JPS6027701B2 - solid paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new type of paint product, namely a solid paint with dimensional stability based on ionic bonds.

Various types of resin compositions made of homopolymers and copolymers having partially neutralized carboxylic acid groups are known.

These compositions contain 3% to 20% carboxylic acid residues, less than 50% of which are neutralized with monovalent, divalent or trivalent cations. Conventional resins known as ionomers are industrially desirable because they combine the functionality of thermoset polymers with the dynamic properties and processability of thermoplastics. Ionomers have applications as protective films in the food packaging industry because they have lower densities than vinyl or cellulosic plastics and are similar to polyethylene. U.S. Pat. No. 3,266,2 for ethylene-methacrylic acid copolymer
No. 72, No. 33, No. 73y and Belgian Patent No. 674,5
No. 95 and No. 600,397. Ethylene-sodium acrylate copolymer has Dutch patent 6
, 511,920. The favorable physical properties of these polymers, such as stress-crack resistance, transparency, grease and abrasion resistance, low permeability, high elongation, high tensile strength, and low modulus, are partially attributable to the type of ionic bonding. It is something. In the present invention, solid paints having effective gel properties necessary for dimensional stability can be obtained by binding certain reactive polymers with "ion groups" having polar molecular components. was discovered.

This type of ionic bonding is substantially different from the solvent-free ionic bonding of conventional compounds. One of the objects of the present invention is to provide a solid paint composition with dimensional stability based on ionic bonds, i.e. ionic group crosslinking of polymers, comprising a mixture of the following components: IA 1,0
A solution of 25 to 9% by weight of a curable resin having a molecular weight of 00 to 7,000 and a sufficient number of carboxyl-reactive acid functional groups to give an acid number of 20 to 80 in a non-polar solvent, or B 25,000 to 1,000,
000 molecular weight and a reactive acid functional group selected from carpoxyl group, sulfonic acid group and phosphonic acid group.
A stabilized non-aqueous dispersion in which a polymer having a sufficient number to give an acid number of 0 is dispersed in a non-polar solvent as a 25 to 9 weight percent suspension, or C 25,000 to 1,00.
A non-bonding NAD resin consisting of a stabilized dispersion of a polymer having a molecular weight of 0,000 and no reactive functional groups as a 25 to 9 weight percent suspension in a non-polluting solvent. A mixture of the ion-binding solutions described in A in a ratio of 2:1 to 8:1, sodium dissolved in a lower aliphatic alcohol having 1 to 8 carbon atoms, and potassium hydroxide. 10 to 5% by weight solution of
and m optionally about 0.1 to 5% by weight of a metal desiccant based on the total weight of the polymer.

The composition contains about 100 to 500 per mole of acid functionality.
Contains mol% metal hydroxide. Furthermore, it is an object of the present invention to provide ionic bonding with dimensional stability and a
The object of the present invention is to provide a method for producing a solid paint having a gel strength of millimeter penetration, the method comprising: [a' 1. above. A or 1. B. Or 1. When the curable polymer resins of the type described in C are dissolved or suspended and the respective polymer compositions or mixtures thereof are crosslinked with an ionic crosslinking agent, the above-mentioned dimensional stability is limited. [b-
Next, pigments, fillers, colorants, and a drying agent of 0.5 to 5% by weight of an organic acid metal salt are mixed into this resin solution or dispersion. loo necessary to neutralize the reactive acid functionality.
C,- containing metal hydroxide in an amount of 600 mol%
8 20 to 3 dissolved or suspended in aliphatic alcohol
Add a solution or suspension of metal hydroxide at a weight percent of '
d} The product is then aged for 3 to 2 hours at a temperature of 15 to 70 qo.

Furthermore, it is an object of the present invention to provide a paint comb based on the above composition and method.

Solid paint compositions with dimensional stability and desirable paint properties are obtained by dissolving certain polymers with reactive functional groups and metal hydroxides in high dielectric constant polar solvents. It is obtained as a result of the action with a crosslinking agent.

Crosslinking of polymer chains is carried out by ionic groups made up of many ions associated with polar solvent molecules. By solid paint is meant one that has sufficient dimensional stability under storage conditions, ie, is self-supporting, and can be used as a paint stick (similar to a hard lump of butter or cheese). Such solid paints are convenient because they can be applied by hand, without the use of brushes or rollers, to surfaces normally protected by paints and coatings. In practice, for protection purposes, such paint rods are usually placed in a hide or bag suitable for storage. Due to the nature of such bags as instruments, it is advantageous that they have a closing opening. Solid paints are used by placing a paint rod against the painted surface and moving it up and down and side to side over the substrate, thus depositing a non-flowing, air-curable paint film.
The shear force by which the paint rod is pulled across the painted surface need only be sufficient to deform the solid paint to the point of flow coating at the point of contact. Such solid paint coatings have desirable properties such as adhesion, flowability and uniform coverage of the surface. The solid paints of the present invention contain conventional pigments, fillers, driers, binders, etc. to obtain films with desirable properties such as gloss, color and hiding power.
It may also contain other additives. Such solid paints can be formed into blocks or strips ranging in width from 3 ribs to about 240 square feet or more for industrial applications such as coating metal coils. When the curable resin is a non-polar solvent solution of a curable polymer as shown in IA above, the resin used in the present invention may be present in the polymer chain or grafted by conventional grafting methods. Homopolymers, copolymers or mixtures thereof with suitable functional groups are included.

