JPS6023706B2 - Water-based coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to coating or impregnating compositions.

When using an aqueous dispersion of an emulsion polymer in which the particles are water-insoluble, the effectiveness of the dispersion in forming a film after coating the polymer dispersion on the surface to be coated is determined by the dispersion of the dispersed polymer. depends on the glass transition temperature and the temperature at which the coating is dried.

This is particularly true in U.S. Pat. No. 27955 to Conn et al.
No. 64, which describes the applicability of many acrylic polymers in the production of water-based paints. As pointed out in this patent, polymers obtained in aqueous dispersions by emulsion polymerization of one or more monoethylenically unsaturated monomers (having the group QC=C<) have an apparent quadratic transition temperature. , or have a glass transition temperature that depends on the components and the proportions of these components in the polymer. This patent describes some of these monomers, such as methyl methacrylate (styrene,
(vinyl acetate, vinyl chloride, and acrylonitrile are similar in this respect) have been shown to have a tendency to form homopolymers with relatively high glass transition values, and the specific glass transition temperatures shown in this patent It is represented by the symbol Ti as defined by . When homopolymerized, the monomers disclosed herein yield rigid polymers, ie, polymers with glass transition temperatures or Ti values of 20 oo or greater. On the other hand, this patent describes a number of monomers in the monoethylenically unsaturated form that are relatively soft and give rise to homopolymers, the properties of which are polymers with glass transition temperatures or Ti values of 20°C or lower. It is a combination. This patent discloses that by copolymerizing various hard and/or soft monomers in predetermined proportions, a sufficiently wide range of predetermined glass transition temperatures from 140 qo to 150 °C or higher or Ti It is disclosed that a copolymer having a value is obtained.

Coatings made from aqueous dispersions of various polymers may be applied to coating compositions made from these polymers or water-based paints provided that the Ti value of the particular polymer involved is not greater than the ambient temperature at which the coating is carried out. In some cases, good film-forming properties are expected and can be carried out at normal room temperatures or even lower temperatures. For example, about 1
Coatings made from water-based paints containing polymers with a Ti value of 5 qo can generally be applied at room temperature;
Simply drying the coated film in an ambient atmosphere then results in good film formation. On the other hand, if the coating composition contains as its main film-forming component an emulsion polymer having a Ti value above room temperature, e.g. Elevated temperatures of, for example, 350°C and above are required during drying to ensure that the coalesced particles properly coalesce or fuse into a continuous cohesive film during drying. Although some polymers are characterized by a glass transition temperature substantially above room temperature, e.g. up to 300-35°C,
Furthermore, due to the affinity (hydrophilicity) of specific polymer units for water in the dispersed polymer particles, a continuous film can be formed at normal room temperature. An example of this monomeric component is vinyl acetate. As a result of the inclusion of a sufficient amount of vinyl acetate (or its equivalent monomer) the affinity of the polymer is such that the polymer particles coalesce into a continuous film at temperatures below the Ti value of this polymer as determined by standard tests. help you do. The manufacture of water-based paints with polymers with low Ti values so that water-based paints can be applied at normal room temperatures without the use of plasticizers often produces films that are unsuitably hard and tough after drying. will occur.

On the other hand, the use of polymers with high glass transition temperatures substantially above room temperature, e.g. 35°C or higher, is generally combined with permanent or temporary plasticizers (low Ti plasticized polymer with a value)
or require high drying temperatures. 197#King U.S. Patent Application SehaIM., filed on March 8th. No. 664,597 [CIP U.S. Patent Application Serial M. No. 851325
(U.S. Patent No. 4131 Madarabi) discloses the incorporation of dicyclobentenyl acrylate or dicyclobentenyl methacrylate as a coalescent into this aqueous film-forming polymer dispersion, and the compounds are individually They are referred to as DCPA and DOPMA, and collectively as DCP(M)A.

