JPS59197402A - Oxidation-curable water-dispersible resin composition - Google Patents

Abstract

PURPOSE:The titled composition which has low viscosity and a solid content of which can be readily increased, containing a reaction product between a maleinized product of an addition polymer containing oxidation-curable groups and a water-insoluble hydroxyl group-containing addition polymer. CONSTITUTION:A resin composition obtained by neutralizing a reaction product between (A) a maleinized product of an addition polymer having drying oil fatty acid residues and/or semidrying oil fatty acid residues which are bound to the main chain through ester linkages as side chains (e.g., a maleinized product of a resin obtained by a dehydration reaction between a styrene/allyl alcohol copolymer and linseed oil fatty acid, and (B) a water-insoluble hydroxyl group- containing addition polymer (e.g., the addition polymer which is polymer A before maleinization) and dispersing the neutralized product in water. When this resin is neutralized to impart water solubility, it tends toward forming an aqueous dispersion rather than an aqueous solution. Therefore, the formed dispersion has low viscosity and its solid content can be easily increased.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oxidation-curable water-dispersible resin composition, and more particularly, the present invention relates to an oxidation-curable water-dispersible resin composition, and more particularly, a reaction product of a maleated addition polymer having an oxidation-curable group and a water-insoluble addition polymer containing a hydroxyl group. The present invention relates to an oxidation-curable water-dispersible resin composition containing a compound as a main component.゛Conventionally, maleated addition polymers having drying oil fatty acid residues and/or semi-drying oil fatty acid residues connected to the main chain by ester bonds as side chains, the main chain is a carbon-carbon compound that is resistant to hydrolysis. Because it is a bond, it has excellent storage stability, and when used as a resin for water-based paints, the coating film formed from it has excellent water resistance, so it is widely used. It has been put into practical use. However, conversely, because the main chain has many carbon-carbon bonds, it is highly oily, and when this polymer is made into an aqueous solution, the viscosity tends to increase, making it impossible to increase the solid content. There are drawbacks to receiving it.

Therefore, the present inventors conducted extensive research with the aim of improving the drawback of high viscosity when making the maleated product of the conventional addition polymerized polymer solubilized in water. When a hydroxyl group-containing water-insoluble addition polymer is reacted, the resulting resin tends to become a water dispersion rather than water-soluble when it is neutralized and made water-soluble, resulting in a low viscosity and easy dispersion. The present invention was completed by remembering that the above problems can be solved by increasing the solid content.

Thus, according to the present invention, (4) Maleated addition polymer having a drying oil fatty acid residue and/or a semi-drying oil fatty acid residue connected to the main chain by an ester bond as a side chain [hereinafter referred to as this product] Reaction with [sometimes abbreviated as addition polymerization polymer (4)]] and (J) hydroxyl group-containing water-insoluble addition polymerization polymer [hereinafter, this product may be abbreviated as [addition polymerization polymer (E) J]] An oxidation-curable water-dispersible resin composition obtained by neutralizing the product and dispersing it in water is provided.

In the present invention, the addition polymer having a drying oil fatty acid residue and/or a semi-drying oil fatty acid residue as a side chain forming the addition polymer (4) can be obtained, for example, as follows. One of them is, for example, a homopolymer of a hydroxyl group-containing or glycidyl group-containing bi'-t lemonmer or a copolymer with a vinyl monomer that does not contain a hydroxyl group or a glycidyl group, and a drying oil fatty acid and/or a semi-drying oil fatty acid. When the above-mentioned copolymer is used, it is preferable that the copolymer contains 5% by weight or more of a vinyl monomer component containing a hydrous acid group or a glycidyl group. Examples of the method include a method of adding a drying oil fatty acid and/or a semi-drying oil fatty acid to glycidyl methacrylate or glycidyl acrylate to obtain a homopolymer of the monomer or a copolymer with the above vinyl monomer. Also in this method, It is preferable to use a copolymer, and the copolymer preferably contains 5% or more of the above-mentioned additional monomer.

Here, the above-mentioned hydrated acid group, t<, etc. as the glycidyl group-containing vinyl monomer include allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, glycidyl methacrylate,
Glycidyl acrylate, Mettsuk-P (manufactured by NOF Chemical Co., Ltd., trade name), and the like can be mentioned.