By way of non-limiting example, useful resins include polyether, polyester, unsaturated polyester, polyurethane, polyolefin, polyacrylate,
Examples include polyhydrocarbons obtained from aliphatic and aromatic hydrocarbons having Q,8 unsaturated bonds, pinyl resins and chlorine-substituted vinyls, and other known combinations. The reactants and their amounts are selected to produce a resin with pendant and/or terminal functional substituents that can be further reacted with the ionic reagent to form a gel of suitable dimensional stability and gel strength. Desired properties are obtained when the gel strength, measured 2 hours after gelling, is between 10 and 190, preferably between 135 and 180. Gel strength was determined using a universal penetrometer (Universal Penetrometer).
It is expressed in millimeters using e and r), and the smaller the penetrometer reading, the higher the gel strength. Regardless of the type of resin used in the practice of this invention, it is essential that the resin be soluble in non-polar solvents and have pendant and/or terminal functional groups that are easily ionized. .

Such ionizable groups include both cationic and anionic reactive functional groups. The anionic functional group used to modify the resin is preferably of the carboxylic acid type. In particular, polymers having carboxylic acid functional groups are preferred because they are easy to obtain or manufacture; preferred reaction products are carboxylic acid-substituted polyesters with about 1000
It contains 1 to 4 reactive functional groups per 2,000 molecular weight units obtained by combining alkyd polyesters having a molecular weight in the range of 7,000 to 7,000. 400-2000
Particularly preferred are polyesters and polyethers having a molecular weight of .

Alkyd resins modified with fatty acid groups having terminal carboxyl functional groups are exemplified in the most preferred embodiment examples. In the case of polyolefins, polyacrylates, and other systems that do not undergo air curing, usually 100,000
A high molecular weight of the order of zero is required. However, 1 to 4 reactive functional groups per 2,00 molecular weight unit are still required. Alkyd resins useful in the practice of this invention are prepared by melt polymerizing polymerized monomers and other intermediates at temperatures of about 204 to 316 degrees to obtain an acid value (A.V. .) is obtained. Certain "high oil ratio" oil-based resins, exemplified in Examples 1 and 2 below, have an A of 43.0 at 2320.
．． V. Polymerized into The polymer having ionizable reactive groups is dissolved in sufficient non-polar solvent to obtain a solution having a non-volatile content (N.V.) of about 10 to 9 u, preferably 35 to 6 wt. be done.

Especially 50%N. V. Suitable non-polar solvents for dissolving the polymer include aromatic and aliphatic hydrocarbons, and are dependent on the type of resin used, the functional groups of the resin, and the ionic reagents. Selected according to characteristics. Generally suitable solvents are hydrocarbons having a boiling point of about 52 to 204° C. and less than 1 carbon number. Various types of octane are preferred because they have suitable evaporation rates. Mineral spirits are particularly preferred solvents due to their ready availability and desirable properties of the resulting solid paints. In some cases, it may be advantageous to use aromatic hydrocarbons such as toluene or xylene, which are particularly useful when dissolving high molecular weight polymers. Solvents, resins and proportions in individual cases will depend on the type of resin, type of solvent, and type of resin required for the intended solid paint.
It varies depending on fillers and other additives. Additives, desiccants and other conventional dispersants can be added to Cowles.
es) It is mixed with resin solution using a sea bream machine. The order of addition is usually not important. If necessary, pigments and other additives may be mixed with the resin material before dissolving the resin in the non-gutter solvent. After the additives have been thoroughly mixed, the resulting composition is advantageously aged for 12 to 2 feeding hours before reacting with the ionic component. When the curable resin is a stabilized dispersion in which a polymer is dispersed in a non-gutter nonsolvent as shown in IB above, the resin used in the present invention is in the polymer chain. or homopolymers, copolymers or mixtures thereof with suitable functional groups grafted by conventional grafting methods.

Examples include, but are not limited to, polyethers, unsaturated polyesters, polyurethanes, polyacrylates, vinyl resins and chlorinated vinyls, and other combinations known in the art. Additionally, the reactants and amounts are selected to produce a resin with pendant functional substituents that can be reacted with the ionic reagent to form suitable dimensional stability and gel strength. Favorable application characteristics are obtained when the gel strength is 130 to 21 when measured 2 hours after gelation is 150 to 195. Gel strength is expressed in millimeters using a universal penetrometer, the lower the reading, the higher the gel strength. When using IB type resin formulations in the practice of this invention, it is essential that the resin be insoluble or only slightly swollen in non-solvents and have pendant functional groups that are easily ionized. It is.

Such ionizable groups include both cationic and anionic reactive groups. The anionic functional group used for modifying the resin is preferably of the carboxylic acid type.
Carboxylic acid functional groups are particularly preferred since a variety of polymers having such reactive ionizable groups are readily available or prepared. A preferred resin has a molecular weight of 10
There are copolymers of unsaturated hydrocarbons and unsaturated acids ranging from 0,000 to 300,000. Particularly useful resins in the practice of this invention are acrylate esters and vinyl polymers having particle sizes of 0.01 to 30 microns. Acrylate and methacrylate copolymers with terminal carboxyl functionality are particularly preferred and are exemplified in the most preferred embodiment examples. Non-aqueous dispersions (NAD
) (provided they have groups on the surface that can be ionized by modification) include those described by Daubenko and Hart.
t,lnd. Eng. Chem. Prod. Res. D
evelop. , Vol. 12, No. 1,1973,
14-28). The polymers and stabilizers described therein apply mutatis mutandis to the present invention. In forming such NADs, the selection and amount of stabilizer is particularly important to obtain a solid paint with the desired application flow and coalescence properties. Other useful NAD resins include those derived from poly(methyl methacrylate), polyacrylate and polymethacrylate resins, and these and polyolefins such as polyethylene, poly(pinylethyl ether), vinyl acetate, hydroxy Ethyl acrylate and 2-hydroxyph. Examples include copolymers obtained by addition polymerization with lopyl methacrylate. In this case, the polymer resin of the present invention is produced by solution polymerization followed by dispersion in a nonsolvent or by dispersion polymerization.