However, despite their low volatility, these compounds have a very characteristic, diffuse, persistent, and unpleasant odor under certain conditions when used by certain operators. They are also too volatile for use* in certain water-based topcoats, especially those used industrially or in applications requiring firing at elevated temperatures. D
CP(M)A also tends to produce extremely hard and brittle products requiring plasticizers. In accordance with the present invention, water-insoluble addition polymers are dissolved and dispersed as immovable particles of microscopic dimensions, such as those obtained by emulsion polymerization, with an average diameter of 0.1 to 5 or 10 microns. The aforementioned disadvantages have actually been overcome by the addition of monomeric materials of formula 1 below to aqueous coating compositions, such as water-based paints, prepared from aqueous dispersions of vinyl addition polymers containing polymers.

The use of these compounds, as explained below, provides many previously unobtainable uses for the present compositions without significant hassle or expense. The compounds used in the present invention have the following general formula 1: where R is H or C, and R0 is an alkylene group having from 2 to 12, preferably from 2 to 6 carbon atoms, or at least 4 None, 12 carbon atoms and a separate segment of the alkylene group (segme
nts), each segment of which is an oxaalkylene group containing at least one carbon atom.

In a preferred embodiment R〇 is a diol containing one or two oxygen atoms bonding the 2- or 3-carbon atom portion of the alkylene group (without C2, to C6) or (without C2, to C6).
6) An ester ether chain representing an alkylene or oxaalkylene group of a glycol is attached to either the 5th or 6th position of the ring nucleus as shown in general formula 1. In fact, it comprises a mixture of two compounds, in one of which the ester ether chain is substituted in the 5 position and in the other the ester ether chain is substituted in the 6 position.
The monomer of formula 1 is prepared using an acid catalyst by first reacting the excess diol with dicyclobenzene to form the intermediate ether (
hydroxy-R0-dicyclobentadiene) and then reaction of the intermediate with acrylic acid or methacrylic acid using acid catalysts such as sulfuric acid, P-toluenesulfonic acid, and: boron fluoride. It can be produced by esterifying hydroxyl.

Examples of diols include ethylene glycol, propylene glycol, neobentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and triethylene glycol. The monohydroxy glycol ester obtained in the first step is preferably separated off, for example by distillation, and then esterified with acrylic or methacrylic acid using an acid catalyst. Alternatively, the second step can be acylation of the monoester with a (meth)acrylic acid chloride or anhydride or transesterification with a simple ester such as methyl (meth)acrylate in the presence of a neutral or basic catalyst. be. The method for producing this monomer was published in the United States Patent Application No. 197 on July 7th. No. 703,348 (U.S. Pat. No. 4,097,677), the description of which is incorporated herein by reference. 0 According to the invention, monoethylenically unsaturated monostars, in particular end group QC
The addition of the non-volatile reactive monomer of formula 1 described above to coating compositions based on pinyl addition polymers having =C< improves ease of coating and ease of film-forming action during drying at normal room temperature. It is extremely valuable and useful for the purpose of making coatings more convenient and also for coating films of greater hardness and toughness as a result of the reactivity, air curing properties of the monomers of formula 1 above. be.

Generally, small amounts of desiccants, meaning salts or polyvalent metal rust bodies of the type commonly used to promote the oxidation of baggage oils, can be added to accelerate the hardening of the coating film during drying. The proportion of the compound of formula 1 in the coating composition falls within a wide range depending on the particular composition, its components and especially the content of film-forming polymer and the apparent second-order transition temperature. When added to emulsion polymer dispersions, compounds of formula 1 play a very beneficial role.

Similar to DCP(M)A, it can serve as a cohesive agent in that it acts as a plasticizer for the dispersed polymer particles. The dispersed polymer has a Ti higher than room temperature, e.g. If no film is to be formed, sufficient compound of Formula 1 is mixed into the polymer dispersion or a coating composition containing the polymer dispersion to sufficiently lower the Ti and effective film-forming temperature to coat the composition. allows the resulting coating to form a continuous film at ambient temperatures. At the same time, when the film is air-dried, the product becomes hard and block-resistant due to the autoxidizing nature of the composition. However, the ester ethers of Formula 1 may have unpleasant (or detectable)
It has an advantage over DCP(M)A in that it has no odor. During manufacture or use, these compositions are subjected to elevated temperatures, for example by applying the composition in an elevated temperature atmosphere or by subjecting the coated or impregnated article to an elevated firing temperature of 150° or more. Even the compounds of formula 1 emit little or no unpleasant odor due to their extremely low volatility. D.C.
Due to the special "0-Ro" present in this compound of formula 1 compared to P(M)A, an extremely low volatility is clearly obtained.Furthermore, an expanded variation in the specific composition of the radicals Ro hardness (brittleness) and softness (toughness) in the cured product
The combination of provides widely variable factors. Ro and R
The selection can be made in conjunction with the particular film-forming polymer in the aqueous polymer system to provide a wide range of properties in the final product. Thus, the compound of formula 1 provides a wide range of versatility for the application of its polymer dispersions, where it is not desired to replace the constituent polymers with polymers having a different compositional structure. Similarly, coatings based on aqueous dispersions of emulsion polymers with low Ti such that film formation occurs with monomers of formula 1 at room temperature
When the monomer of Formula 1 is added, the film obtained from the polymer containing the monomer of Formula 1 is cured and toughened upon air curing of the monomer component of Formula 1.