Examples of the vinyl monomers mentioned above include styrene, vinyltoluene, α-methylstyrene, acrylonitrile, methacrylatetrile, alcohols having 1 to 26 carbon atoms, preferably 1 to 18 carbon atoms, and acrylic acid or methacrylic acid. Ester, ester of ethylene glycol monoalkyl ether or diethylene glycol monoalkyl ether (alkyl group has 1 to 8 carbon atoms) and acrylic acid or methacrylic acid, propylene glycol monoalkyl ether or dipropylene glycol monoalkyl ether (alkyl group) 1 to 8 carbon atoms) and acrylic acid or methacrylic acid, monocarboxylic acids having 4 to 26 carbon atoms other than drying oil fatty acids and semi-drying oil fatty acids, and glycidyl methacrylate (< indicates glycidyl acrylate) Examples include monomers with added hydrous acid groups, glycidyl group-containing vinyl monomers, glycidyl acrylate-added fatty acid monomers, and glycidyl acrylate-added fatty acid monomers, and the resulting polymers are stable at high temperatures. Preferably, monomers are used. In addition, seven polymers commonly used in radical polymerization, such as phtadiene, isoprene, chloroprene, pentadiene, vinyl acetate, vinyl chloride, and polymer monomer (trade name, manufactured by Shell Chemical Co., USA), can also be used.

In addition, as drying oil fatty acids and semi-drying oil fatty acids, fatty acid oil lengths can be used in the range of 5 to 90, and bipartite fatty acids,
Particularly preferred are hempseed oil fatty acids, poppy oil fatty acids, sunflower oil fatty acids, walnut oil fatty acids, etc., which contain many non-conjugated double bonds, easily undergo maleation and polymerization reactions without gelation, and have good curability. In addition, corn oil fatty acids, cottonseed oil fatty acids, mustard oil fatty acids, oicilla oil fatty acids, peanut oil fatty acids, eno oil fatty acids, poppy oil fatty acids, rubber oil fatty acids, sesame oil fatty acids, tall oil fatty acids, tung oil fatty acids, dehydration and mustard oil fatty acids , heidiene fatty acids, etc. can also be used.

The addition polymer (4) of the present invention is synthesized by maleating an addition polymer having a drying oil fatty acid residue and/or a semi-drying oil fatty acid residue connected to the main chain through an ester bond as a side chain. Maleation can be carried out by a conventional method, and maleic anhydride is added to about 120 to 250
The reaction should be carried out at ℃. In particular, when many hydroxyl groups remain in the polymer, it is preferable to esterify with a low-molecular or high-molecular acid such as acetic acid, propionic acid, stearic acid, etc. to remove excess hydroxyl groups, and then maleate the polymer. The amount of maleation in the addition polymerization polymer (a) is such that the total acid value is 5.
-300, preferably 10-150, more preferably 20-100.

If the acid value is too low than 5, the resulting water-dispersible resin composition will be a stable aqueous dispersion.
If it is too high, the coating film performance such as water resistance will deteriorate.

In addition, if the molecular weight is too low, it will not be possible to form a stable aqueous dispersion, and if the molecular weight is too high, dispersion will be difficult.
The number average molecular weight is usually in the range of 800 to 500,000, preferably 1,000 to 00,000.

Further, the addition polymerization polymer (B) used in the present invention has a hydroxyl group and is substantially water-insoluble, and may be, for example, an addition polymerization polymer before maleation of the addition polymerization polymer (4). can. Since this product does not require a maleation reaction, drying oil fatty acids or semi-drying oil fatty acids having a large number of conjugated double bonds, which are particularly suitable for addition polymerization polymer (4), can also be freely used as the constituent number 1. I can do it.

However, since the addition polymer (paddy) is reacted with the addition polymer (A), the addition polymer (A)
Although it is not necessarily necessary to introduce the drying oil fatty acid or the semi-drying oil fatty acid that takes part in the crosslinking reaction into Bl, it is preferable to introduce the above-mentioned fatty acids in order to ensure the crosslinking reaction of the reaction product. That is, the oil length is in the range of 0 to 90, preferably 0 to 70 in terms of coating film performance, and more preferably 20 to 60.

Sorry, the amount of hydroxyl groups in the addition polymerization polymer (B>) does not need to be large because the reaction between the hydroxyl groups and the acid anhydride groups of the addition polymerization polymer (A) is ensured, and the hydroxyl group value is 0. ．．
It can range from 5 to 300, more preferably 1
~50. If the amount of hydroxyl groups is too large, gelation tends to occur during the reaction.

The above-mentioned addition polymerization polymer (4) and addition polymerization polymer (
The reaction with Be is carried out by the reaction between the acid anhydride group of the former and the hydroxyl group of the latter, and the bonding is reliable, so even when a combination of resins with poor compatibility is used, a transparent and glossy coating film is formed. be able to.