In the first method, monomers or comonomers and other intermediates are
free radical polymerization at a temperature of 460 to 121°C,
A resin having an acid value (AV) in the range of 20 to 8 u, preferably 25 to 60 is obtained. A second preferred method is to prepare monomers, comonomers and other intermediates in a non-solvent from -46o to 121
Free radical polymerization is carried out at a temperature of 0.degree. C. to obtain a resin dispersion with the desired acid value. The above polymer having ionizable reactive functional groups is dispersed in a non-polar non-solvent to contain a non-volatile component (N/V) of 10 to 90% by weight, preferably 30 to 6%.
A dispersion liquid containing

Particularly preferred is a 50% N/V dispersion. Suitable nonsolvents include hydrocarbons of aromatic and aliphatic types, and are selected depending on the resin used, the functional groups on the resin, and the ionic reagent. Generally suitable non-solvents are about 37.
It is a hydrocarbon with a boiling point of 80 to 204q0 and a carbon number of less than 1. Examples include hexane, heptane, octane, nonane, decane, dodecane, and mixtures thereof. Octane is a preferred hydrocarbon because of its suitable evaporation rate. Natural oils are particularly preferred due to their ready availability and the desirable properties of the resulting solid paints. Some resin systems can use aromatic hydrocarbons such as toluene and xylene. The NAD resin can be appropriately blended with various known stabilizers.

The function of these stabilizers is primarily to prevent resin particles from coalescing during storage and formulation into solid paint products. Useful stabilizers include those described and cited in Daubenko and Hart, supra. Polyene-based stabilizers useful in certain solid paint compositions include low molecular weight polybutadienes grafted onto the backbone of acrylic copolymers. NAD stabilized by a copolymer of methyl methacrylate and glycidyl methacrylate and further reacted with 12-hydroxystearic acid and/or poly(lauryl methacrylate) is particularly preferred for the solid paint of the invention. The nonsolvent, resin, and their respective proportions vary depending on the resin, stabilizer, nonsolvent, filler, and other additives of the intended solid paint.

Additives, desiccants, and other dispersion aids are mixed with the resin dispersion using a Cowles rope mill. The order of addition is usually not important. Typical formulations of solid paints are latex-type, non-aqueous resin dispersions and do not require special desiccant components to obtain suitable film properties. If a desiccant is used, it is used in an amount of less than 2% of the total composition, preferably less than 1%. Desiccants are usually added with small amounts of oil or alkyd added to aid in pigment dispersion and film coalescence. After application, the resin particles coalesce and fuse to form a dry film within minutes. The polymer formulations shown in IA (a non-polar hydrocarbon solution of the polymer) or IB (a stabilized dispersion in a non-gutter non-solvent) were then dissolved in a high yield polar solvent. Combined with ionic crosslinking agent.

Suitable ionic crosslinking agents are usually inorganic salts that generate cations or anions in solution that can bond with the terminal reactive functional groups of the resin to form gel-forming ionic groups. Such ionic groups containing highly conductive solvent molecules act as reversible crosslinks to network the reactive resin molecules, imparting gel strength and dimensional stability to the resulting solid paint. When the reactive terminal functional group is a carboxylic acid group (mono-COOH), the preferred crosslinking reagents are alcoholic solutions of mono-, di- and trivalent metal hydroxides. Such crosslinking reagents include sodium and potassium hydroxides. Similarly effective crosslinking agents include the corresponding metal alkoxides, such as sodium methylate. A suitable gel is formed by combining an effective amount of cationic base with the free carboxylic acid groups. In either case, an amount substantially in excess of the amount required for neutralization is required as an effective amount. Substantial excess refers to about 100-600 mole percent of the ionic reagent dissolved in the polar solvent. The degree of excess varies depending on the resin system, the molecular weight of the resin, the type and number of ionizable functional groups, and the valence of the metal hydroxide, but is satisfied when the ionic reagent is used in excess of 100 to 600 mol%. A gel is formed. If less than 100 mole percent nose is used, the resin will not exhibit the necessary dimensional stability. When used in amounts greater than 600 mole percent, the resin no longer exhibits desirable flow and surface properties.

For gel formation, metal hydroxides or other ionic crosslinking agents are added to the polymer resin formulation as a 10-5% by weight solution in a high dielectric constant solvent. Preferred solid paints are obtained by using between loo and 250 mole percent of sodium hydroxide based on the molar content of reactive functional groups, ie, the number of moles of free COO. Polar solvents useful for dissolving the ionic crosslinking agent are generally those having a dielectric constant greater than 10, such as those having a carbon number of 1 to 10 and a carbon number of 1 to 2.
Examples include aliphatic alcohols having hydroxyl groups.

Although C,-8 aliphatic alcohols are generally preferred, glycols of similar carbon chains may sometimes be used to impart desirable gel properties to the resulting solid paints. Examples of useful alcohols include methanol, ethanol, isopro/gol, n-pro/g/ol, n-butanol and butanol isomers, pentanol, hexanol, heptanol, octanol and the corresponding glycols obtained therefrom. be. Methanol is preferable due to its low price, easy availability, favorable solubility of the ionic reagent, and the like. It may be preferable to use glycols or mixtures of glycols and alcohols as plasticizer carriers for the ionic reagents. Preferred glycols are ethylene glycol and propylene glycol, although higher glycols such as pentanediol and hexanediol may act as plasticizers and provide desirable lubricity depending on the resin. High yield polar solvents useful in the practice of this invention further include water, formamide, dimethylformamide, dimethyl sulfoxide, and the like. Metal desiccants suitable for the solid paint compositions of the present invention may be any of the known metal desiccants.
Metal salts and/or esters of various organic carboxylic acids having the following carbon numbers and mixtures thereof are included.