The coating composition preferably contains one or more desiccants.

The desiccant used is any polyvalent metal-containing complex or salt that catalyzes the oxidative curing of the drying oil or drying oil-modified alkyd resin. Examples of desiccants are various polyvalent metal salts containing calcium, copper, zinc, manganese, lead, cobalt, iron and zirconium as cations. halides,
Simple inorganic salts such as chlorides, nitrates, and sulfates are useful. Also useful are organic salts such as acetylacetonate, acetate, propionate, butyrate. The desiccant may also be a sulfurization reaction product of a metal oxide, acetate or borate and a vegetable oil. Useful desiccants also include salts of naphthenic acids or (C8-C3o) aliphatic acids. Examples of aliphatic or fatty acid components or anions of desiccant salts are naphthenic acid, resinic acid (i.e., rosin acid), tall oil fatty acid, linseed oil fatty acid, 2-ethylhexotic acid,
Lauric acid, palmitic acid, myristic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, behenic acid,
those of cerotic acid, montanic acid and apietic acid. Preferred desiccant salts are cobalt and manganese salts;
Examples are cobalt octoate, cobalt naphthenate and manganese octoate and naphthenate. Mixtures of various desiccants are used. ''Encyclop
edja of Chemical Technology
gy” Kirk Osmer, Vol. 5, pp. 195-205,
Published by Interscience Cyclobedia, N.
Y. (1950) can be used. The proportion of this desiccant is very low and is generally used in amounts of 0.0005 to 2% metal content, depending on the weight of the monomeric material of Formula 1. The desiccant can be added to the composition before storage if the addition is carried out in the absence of oxygen or if a volatile stabilizer is included in the composition to inhibit the oxidative effects of the desiccant;
The composition is then placed in a closed storage container to prevent volatilization of the inhibitor. Thus, the volatile stabilizer can be expressed as formula 1
can be used in coating compositions containing reactive monomers that can inhibit polymerization of the formulated composition at any time during film formation.

The temporary stabilizer must exhibit sufficient volatility in thin films so as not to appreciably inhibit film formation. The stabilizer can be used in proportions as low as 0.1 to 2% by weight based on the weight of the Formula 1 compound components.
The stabilizer is generally a ketone having from 3 to 10 carbon atoms, resulting in a volatile ketone-oxime or without
It is an aldehyde oxime obtained from an aldehyde having 10 carbon atoms. Specific examples are methyl ethyl ketone-oxime, methylbutyl ketone-oxime, 5-methyl-3-heptanosoxime, cyclohexanone-oxime, and butyraldehyde oxime.
The addition of this inhibitor is essential if long stability and convenience time of the aqueous composition containing the dispersed polymer, monomer of formula 1 and desiccant is desired. vinyl type addition polymer,
The compositions of the present invention comprising an aqueous dispersion of a monomer of formula 1, a desiccant and a volatile oxime exhibit a characteristic rapid onset of tack-free curing of the film by autoxidation, while one of the monomers of formula 1 The rate of hardening can be accelerated by replacing part of the drying oil fatty acid or its salts, such as ammonium or alkali metal (eg, sodium, potassium or lithium) salts. Since the aqueous coating compositions of the present invention, especially pigmented, e.g. water-based paints, contain dispersants, the drying fat acid may be in the form of an alkali metal salt, e.g. a calcium or magnesium salt, but is usually Ammonium or alkali metal salts are preferred. The degree of promotion obtained in this way depends on the proportion of the monomer of formula 1 that is replaced by the drying oil fatty acid, and while one-third or more can be replaced by this fatty acid, generally the ether of formula 1 A substitution of 1 to 25% by weight of ester monomer provides a very practical operating range, and preferably a substitution of 5 to 10% is most useful. Examples of drying fatty acid include: linoleic acid, linolenic acid, linseed oil fatty acid, tung oil fatty acid, tall oil fatty acid, soybean oil fatty acid, dehydrated castor oil fatty acid. etc. Since the coating composition is alkaline in nature, this fatty acid may be in salt form, especially ammonium salt. Of course, the coating composition may also contain pigments, dispersants, sequestrants, antifoam agents, wetting agents, thickeners, disinfectants, tougheners, oxidants, modifiers, and other resinous materials in dispersed form. Other materials mentioned in the above-mentioned patents may also be included.

