dimethacrylate and acrylic acid used were outside the scope of the claims of the present invention, as shown in Table 4.

The special numbers were as shown in Table 4.

Example 26 The aqueous copolymer dispersion obtained in Example 2 was used as a vehicle (hereinafter simply referred to as dispersion).

) was used to knead the mill base with the formula -F in a sand mill.

Dispersion of Millbase Formulation Example 2 80. O Rutile type titanium white 50.0 Water 10.0 20 parts of the dispersion of Example 2 and 67 parts of water were added to the kneaded millbase of the above formulation and mixed well to obtain an aqueous coating composition.

The solid content of this product is 60%, pigment weight production (hereinafter referred to as PW)
It is written as C.

) is 50%, and the viscosity (hereinafter referred to as KU value) is 50%.

) was 77.

Examples 28 to 38 Aqueous coating compositions were obtained according to the same procedure as in Example 26, except that the vehicle, pigment, and pigment kneading device were changed as shown in Table 5.

The special numbers were as shown in Table 5.

Example 41 Using the aqueous copolymer dispersion obtained in Example 7 as a vehicle, the following formulation was kneaded in a roll mill.

Formulation (parts) Dispersion liquid of Example 7 63.7 Anatase type titanium white 325 Zinc white 2.0 Ethylene glycol 20 Butyl cellosolve 10 Water 138 The solid content of the obtained aqueous coating composition was 60%, and the PWC was 50 %, and the viscosity (KU value) was 78.

Examples 43-50 Aqueous coating compositions were obtained in the same manner as in Example 41, except that the vehicle, pigment, and pigment kneading device were changed as shown in Table 6.

The number of hours was as shown in Table 6.

Comparative Example 6 The viscosity (KU value) of an aqueous coating composition obtained by repeating the same operation as Example 26 except that the dispersion of Comparative Example 1 was used as a vehicle was 150 or more, and it was impossible to coat. .

Comparative Example 7 An aqueous coating composition obtained by repeating the same operations as in Example 26 except that the dispersion of Comparative Example 2 was used as a vehicle had a solid content of 60%, a PWC of 50%, and a viscosity (KU value).
was 90.

Comparative Examples 8-9 The same operation as in Example 26 was repeated except that the dispersions of Comparative Examples 3 and 4 were used as vehicles, but in both cases the pigments agglomerated during kneading.

Comparative Example 10 An aqueous coating composition obtained by repeating the same operation as Example 26 except that the dispersion of Comparative Example 5 was used as a vehicle had a solid content of 60%, a PWC of 50%, and a viscosity (KU value)
was 90.

Comparative Example 11 In this comparative example, an aqueous copolymer dispersion is added and mixed to a pigment that has been kneaded in advance using a pigment dispersion aid or the like to obtain an aqueous coating composition.

The mixture was kneaded using a ball mill.

Blend Rutile type titanium white 50.0 parts Demol EP 2.0 parts Polycarboxylic acid type dispersant manufactured by Houo Atlas Co., Ltd., 25% aqueous solution) Emulgen 909 1.0 part (manufactured by Kako Atlas Co., Ltd., nonionic wetting agent) Water 15 100 parts of the dispersion of Example 2 and 5 parts of water were added to the kneaded millbase of the above formulation and mixed well to obtain an aqueous coating composition.

The solid content of this product is 58.5%, P'WC 1150%,
The viscosity (KU value) was 80.

Comparative Example 12 In Example 16, the composition of the first polymerizable monomer mixture was 20 parts of styrene, 60 parts of ethyl acrylate, and 15 parts of methacrylic e, and the composition of the second polymerizable monomer mixture was 15 parts of styrene. An aqueous copolymer dispersion was prepared by repeating the same procedure as in Example 16, except that 5 parts of methacrylic acid and 3 parts of methacrylic acid were used, which was outside the scope of the present invention.

The pH of this aqueous copolymer dispersion was 8.8, and the solid content was 47.
．． 6%, and the viscosity was 5830 cps.

Furthermore, except that the above-mentioned aqueous copolymer dispersion was used after the vehicle was used (the solid content of the aqueous coating composition obtained by repeating the same operation as in Example 26 was 60%, and the P'WC was 50%).
, the viscosity (KU value) was GjllO.

Example 54 A polished mild steel plate (thickness 0.3 mm)
, 2 coats of brush or spray on slate board, cedar board
I blew it again.

The performance test results of the coating film were as shown in Tables 7 and 8.

Table 7 shows when applied on polished mild steel plate, Table 8 shows when applied on slate plate,
These are performance test results when applied on a cedar board, and in each case, the test was conducted after drying at 25° C. for one week.

The conditions for each performance test are as follows.