Cobalt, zinc, zirconium, magnesium, aluminum and manganese salts made from branched C8-,2 carboxylic acids are preferred desiccants. Typical paint formulations described in this invention required unusually high amounts of metal desiccant, on the order of 0.5 to 5 weight percent based on resin weight. The amount of desiccant depends in part on the oil or other double bond source used in the paint system, ie, the number and type of double bonds. Additionally, resins having other pendant and/or terminal functional groups of acid or carboxyl groups may also be used in the present invention.

When the ionizable groups on the polymer are cationic group precursors instead of acid or carboxyl groups, the ionic crosslinking agent is an anionic precursor. As cation forming agents, '1' primary, secondary, tertiary and cyclic amines that react with hydrogen halides and halogenated hydrocarbons to form quaternary halides or quaternary salts; Substituted phosphines that form salts; sulfides that react with '3' alkyl halides to form sulfonium salts; and cyclic ethers that react with (4) acids to form oxonium salts. Anion source crosslinking Examples of agents include acetic acid, nitric acid, hydrochloric acid, sulfuric acid, and relatively short organic polybasic acids such as oxalic acid, malic acid, succinic acid, maleic acid, adipic acid, and the corresponding anhydrides. For industrial coating purposes, blocks of solid paint are advantageously housed in conventional support and application equipment.

Such equipment varies depending on the nature of the coated substrate and can be adapted for continuous application, but typically includes equipment to support the solid paint and the modifications necessary to obtain liquid coatings and films of the required thickness. It has a mechanism that controls the pressure applied to the paint block to cause it to rise.
Thicker coatings are obtained by increasing the pressure applied to the solid paint. Although the solid paint of the present invention can be air dried, industrially the curing of the film can be accelerated by heat or other known energy techniques. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

All parts and percentages are by weight unless otherwise noted.
The desiccant used is a commercially available conventional desiccant. "Minerari Spirit" and "Odorless Mineral Spirit" had boiling point ranges of 149-204°C and 174-210 qo, respectively. Molecular weights are number average molecular weights unless otherwise specified. Examples 1 to 12 are 1. A. Examples 13 to 19 illustrate the type of polymer solution formulations 1. B. 2 illustrates a type of polymer dispersion formulation. Examples 20 to 23 are 1. A. Examples are mixtures of type polymer solution formulations and non-binding (no reactive acid groups) non-aqueous dispersions. Example 1 Trimethylolethane (TME), dehydrated castor oil (DCOFA), azelain dimer-acid (field A LNC1I10) and dimer-acid (E
Resin A was prepared by polymerizing a mixture of MPOLIO 14) to an acid value of 41 (normal range of 41±2) by melt processing at 23°C.

Resin B, which is a "high oil percentage" oil resin, was produced by polymerizing 23 to 0 and an acid value of 42.0 using the same method as Resin A.

Two pieces of resin C manufactured using pentaerythritol (PE) instead of trimethylolethane (TME).

Polymerization was achieved with an acid value of 42.0. Resin D, prepared using a combination of DCOFA and tung oil instead of DCOFA alone, was polymerized at 23,800 to an acid value of 43.0.

Table 1 Example 2 Polyester resin A (25 parts) was mixed with 1 Yukuni tung oil, 13 parts mineral spirit, 2. Cobalt desiccant (metal 12.0%) in the eaves, 2. Manganese desiccant for foundation (metal 9.
0%) and 3.5 parts of zirconium desiccant (metal 12.
0%) to form a hydrocarbon solution, and the resulting composition was left at room temperature for 16 hours.

Under a Cowlee lamp, titanium dioxide (4 parts) and calcium carbonate (10 parts) were mixed with the resin solution to obtain a #6 Hegmangrind.
Various weights of sodium hydroxide were added as 25% solutions in methyl alcohol to produce the solid paints shown in Table 0'. Solid Paint 2A had a striped film appearance and was also slightly too hard to apply. That is, there was resistance during application. Also, the coating properties were said to be too hard. Gel strength 147 and 16 respectively
1 solid paints 2B and 2C had satisfactory application properties and coating appearance. That is, these paints did not require much force to apply, and the resulting coverage was uniform. All three paints were dimensionally stable and provided satisfactory dry application to test panel surfaces. Table B *Average of 3 measurements Example 3 In the same manner as in Example 2 and with the same relative amounts of resin, tung oil, mineral spirits, cobalt desiccant, manganese desiccant, zirconium desiccant, titanium dioxide and calcium carbonate. Paints 3A and 38 were prepared from Resin C using

A third paint 3C was similarly prepared from Resin C but with 1.3 parts cobalt desiccant (12% metal), 0.5 parts manganese desiccant (9.0% metal), 3.0 parts It contained zirconium desiccant (12% metal) and 0.1$ aluminum stearate. Solid paints 3A, 3B, and 3C formed by adding 25% sodium hydroxide in methanol exhibited good gel strength, coating properties, coating appearance, and drying properties.

Example 4 12 parts tung oil, 1 part mineral spirits, 0.95
part cobalt desiccant, and 2.1 parts zinc desiccant (16
Polyester resin C (2% metal) by mixing with polyester resin C (2% metal)
5 parts) was made into a hydrocarbon solution.

Separately, a resin solution of the second type of resin C was prepared, but this
．． It was the same as above except it contained $ parts of cobalt desiccant and an additional 0.45 parts of manganese desiccant. Containing these resins and 50% titanium dioxide prepared therefrom,
Paints that do not contain calcium carbonate are designated 4A and 4B, respectively, in the table below. Paints 4A and 4B with neutralization values of 160 and 170 have gel strengths of 176 and 13, respectively.
8 was shown. The application properties of 4A were slightly poorer, with the solid paint being too soft.