A variety of pigments and materials mentioned in previous patents can be used. Generally, the proportion of monomeric materials of Formula 1 used in the coating composition is about 1 based on the weight of the vinyl addition polymer that constitutes the main film-forming component of the coating composition.
None, 20% by weight, preferably 5%, 150% by weight.

No. 2,795,564 to Conn et al.
It is to be understood that the acrylic polymers described in this issue are not the only types of vinyl addition polymers that can be modified and improved by the inclusion of monomers of formula 1 along with desiccants.
In the copolymer system of this patent, the curing component is a lower methacrylate, such as methyl methacrylate, but the hard lower methacrylate is a curing monomer such as styrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, or vinyl acetate. Similar copolymer systems which are partially or fully replaced by monomers of formula 1 are also improved by the inclusion of monomers of formula 1 and a desiccant. Monomers of formula 1 can also be natural latexes or butadiene, chloroprene, styrene/butadiene copolymers,
It is useful with aqueous coating systems based on synthetic latexes made from acrylonitrile-butadiene-styrene copolymers and related synthetic rubber systems having low Ti values. The films obtained from these dispersions are also improved with respect to hardness by incorporation of monomers of formula 1 together with desiccants. The use of reactive monomers of formula 1 makes it possible to obtain hard, durable coating films from coating compositions containing polymers with low Ti, which normally form soft films.

This advantage can be obtained without the use of plasticizers or with significantly reduced amounts of permanent plasticizers in the composition. The formulation of monomers of Formula 1 in coating compositions is not limited to those in which the film-forming component comprises or consists essentially of water-insoluble dispersed particles of a polymer or copolymer.

It is also useful in connection with aqueous solutions of vinyl addition polymers in which the solubility of the polymer is essentially that of low molecular weight polymers containing hydrophilic groups, as well as those characterized by the formation of colloidal solutions. This soluble polymer derives its solubility from a large content of hydrophilic groups such as acids, which may be in acid or salt form.

Examples of this acid are acrylic acid, methacrylic acid, crotonic acid,
Contains citaconic acid, maleic acid, citraconic acid, aconitic acid, etc. This salt may be ammonia, a salt of an amine, such as dimethylaminoethanol, triethylamine, 2-amino-2-methyl-1-propanol, etc., or a salt of an alkali metal, especially sodium, potassium or lithium. Polymers containing a large proportion of acid units, such as polyacrylic acid, polymethacrylic acid, or copolymers, such as 1
In addition to copolymers of 5% methacrylic acid and 85% butyl methacrylate, copolymers containing a large proportion of acrylamide or methacrylamide units or polymers containing a large proportion of amine units, such as oxazolidinyl.
Homopolymers of oxazolidinyl alkyl acrylates or methacrylates, such as ethyl acrylate, or copolymers of up to 2% by weight of methyl acrylate with amine-containing polymers of the latter can be used. Water solubility can also be obtained from polymers from monomers containing hydroxyl groups, such as hydroxyalkyl acrylates or methacrylates, such as hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate. Water solubility may also be the result of copolymerization of two or more of the hydrophilizing monomers mentioned herein. In these cases the use of a monomer of formula 1 in conjunction with a desiccant serves to modify the properties of the final coated film. The use of monomers of Formula 1 in coating compositions serves several functions or purposes.