Glossiness: 60° specular reflection glossiness Adhesion; Goba/eye test Pencil hardness: Mitsubishi Uni, scratch hardness Water resistance: Appearance alkali resistance after immersion in deionized water, 30°C, 7 days, 5% Appearance after being immersed in a caustic soda aqueous solution at 30°C for 7 days Acid resistance; Appearance after being immersed in a 5% sulfuric acid aqueous solution at 30°C for 7 days Weather resistance Last name: Appearance after being exposed outdoors for 1 year and 6 months ◎～× means test,
These are the test results and show the following conditions.

◎; No abnormalities ○; Slight peeling, slight foaming, slight matting, or slight cracking △; Peeling, foaming, matting, or cracking ×; Severe peeling, severe foaming, severe matting , or severe cracking Example 55 4 parts of butyl carpitol acetate was added to 100 parts of each of the aqueous copolymer dispersions of Example 1 and Comparative Examples 1 and 2 to obtain a coating composition.

Each of these coating compositions was brushed onto lauan plywood and dried at 80° C. for 20 minutes.

The performance of the coating film thus obtained was as shown in Table 9.

(Note-1) Coating composition A: 100 parts of the aqueous copolymer dispersion of Example 1 4 parts of t-butyl carpitol acetate 4
Part C: 100 parts of aqueous copolymer dispersion of Comparative Example 2 - 4 parts of butylcarpitol acetate (Note-2) Test method Water resistance: Alkaline resistance when immersed in water at 60°C for one day and night: 30% in 10% sodium carbonate aqueous solution
Appearance after being immersed at 30°C for 1 day and night Resistance to volatile oil: Appearance after being immersed in test volatile oil No. 2 at 30°C for 1 day and night Impact resistance 1: JAS impact A test rating ○・・・・・・・・・・・Good △ ・・・・・ Slightly poor× ・・・・・・・・・ Poor

Claims (1)

[Scope of Claims] 1 General formula [wherein R1 to RIO represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, and R11 represents an aliphatic hydrocarbon group having 1 to 13 carbon atoms] group, aromatic hydrocarbon group, alicyclic hydrocarbon group, or a halide or heterocyclic compound of these groups. W is O or an integer of 1, (A11 is a divalent to tetravalent organic group represented by [:(R12-0%→RI3-0h-R14), or M, H, 12 to R14 are R
Represents the same group as 11, M is tin, zinc, magnesium,
Represents a di- to tetravalent metal ion such as calcium, barium, aluminum, etc. h, i, j. k+I, m+n and p are O or an integer from 1 to 4, and I
+m+n+p=2 to 4, h≦I, i≦m, j≦n, and ≦p, x+y and 2 are integers of 0 or 1, and q and r are O or integers of 1 to 100. However, if A1 is M, h = j = l = n
20, i double - an integer from 2 to 4, k2 p = an integer from 2 to 4, i + 0 that is ≦4 (if AJW is IAo, h G
t Q or an integer from 1 to 2, l, J and l (is an integer from 0 or 1, I morn ten n −) p = 2
, h is null, i<m, J≦2n, and h+1 is ≦p.
! If any one of J l k is not O, the other three are always O. However, h = i2j2 = n = p20, and when l and [n are 1, R2, u R5 may form bonds with each other to form a cyclic compound. ] Polymerizable monomers having at least two ethylenically unsaturated double bonds (excluding bucdiene and substituted bucdienes) (B) General formula % Formula % [In the formula, Rb is - R15 is a group represented by R,16- or R15 and R]6 are a hydrogen atom or a methyl group. RoGt is a hydrogen atom, -COOH or -COOR17, and R17 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or R19-0 (7R18-00 -8R18-, R18 is an aliphatic hydrocarbon group having 2 to 3 carbon atoms, and R19 is an alicyclic hydrocarbon group having 1 to 4 carbon atoms. S is O or 1 to 3 ] A polymerizable monomer having one ethylenically unsaturated double bond and at least one carboxyl group, and (D): a polymerizable monomer other than the above (however, General formula CH
R202CR2' (CH2)I Rd [wherein, R
20 and R21 are hydrogen atoms or methyl groups, and R
d is either H25, (22 represents an aliphatic hydrocarbon group having 2 to 6 carbon atoms, R23 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 2 carbon atoms, and R24 is a hydrogen atom or represents a methyl group, R25 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. t is O or an integer of 1, U is O or an integer of 1, ■ is 1
W is an integer of 1 or 2, and X is an integer of O or 1. ] Polymerization t'4E i? - Excludes molecules. ), the ratio of each polymerizable monomer is in the range of 0.5 to 32 parts by weight of the polymerizable monomer shown in (5) per 100 parts by weight of the mixture. , the amount of the polymerizable monomer represented by fBl is equivalent to bringing the acid value of the mixture into the range of 4 to 40, and the remainder is the polymerizable monomer represented by (U). The mixture is subjected to emulsion polymerization to prepare an aqueous copolymer latex, and then a basic compound is added to the latex to adjust the pH to 6 or more. The resulting aqueous coating composition.