The film appearance and drying properties of both paints were satisfactory. Example 5 Experiments 2A, 2B, 3A, 3B and 3C were repeated, except that the desiccant was added after the pigment was added to the resin, and substantially similar satisfactory gel strength, application properties and drying rates were obtained. Ta.

Example 6 Paint blocks measuring approximately 10 skins x 1 x 100 cm were stored in thin Saran (trade name of Dow Chemical Company) bags for 6 months.

After this storage period, the paint was applied to test panels without any deterioration in application or film properties. In addition, a solid paint was prepared from the same resin, but with an acid number of 30-60, and had satisfactory solid paint properties. Similar good results were obtained when using oitica fatty acid, safflower fatty acid, soya fatty acid or linseed fatty acid in place of dehydrated castor oil fatty acid. Gel strength measured with a universal penetrometer is 130 to 1
The best spreadability was obtained with 8 ribs. gel strength loo
In the case of 130 to 180 to 190, effective group paint was obtained although the characteristics were slightly inferior. Example 7 Resin D was prepared by esterifying dehydrated castor oil fatty acids (1 part) with trimethylolethane (12 parts) at a temperature below 24 psi to obtain a product with an acid number of 4.0.

After that, 2. Transesterification was carried out by reacting with tung oil (168.5 parts) in the presence of base surge catalyst until the product was completely miscible in methanol. The resulting product was combined with A-LAIC III0 (91.6 parts) and EMPOLIO14 (555 parts) and heat treated to an acid value of 43.0. The molecular weight of the resulting resin is approximately 13
It was 00. Lissage (
2.0 parts) Cationic resin E was prepared by condensing Resin D (1040.4 parts) with N,N-jethylaminoethanol in the presence of a catalyst.

After removal of water and excess N,N-jethylaminoethanol, Resin E had a molecular weight of 1500. Resin E
50'50% by weight solution in mineral spirits of 37%
Resin E was gelled by neutralization (100 and 300%) with hydrochloric acid. The resulting solid paint had inferior properties to a gel neutralized to 200% with tristate sulfuric acid;
Gel strength was loo-150. Example 8 1 Moribe tung oil, 13 parts mineral spirits, 0.6 parts cobalt desiccant (120.0% metal), 0.6 parts manganese desiccant (9.0% metal) and 6.0 parts Polyester resin C (25 parts) was made into a hydrocarbon solution by mixing with zirconium desiccant (12.0% metal) and the resulting composition was left at room temperature for one hour.

Under Cowlee rope azusa, titanium dioxide (4
#0 parts) and calcium carbonate (No. 1) were mixed with the resin solution to obtain #fine egmangrind. Next, “Vacuum C
Various weights of sodium hydroxide were added as a 25 wt. % solution in methanol under reduced pressure in a 200 methanol tank to obtain a solid paint (Table 2). This method of addition reduces the chance of air becoming incorporated into the "final" mass paint. Paints 8A and 8B (front row) exhibited excellent border appearance and coatability. Both paints were dimensionally stable and exhibited good drying properties when applied to test panel surfaces. Example 9 Resin F was prepared in the free radical state as follows.

Methacrylic acid in 1st anchorage, lauryl methacrylate in 9th pass area
1 part of bis(4-t-butylcyclohexyl) peroxycarbonate (initiator) and 300 parts of mineral spirit were placed in a kettle.

Polymerization was carried out by heating the mass in the kettle to 60 qo and maintaining this temperature for 2 hours. A conversion of 99% was obtained.

The acid value of the polymer was 65.0%. Approximately 10 parts of mineral spirits were removed by vacuum distillation. Various weights of sodium hydroxide were added as a 25 weight percent solution in methanol to 75 parts of 33% N/V resin, as described below.

These two types of "transparent" paints can be explained as follows.

The product obtained from Experiment A had little dimensional stability and poor application properties. That is, upon application, the paint film was too thick and required much more force (compared to the previous example) to stretch it on the test panel.
Experiment B resulted in a strong product, which exhibited good dimensional stability (gel strength of about 16 ribs) and good application properties. Paint B exerted almost no drag during application. Both of these paints performed well on the test panel.
A dry coating film was formed. Example 10 Resin G, which is 100% N/V dicarboxypolybutadiene with a molecular weight of 1410 and a carbon value of 65.0, was prepared into the following solid paint.

Paint A with a gel strength of 250 did not exhibit dimensional stability.

Paints B, C and D were dimensionally stable. When applying, Paint B has a tendency to form a too thick film.
Also, it was a little too elastic. (i.e.) had a tendency to become toffee-like. Paint C was too hard and therefore had poor applicability. Paint D had dimensional stability and satisfactory application properties. All paints formed baggy films in the test panels. Example 11 146 parts trimethylolpropane, 146 parts pentaerythritol, 908 parts dehydrated castor oil fatty acid and 41 parts
3 parts of azelain dimer acid (A-LAICIIIO)
A mixture consisting of the following was polymerized by heat treatment to an acid value of 249 oo and an acid value of 42 to produce an alkyd resin.

The resulting resin was measured using the Gardner-Boldt foam viscosity measurement method AST.
It had a viscosity Z2 measured using MD1545.
116.5 parts trimethylolpropane, 116.5 parts pentaerythritol, 296 parts dehydrated castor oil fatty acid and 821 parts azelaine dimer acid (AZELMCI).
Alkyd resin 1 was prepared by polymerizing a mixture consisting of IIO) with an acid value of 46 and an acid value of 30.