In aqueous solutions of water-soluble polymers, the formula 1 monomer helps control viscosity and facilitates coating without the need for excessive dilution of the solution with water or other water-immiscible volatile solvents. The monomer of formula 1 then becomes part of the binder component when air-dried and improves the solvent resistance, water resistance, and
Contributes to alkali resistance, gloss, hardness and durability. In coating compositions based on aqueous dispersions of water-insoluble polymer particles, obtained for example by emulsion polymerization, the monomers of formula 1 serve as adhesives, hardeners, tougheners, viscosity modifiers, etc. In all cases, a vinyl polymer, a monomer of formula 1,
Upon air dry curing of the coating composition containing a desiccant and a desiccant, the monomer of Formula 1 becomes part of the binder in the final cured coating film. Avoiding volatile organic solvents also reduces contamination. This non-volatile, reactive component may be, and preferably consists essentially of, the monomeric material of formula 1, but if desired it may contain at least a major portion (e.g. 51%, 9% by weight). ) and '1} higher (CM-C2o) aliphatic ester of acrylic acid or methacrylic acid,
For example (C,.-C2o)alkyl and (C,.-C2
. ) alkenyl acrylates and methacrylates, and '
2-a small portion of other non-volatile reactive ethylenically unsaturated monomeric materials selected from vinyl esters of higher (C,o-C2o) aliphatic acids, or 4-a portion of non-volatile, reactive di(C,o-C) , -C8) containing mixtures of alkyl maleates, fumarates and itaconates. Optionally, non-volatile reactive Formula 1 monomer-containing materials can also contain up to 30%, based on binder weight, to improve water resistance, solvent resistance, abrasion resistance, and blocking resistance. , preferably without 2, with a small amount of polyethylenically unsaturated material such as glycol or polyol (meth)acrylate, such as ethylene glycol di(meth)acrylate, 1,4
-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,3-butylene glycol dimethacrylate, neobentyl glycol di(meth)acrylate, ventaeri tritoltri and tetra-( meth)acrylate, trimethylolpropane trimethacrylate; also aryl (meth)
Can include acrylates. Examples of esters {11 are decyl acrylate, isodecyl acrylate, undecyl acrylate, lauryl acrylate, cetyl acrylate, pentadecyl acrylate, hexadecyl acrylate, octadecyl acrylate, the corresponding methacrylates, and unsaturated analogs such as oleyl acrylate. or methacrylate, linoleyl (meth)acrylate, linolenyl (meth)acrylate, etc.
Examples of '2} are vinyl decanoate, pinyl laurate,
These are vinyl oleate, vinyl balmitate, vinyl myristate, and vinyl stearate. Examples of esters include dimethyl, diethyl, dibutyl, dihexyl and di(2-ethylhexyl) maleate, fumarate and itaconate. In the following examples illustrating the invention, parts and percentages are by weight and temperatures are in degrees Celsius, unless otherwise indicated.

Various latexes of emulsifying copolymers also used are as follows: Latex A-42. Spot A/56.9MM
A/1.0 MAA copolymer, neutralized with ammonia to a pH of about 9.5, 47% solids, Ti about 41°C, particle size about 0
．． 1 micron, latex B-3 A/64MMA/I
Copolymer of MAA, pH of 9 (NH3), 45% solids,
Ti terms.

○, particle size approximately 0.15 microns latex C-45. String A/53.4 MMA/IMAA copolymer, pH 9 (
NH3), 45% solids, Ti approx. 24°C, grain height approx. 0.15
Micron, latex D-54.7BA/43. Skin MA
/1. Egg Buddha A copolymer, pH (N&) of 9, 45% solids, Ti 130○, Latex E - 85% vinyl acetate and 15% butyl acrylate copolymer, 45% solids, Ti about 1500, FH of 4, Latex F - 40% vinyl acetate, 37% butyl acrylate and 23%
Copolymer of pinyl chloride, 45% mass, Tj about 1500,
PH of 4 and latex G-1 spots A/81. Small MA
Copolymer of /0.9 MAA, neutralized to FH of about 9.2 with trimethylamine, 37.3% solids, Ti at 60°C, particle size about 0.1 micron, Kono: EA = ethyl acrylate; BA=butyl acrylate, MMA=methyl methacrylate, and MAA=methacrylic acid, the proportions in the copolymer are by weight.