The resulting resin exhibited a viscosity of Z0 (Gardner-Bolt). EXAMPLE 12 Solid vents were prepared from resin day and day 1 in the same manner as in Example 2 except that the desiccant was allowed to stand at room temperature for 1' incubation time.

The order of addition of ingredients is as per the table below, mix and add #5
It was a 1'2 Hegman grind. {a diluent alkyd resin that cannot directly participate in ion bonding (
Reichhold Chemicals (Canada) tb) Dramaton is a registered trademark product of GLIDDEN-DURKEE, a division of SCM Corporation.

{c'PennsylvaniaClassSandC
orp. crystalline silica products.

(d) Johns-MEnvjilleCO. diatom silica products.

[e-N. L. Md female tries solid paint 1,
Samples 2 and 3 were dimensionally stable and had properties comparable to or better than the solid vents of the previous examples.

When applied to a substrate by contact and hand pressure, the desired surface coating was obtained, which air cured overnight. NAD resins 1,2,2A,
3 and 4 were manufactured.

Table m shows the relative proportions of its components. Non-solvent and about 50%
Polymerization was initiated by placing 4 parts of the monomers together with the desired stabilizer in a polymerization kettle and heating to a reflux temperature of 40-80°C. After that, the remaining monomer, stabilizer (3
0%) and the free radical initiator along with ethyl acrylate as one feedstream, while the acidic component, i.e. methacrylic acid and the remaining stabilizer (20%), were added as a separate feedstream at reflux temperature. It was added over a period of 3 hours. Further initiator (1/4 of the total amount) was introduced in two parts in ethyl acetate over a further 2 hours of reaction time. After further refluxing for 2 hours, about 90 qo
The low boiling solvent was removed by heating to . In accordance with the present invention, NAD is combined with carboxylic acid sites (or other ionization sites) at the surface (or at least a large portion of the surface) of the particles to form external acid sites on the suspended polymer particles. It is important to manufacture In this case, the acid feed started 10 minutes after the other monomer feeds began. The acid supply was completed 10 minutes after the completion of the supply of other monomers. The conditions shown in this example can be modified as long as the acid sites from which stable NAD is obtained are utilized for gelation and are not embedded in the particles.

It is desirable to measure the acid value of NAD. Table m Preparation of NAD Stabilizer 100 parts of 12-hydroxystearic acid, 3.5 parts of tetralinepropyl titanate, and 6 parts of xylene were heated together to 200 degrees under a nitrogen atmosphere.

The reaction was monitored by collecting the by-product water. The product obtained had an acid number of 34.2 (calculated value 33).
This product was treated with 400 parts of methyl ethyl ketone and 1 part of triethylamine at 900 °C under nitrogen for 82.
Further reaction with 3 parts of glycidyl methacrylate gave a second intermediate with an oxidation of 4.3 and a non-volatile content of 93.4. (Methyl ethyl ketone was removed at the end of the reaction.) This second intermediate (321 parts) was combined with ethyl acetate (50 parts), dodecyl mercaptan (1.5 parts) and azobisisoputilonitrile (3. ) Polymerized with 225 parts of methyl methacrylate at free standard conditions in the presence of a free radical initiator. A stabilizer was obtained with a yield of 98%. Preparation of alkyd modifier 136 parts pentaerythritol, 56 parts dehydrated castor oil fatty acid, 135 parts AZEL Mountain C IIIO dimer
A polyester alkyd condensation polymer was prepared by condensing the acid and 168 parts of EM Yen OL IO14 dimer acid in a melt cook at 238°C to produce an alkyd resin with reactive carboxylic acid functionality, an acid number of 41, and a molecular weight of 1500. Obtained.

Example 13 Resin NAD-2 (87 parts of a 50 N/V suspension in mineral spirits) was prepared and treated with 3 Bose alkyd modifiers and 12
This amount of titanium dioxide was mixed to form a #6 Hegman grind.

No desiccant was used. Similarly, resin NAD-2A (
94 parts of 50N/V in mineral spirits) was mixed with 25 parts of alkyd modifier and 115 parts of titanium dioxide. Then various weights of sodium hydroxide (2
5% solution) to form a solid paint and designated Experiments IA and IB in Table W. Gel strength 164 peel 1 each
The solid paints IA and IB with 85 were dimensionally stable, had good application properties, and gave satisfactory dry coverage when applied to test panels. Good application properties were defined as a uniform paint film formed on the test panel when the paint was spread on the panel, and the work required to do so was not excessive. In the third paint, resin NAD-2 (50N/V in mineral spirits)
94 parts) of 25 parts of alkyd modifier, 115 parts of titanium dioxide, 0.5 part of cobalt desiccant (12% cobalt), 0.5 part of manganese desiccant (8% metal), 4. Mixed with $ parts zirconium desiccant (12% metal).

The desiccant was added to the alkyd modifier. then 16
．． One part of sodium hydroxide (25% solution in methanol) was added to yield a solid paint shown as Experiment IC in Table N. The paint exhibited dimensional stability, had good application properties, and exhibited excellent drying properties when applied to test panels. Table W Average of 3 readings Example 14 Resin NAD-1 (110 parts) was prepared, 5, 10 and 1
In three compositions A, B and C each containing 5 parts tall oil alkyd (100% solids) 100 parts titanium dioxide, 0.015 parts cobalt desiccant (12% cobalt), 0.1 This was mixed with zirconium desiccant (12% zirconium) to form a #6 Hegman grind.

Various weights of sodium hydroxide were then added as 25% by weight solutions in methyl alcohol to form mass paints designated Experiments OA, OB, and ROC in Table W. Solid paints OA and OB with gel strengths of 135 and 195 respectively
showed satisfactory application properties. The application properties of the solid paint OC were poor. All of these solid paints were dimensionally stable and provided excellent dry coverage when applied to test panels. Example 15 Resin NAD-2 (105 parts) was prepared with 100 parts titanium dioxide, 0.015 parts cobalt desiccant (12% cobalt), 0.10 parts zirconium desiccant (12% zirconium) and 10 parts titanium dioxide. Part of tall oil alkyd (100%
) to form a #6 Hegman grind.

Various weights of sodium hydroxide in methyl alcohol
It was added as a 5% by weight solution to form a solid paint designated Experiments mA and mB in Table N. The solid paint mA with a gel strength of 240 had poor application properties (too soft and hard to spread), contrary to the good properties of the solid paint mA with a gel strength of 190. Although these paints exhibited dimensional stability, the appearance of the coatings was poor due to insufficient adhesion. Example 16 Example using resin NAD-3 (101 parts) in one case using 1 part tall oil and in the other case using 15 parts PoIJ ester alkyd modifier in place of tall oil. 1
It was prepared in the same manner as NAD-2 in No. 3.

Solid paints prepared by adding a 25% by weight solution of sodium hydroxide in methanol were designated solid paints WA and WB in Table W. Solid paints WA and NB have a gel strength of 1
50 and 200, and had dimensional stability and satisfactory application and film properties. EXAMPLE 17 Paint blocks formed from the solid paint described above and measuring approximately 10 skins x 1 roll were stored for 6 months in thin Saran (a product of the Dow Chemical Company) bags.

After the storage period, these paints were applied to test panels and no deterioration in application or film properties was observed. Acid value 2
Solid paints made from the same but identical resins having a ratio of 5-60 exhibited satisfactory solid paint properties. Gel strength measured with a universal penetrometer is 130 to 19
5 gave the best coating properties. On the other hand, gel strength 10
The characteristics of 0-130 and 195-200 are
A low but effective solid paint was obtained. Example 18 Resin NAD-4 (94 parts 5/V suspension in mineral spirits) was prepared with 3 parts alkyd modifier, 10 parts titanium dioxide, 15 parts calcium carbonate, 0.65 parts
1 part cobalt desiccant (12% cobalt), 0.65 parts manganese desiccant (8% metal) and 6.0 parts zirconium desiccant (12% zirconium) to form a #6 Hegman grind.

Sodium hydroxide (25% solution in methanol) was then added to form a solid designated WA in Table W. This solid paint had good application properties, exhibited dimensional stability, and formed a sticky coating on test panels. Reference Example A "non-aqueous dispersion" was prepared without using a stabilizer.

A particular monomer system was selected that was sufficient to partially swell in the septic solvent and to maintain the stability of the dispersion. In this case, 78 parts of butyl acrylate, 10 parts of methacrylic acid, 8 parts of dodecyl mercaptan, 1 part of azobisisoputilonitrile, and 600 parts of mineral spirits were charged into the reactor.

This charge was held for 5 hours at 80:00. Conversion rate is 97
%, the oxidation of the dispersion was 43.7. Theoretical oxidation is 7
2. When using this manufacturing method, some amount of acid was introduced. Two parts (60% N/V resin) of 180 parts each were mixed into 25.0 parts (neutralization rate 200%) and 37.5 parts (3
00% neutralization) of 25% sodium hydroxide solution in methanol.

Both products exhibited dimensional stability but poor coating properties. This product was not true NAD, at best a very coarse dispersion.

However, it shows that internal stabilization is possible if the monomers are chosen correctly. This system was not stable and had many ionizable sites embedded within it. Example 19 Preparation of a non-aqueous dispersion of a non-bonding NAD resin A non-bonding NAD resin (i.e., having no reactive functional sites and gelling sites) is treated with a non-solvent, a free radical initiator, and a stabilizer. prepared by addition polymerization of various monomers in the presence of

An example is shown in the table below. Polymerization was initiated by charging a small portion of monomer to a polymerization kettle along with a non-solvent (mineral spirits, etc.) and 50% of desired stabilizers and heating to 75-80 qo. After about 15-30 minutes, the remaining monomers, stabilizers, etc. were started to be fed and continued for 3-4 hours.
The batch, kept at reaction temperature for an additional hour, was then cooled to yield a milky dispersion with a low viscosity (100-20 ps) and a non-volatile content of 4% by weight. 'a' boiling point 17
4-21000 'b' Boiling Point 149-204q○ Example 20 Although various variations of the NAD stabilizers exemplified in Examples 13-18 are also suitable for making non-binding NAD resins, the following are particularly preferred useful stabilizers. shows the production of the agent.

90 parts of 12-hydroxystearic acid, 31 parts of tetranepropyl titanate, and 9 parts of odorless mineral spirit were heated together to 210<0>C in a nitrogen atmosphere.

The reaction was monitored by collecting the water that formed. The product had an oxidation of 36 (calc. 33). 1 as a catalyst
The product was further purified using triethylamine from Ikarigun.
C. and reacted with 97.6 parts of glycidyl methacrylate under nitrogen. The reaction product is oxidized 1.8 and non-volatile content 9
It had a value of 1.0. This second intermediate (44 parts) was prepared in the presence of odorless mineral spirits (80 parts). 8 under free radical conditions using azobisisobutyronitrile from Japan.
Polymerization was carried out with 300 parts of methyl methacrylate at 5°C. The product was reduced with 30 parts of odorless mineral spirits. The final non-volatile content was 3% by weight. Example 21 Alkyd resin J, which has binding sites and is particularly useful for making solid paints when combined with the non-binding NAD resin non-aqueous dispersion of Example 19, is combined with 295 parts of trimethylolpropane, 69 parts of A mixture consisting of 250 parts of dehydrated castor oil fatty acid, 340 parts of Azelain Timer (AZELMC IIIO) and 423 parts of EM Yen OLIO14 was
It was produced by polymerizing to have an acid value of 42 at qo.