In some of the examples below, compared to conventional non-reactive materials previously used as latex polymeric adhesion agents (poIM mercoalescent), this material has a gradual but Because of its tendency to evaporate, it is referred to here as a "temporary" adhesive.

These non-reactive, temporary adhesion agents include:
2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, hereinafter referred to as TPM; 2-butoxyethanol, hereinafter referred to as BE.

n-Ptoxypropanol, hereinafter referred to as BP, acetate of butyl ether of diethylene glycol, hereinafter referred to as BD
It is called A. Example 1 40% dicyclobentenyloxyethyl methacrylate (hereinafter referred to as ``monomer la'') was added to the latex solid.
Gradually add to latex A while stirring at the ratio of .

Cobalt(b)acetylacetonate (0.2% metal in latex solids plus monomer) and methyl ethyl ketone oxime (0.26% in latex solids plus monomer)
Stabilizer is added and the mixture is stirred overnight to ensure complete dissolution of the metal desiccant. Similarly, add TPM to another sample of latex A at a ratio of 20% to latex solids.
Add.

The films were cast at room temperature and Table 1 shows the hardness as a function of time.

Table 1 Note): Knoop hardness number
snumber) Indentation hardness test using a pyramid-shaped diamond indenter.

The diagonal angles of the indenter are 172.50 and 1300, and the depression is diamond-shaped. If the length of the diagonal line in the longitudinal direction of this rhombic depression is the length of the diagonal and the load is Pkg, then the Knoop hardness number Hk is Hk=
14. It is given in tsubo/yu 2.

Regarding the temporary adhesion agent TPM and because of its slow evaporation,
This latex film has sufficient hardness (KHN=4-5
) takes several weeks to months at ambient temperature to develop.

In contrast, autooxidatively curable adhesion agents (monomer la
), the hardness development is much faster and the final hardness of the film increases (KHN=6-7). Furthermore, monomer l
A does not add any odor to the preparation. Example 2 Temporary Adhesive TPM in Variable Latex Adhesive Pairs in Latex B and C that Both Form a Cohesive Adhesive Film at Room Temperature The monomer la is further tested as BE and BP.

Latex B and C are similar to latex A with respect to this latter property. A temporary adhesion agent is added to each latex portion with stirring at a level of 10 and 2 weight percent based on latex solids.

Add to other parts of each latex monobase wing a at levels of 10, 20, and 40% with stirring.

Cobalt(0) Acetate (0.1% metal based on weight of monomer and latex solids), 70% aqueous t-octylphenoxypoly(39)ethoxyethanol (1% based on latex solids) and methyl ethyl ketoxime (0.25% based on monomer and latex solids)
) is then added while stirring. A similar set of monomeric la-containing latex preparations is made, but omitting the cobalt and oxime. Films are cast at room temperature on aluminum test panels to yield a dry film thickness of approximately 2.2 mils. The table shows hardness, impact resistance, which develops over time,
and cheese cloth print resistance (here, 14 valence,
Place the cheese cloth against the film under pressure of 2 pounds per square inch for 1 hour). Print resistance was measured after 2 weeks under ambient conditions and graded from lo = no print to 0 = very heavy print. Commonly used adhesion agent TPM
In this case, the appearance of hardness and printing resistance are extremely slow, and the same is true in the case of uncatalyzed monomer la.

Furthermore, the use of volatile BE and BP provides a significantly more rapid development of properties. However, ``the use of the monomer LA in conjunction with cobalt catalysts and oxime stabilizers not only gives the coating superior properties, ``but also avoids wasting raw materials and protects workers from contamination and exposure to solvent vapors.'' Table □ Samples 8-10 contain Co(0) and methyl ethyl ketoxime.

*Sample 20-22 contains Co(□) and methyl ethyl ketoxime. Example 3 Although the novel coating of Example 2 containing the monomer La and cobalt catalyst exhibits excellent rates of property development, this rate is further enhanced by formulating with low levels of drying fat acid. can.