The resulting resin had a Gardner-Holdt viscosity Z. Example 22 A solid paint was made from Resin J using the following formulation.

Each material was added in the above order except that half of the NAD (5 parts) was retained until a grind was obtained (ie, after all pigments had been added).

The grind was 51/2 Hegman. remaining NAD
was added and after the batch had cooled, the desiccant was added. The desiccant was added under reduced pressure in a "vacuum Cowles" with sodium hydroxide, methanol, and allowed to stand for 1 hour before forming a solid paint. This method of addition reduces the chance of air inclusion in the "final" solid paint. Both paints exhibited dimensional stability.

When rubbed onto the substrate (by hand), the paint adhered to the substrate and formed a film. Both coatings dried overnight. Solid paints made by combining non-bonding NAD resins with small amounts of Type IA ionic bonding resins shown in Examples 1-12 and 21 are useful not only for commercial applications such as protective coatings and coil coatings. It is also particularly suitable for retail use in the painting industry.

A particularly great advantage of this combination and internal combination of ionic bonds and NAD resins (both of bonded type) is that dimensional stability is maintained with fewer bonding sides, while application and film properties are greatly improved. Example 23 A similar satisfactory dimensionally stable solid paint is obtained by changing the proportion of non-bonding NAD resin shown in Example 22 from 7.5 to 200 per 25 parts of ion-bonding resin.

Example 24 Example of NaOH/Butanol Gelling Agent for Solid Paints Solid paints were made from ionomer resins according to the following formulation.

Ionomer resin: 90% NV (weight): AV=21.
0 (solid content) VIS=TU (Gardner) Weight % Trimethylolpropane 16.6 Azelaic acid 18.3 D. C. ○
Fatty acid 55.1 Mineral spirit 10.0100.0%Paint formulation Weight% Alkyd AC
-100 (Reichhold) 8.2 Lecithin (grinding aid) 0.4 Ti02 Rutile Titanox 2071 25.4 Minnie Usil 10 (M
in1U1Sill0) 2.6 Mineral Spirit
9.8 Ionomer resin
22.812% cobalt desiccant
0.49% manganese desiccant
0.112% zirconium desiccant 2.
1M. E. K (anti-skin agent) 0.1N
AD (45% MMA, 55% mineral spirits)
9.1 Celite 499
3.7 Silicone solution (slip agent) 1.1 Troiquid (antifoam agent) 0.1 6% NaOH/Butanol 14.1 100% Penetration (after 1 day) 18 mm Example 25 NaOH/KOH for solid paint Mixture Gelling Agent Example A solid paint was made from an ionomer resin according to the following formulation.

Ionomer resin: 90% NV (weight): VIS=S (Gardner): AN (solids) 22.5% by weight Trimethylolpropane 13.5D.
C. 0. F. A55
．． 8 Azelaic acid 18.5 Ethylene glycol 2.2 Mineral spirit 10.0100.0
% Paint Formula Weight % Ionomer Resin Pine. 9 Rheoxl 1 (Bodyg agent) 0.4 (Rheoxl) ByK
300 (antifoaming agent) 0.1 Lecithin (grinding aid) 0.4 Shading base 0.7 Ti02 Rutile type - Titanox 2071 257 Minnie Usil 1
0 2.6 (Min-U-S
ill0) Celite 499 2.6 coarse, cut oil
1.8 Alkyd AC-100
7.7 (line hold)
Mineral Spirit 7-7 N. AD (45% MMA, 55% mineral spirit)
21.2 M. E. K (Anti-Hif agent) 0.1 Silicone solution (slip agent) 1.1 12% Cobalt desiccant 0.2 9% Manganese desiccant 0.1 12% Zirconium desiccant 1.6 24% Na.

H/methanol 2.224%KOH/methanol
〇． 9 100.0% Penetration (after 1 month) 10-11 mm

Claims (1)

[Scope of Claims] 1. Contains each of the following solid components I, II, and III.
A solid paint composition characterized by having a gel strength of 0.00 mm penetration and dimensional stability based on ionic bonding. IA molecular weight of 1,000 to 7,000 and 20 to 8
An ion-binding resin having a sufficient amount of reactive carboxylic acid functional groups to give an acid number of 0 is added to a non-polar solvent from 25 to 9
0% by weight solution, IB 25,000 to 1,
An ionically binding polymer having a molecular weight of 0.000,000 and a sufficient amount of reactive carboxylic acid functionality to provide an acid number of 25 to 60 is dispersed in a nonpolar nonsolvent as a 25 to 90% suspension by weight. Stabilized non-aqueous dispersion containing a NAD resin and an NAD stabilizer, an oil-based alkyd modifier, I
Stabilized non-ionic bond obtained by dispersing NAD resin having a molecular weight of 25,000 to 1,000,000 and not having ionic bonding properties in a non-polar non-solvent as a suspension of 25 to 90% by weight. A dispersion of NAD resin and the above I
In the mixture with the ion-binding resin solution described in Section A, the ratio of non-bonding NAD resin to ion-binding resin is 2.
:1 to 8:1 of the above IA, IB, I
A polymer selected from C, II. A solution or suspension containing 10 to 50% by weight of an ionic crosslinking agent of sodium or potassium hydroxide dissolved in a low-number aliphatic alcohol having 1 to 8 carbon atoms, and III. A polymer. A desiccant comprising 0.5 to 5% by weight of a metal salt of an organic acid based on the total weight, and the above
100 per mole of acid functionality of each component in I and II
600 mol% of metal hydroxide.