Thus, the tack-free time of coating 9 of Table 0 was determined by the monomeric l
from about 2 hours to about 1 song time and about 8 hours each. Example 4 Comparable results were obtained when Examples 1, 2, and 3 were repeated by substituting the corresponding proportions of each of the following monomers in Formula 1 above for monomer la. , in each case the chemical names of the monomers are given short abbreviations in the references below: a dicyclobentenyloxyethyl acrylate (monomer lb) b methacrylate ether of neobentyl glycol monodicyclobentenyl ether Acrylate ester of neobentyl glycol monodicyclobentenyl ether (monomer 3) d Methacrylate ester of l,2-propylene glycol monodicyclobentenyl ether monomer 4) e Acrylate ester of l,2-propylene glycol monodicyclobentenyl ether (monomer 5) f Methacrylate ester of 1,3-butylene glycol monodicyclobentenyl ether (monomer 6) g The above Acrylate ester corresponding to the methacrylate of f (monomer 7) h Dicyclobentenyloxyhexyl acrylate (monomer 8) late (monomer 9) 10) k dicyclobentenyloxyethoxyethyl acrylate (monomer 11) All of these monomers of formula 1 have vapor pressures at least as low as monomer la, yet are free from drying agents and air or Shows identical autoxidation properties in the presence of oxygen.

Example 5 Hard Latex Copolymer Semi-Gloss Paint By mixing and grinding the following materials in specific weight ratios (
Make a pigment paste (for example in a Kahless dissolver at 350 pm for 20 minutes): partial dispersant (ammonium salt methacrylic acid copolymer 7.48 antifoam agent (NopcoNDW) 2.00 polypropylene glycol 59.8 Rutile Ti0
2 269.6 (note):
Nopco NDW is Nopco Chemical CO
．． The resulting pigment dispersion is then placed down with the following materials (Table D), depending on the paint produced.

Younger brother m Table 1 Dioctyl sodium sulfosuccinate 2* H
ercules Inc. 2.5% aqueous hydroxyethyl cellulose 3 Super Ad-lt (S
upper 1 Ad 1 t) is Tenneco Chemical
alsInc. After mixing the di(phenylmercury) dodecyl succinate paint under the trade mark of .RTM., it is adjusted to a 9.6 p-law by adding ammonium hydroxide.

Apply this paint to aluminum panels 1.5-2.
Produces a dry film thickness of 0 mils.

The development of film hardness (Knoop hardness number) and mirror-like gloss continues with time and is shown in Table W. monomer l
Coatings containing a, cobalt, and oxime exhibit good gloss and wet stability. The hardness is excellent and, furthermore, the coating is raw material free and non-staining. Table V Properties of Pigmented Coating Groups Example 6 For comparison, the above-mentioned Latex E and Latex F are prepared using the temporary adhesion agent TPM and the monomer La.

Adhesive (10, 20 or 3% by weight on latex solids)
Gradually add to the latex copolymer while stirring. In this case, Co(0) acetate (0.10% metal in latex solids and monomer) is added with stirring. The film is cast onto aluminum test panels and allowed to dry at room temperature to yield a dry film thickness of approximately 1.7 mils. Even without a cohesive agent, the latex copolymer forms an apparently continuous film at room temperature.
Film hardness and cheese cloth print resistance are shown in Table V.
Table V *24 hours measured after 2 weeks drying at 2 psiF, 25°C.

Coatings containing conventional temporary adhesives required for film formation at temperatures below normal room temperature remain tacky for two weeks.

In contrast, coating compositions containing monomer la produce tack-free films within 2-3 days. Furthermore, the hardness development and printing resistance developed by films containing monomer la are comparable to, or even better than, those of films obtained without added adhesion agents. Example 7 Low-temperature Calcination Latex Polymer Coating Monomer La is used as a cohesive agent and compared to a 1 hour cohesive in Latex B using a short bake at a mildly elevated temperature to accelerate curing. .

The coating is prepared by mixing in the following order: Composition number (note): Rohman ratio asCo. A coating made of octylphenoxy (ethoxy) 40% ethanol is cast onto a test panel and evaluated for hardness several times after various curing conditions as shown below: Taccon hardness Cobalt catalyst after Korean charging In addition, systems containing the monomer la have an excellent reaction with accelerated curing at elevated temperatures, which wastes raw materials and pollutes the environment.

EXAMPLE 8 Coating Composition Comprising Soft Acrylic Latex Copolymer Use of Cohesive Agent Monomer la is tested as a latex cohesive agent in Latex D, which can form a film at room temperature.

Various latexes are formulated with monomer la along with TPM (temporary adhesion agent) and with cobalt acetate catalyst (latex solids plus 0.1% metal in monomer). Freshly prepared compositions are placed on steel test panels. When molded and dried and after 1 and 2 weeks at room temperature yields 1.7 mil films.These were tested for hardness and cheese cloth print resistance and the results are shown in the table. Monomer la provides significantly improved hardness and print resistance to soft latex films.Table VI *25°C, 2 hours or si.

Example 9 Cursive letter L on latex G as a convertible latex adhesion agent
A hard, quickly air-drying, non-staining latex coating vehicle is produced using A and compared to a similar coating using BDA as a temporary adhesion agent.

The Ti of the latex polymer is 60°C and it is not possible to form a film at room temperature without a cohesive agent. The coating composition is prepared by mixing in the following order. *t-octylphenoxy poly(39
) Ethoxyethanol The newly prepared composition was cast onto an aluminum test panel to yield a 1.8 mil thick film when dried and evaluated for hardness development with the following results: Example 10 Repeat Example 5 without and 9 replacing monomer la with the corresponding proportions of each of the following reactive monomers of formula 1: 1
Monomer la 2 Monomer 4 3 Monomer 5 4 Monomer 6 5 Monomer 8 6 Monomer 9 7 Monomer 10 The results obtained were obtained when using monomer la It is completely comparable.

Claims (1)

[Claims] 1. (a) An aqueous dispersion of a vinyl addition polymer, (b) A general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. based on the weight of the dispersed polymer ▼ (R in the formula is H or CH_3 and R^0 is an alkylene group having 2 to 12 carbon atoms or an oxane group having at least 4 to 12 carbon atoms and having at least one oxygen atom connecting distant segments of the alkylene group. 1 to 200% by weight of ester-ether monomers (alkylene groups, each segment having at least two carbon atoms);
and (c) 0.0005 to 2 of the monomer of the above (b)
% metal content by weight, and said vinyl addition polymer comprises methyl methacrylate, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, vinyltoluene, acrylic acid, methacrylic acid, Crotonic acid, itaconic acid, maleic acid, citraconic acid, aconitic acid, ammonia, amine or alkali metal salts of these acids, amides of these acids, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, oxazolidinyl alkyl acrylates and oxazolidinyl alkyl methacrylates at least one member selected from the group consisting of and (C
_1 to C_1_8) alkyl acrylate and (C_4
~C_1_8) A copolymer of at least one member selected from the group consisting of alkyl methacrylates, and the desiccant is any polyvalent metal-containing complex that catalyzes the oxidative curing of the drying oil or the drying oil-modified alkyd resin. or salts, compositions suitable for coating and/or impregnating substrates. 2. A composition according to claim 1 comprising a volatile aldehyde-oxime or ketone-oxime stabilizer. 3. A composition according to claim 1 comprising a drying oil fatty acid or a salt thereof. 4 The vinyl addition polymer is dispersed as water-insoluble particles,
A composition according to claim 1 having an apparent second-order transition temperature in the range -40<0>C to +150<0>C. 5 The vinyl addition polymer is dispersed as water-insoluble particles,
A composition according to claim 1 having an apparent second-order transition temperature in the range 15-100<0>C. 6 The vinyl addition polymer is dispersed as water-insoluble particles,
A composition according to claim 1 having an apparent second-order transition temperature of 15°C or less. 7. A composition according to claim 1, wherein the polymer is a copolymer containing methyl methacrylate units and (C_1 to C_4) alkyl acrylate units copolymerized therein. 8 Composition according to claim 1, wherein R is CH_3. 9. A composition according to claim 1, wherein R is H and R^0 is ethylene. 10 Composition according to claim 1, wherein R is CH_3 and R^0 is ethylene. 11. A composition according to claim 1 comprising drying oil fatty acids in the form of ammonium salts. 12. A composition according to claim 11 comprising a volatile aldehyde-oxime or ketoxime stabilizer.