The mixing ratio of addition polymerization polymer (4) and addition polymerization polymer (B) is 97/3 to 3/97, preferably 10/90 to 90/1-0, and more preferably 20/8 by weight.
0 to 80/20. As the proportion of addition polymer particles increases, the resulting dispersion tends to have a smaller particle size and a higher viscosity. Also, the overall acid value is 3 to 15.
0, preferably 5-100, more preferably 10-5
It is in the range of 0. The higher the acid value, the more likely it is to be water-soluble, while the lower the acid value, the less water-dispersible it becomes.

The reaction between the addition polymer and the addition polymer (B is carried out by mixing the two and heating at 50 to 250°C for 0.5 to 4 hours. After the reaction, remove the remaining acid anhydride with water, alcohol, amine, ammonia, etc.) After the group is ring-opened, it is neutralized with a neutralizing agent such as an alkali metal, ammonia, or an amine.
Use by dispersing in water.

When using the water-dispersible resin composition obtained by Ichiki's invention as a paint binder, pigments, pigment dispersants, thickeners, dryers, other organic solvents, etc. are added as necessary. be done.

The water-dispersible resin composition obtained according to the present invention is used as a room-temperature curing type coating forming agent, but it can also be used as a baking drying type coating forming agent. In this case, a hardening agent such as melamine can also be added. Furthermore, it can also be used for other applications such as resin processing agents. Although the water-dispersible resin composition of the present invention exhibits excellent performance by itself, it may be used in combination with other water-based resins for a wider range of applications.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, unless otherwise specified, parts and percentages used below are by weight.

Example I RJ-100 (number average molecular weight 1,600, OH content 7
．． 7% styrene/allylic alcohol copolymer (manufactured by Monsanto Co., USA) 305f, linseed oil fatty acid 302f, and dibutyltin oxide 0.62 were placed in a 2-t 4-Solo flask and subjected to a dehydration reaction at 240°C for 6 hours under xylene reflux. As a result, a resin having an acid value of 0.5 was obtained. To this, maleic anhydride 372 was added and an addition reaction was carried out at 200°C for 4 hours, and then the solvent was removed by vacuum distillation to obtain a maleated resin.

In another 2t 4-sol flask, RJ-101 (styrene/allylic alcohol copolymer with number average molecular weight 1150 and OH content 7.7%, manufactured by Monsando, USA) sosr,
Linseed oil fatty acid 408 and phthalic anhydride 581 were added and a dehydration reaction was carried out in the same manner as above until the acid value reached 4 to obtain a water-insoluble resin.

The water-insoluble resin 4272 thus obtained is added to the maleated resin and stirred well. The consistency of the mixture was 25 with a 75% butyl cellosolve solution.
When heated for a period of time, the viscosity increased to Z7. Water 102 was added to this mixture and the mixture was left at 100° C. for 1 hour.

Example 2 RJ-101 at 660 f, linseed oil fatty acid at 325? ,
Phthalic anhydride 75! i' and benzoic acid 90f in Example 1
Dehydration condensation was carried out in the same manner as above to obtain a water-insoluble resin (1) with an acid value of 6. Furthermore, 1015 of RJ-101
A water-insoluble resin (2) having an acid value of 1.3 was obtained by dehydration condensation of 7 and a high diene fatty acid 1254 in the same manner. Next, 500 g of the former resin (1) and 100 g of the latter resin (2) were added to 400 f of the maleated resin obtained in Example 1.
? Add and stir well.

The viscosity of the mixture was 25 in 75% butyl cellosolve solution. When this was heated at 200°C for 1 hour, it became 2617. Water 72 was added to the thus obtained reaction product, and the mixture was further reacted at 100° C. for 1 hour.

Example 3 RJ-101 66 Of, high diene fatty acid 325f
? , 437 g of talic anhydride and 143 g of benzoic acid were condensed to an acid value of 6 in the same manner as in Example 1 to obtain a water-insoluble resin. This resin 417f is added to the maleated resin 621' obtained in Example 1 and mixed well. The viscosity of the mixture is 75
% butyl cellosolve solution was 23-4. This 2
The mixture was heated at 00° C. for 2 hours and reacted until the viscosity reached Z5. 10P of water was added to the reaction product thus obtained, and the reaction was further carried out at 100°C for 1 hour.

Example 4 A dehydration condensation reaction was carried out using 3052 RJ-101 and 376 linseed oil fatty acids in the same manner as in Example 1, and then 412 maleic anhydride was added (reaction was carried out at 200°C for 4 hours). A maleated resin with an acid value of 0.4 was obtained.
Water-insoluble resin (2) 465 f synthesized in Example 2 using the hydene fatty acid was added and stirred well. The viscosity at this time was 2-21 as a 75% butyl cellosolve solution. This was heated at 200° C. for 2 hours to react until Z:', resulting in a reaction product. water 112
Add and heat for another 1 hour at 100℃.

Comparative Example 1 A composition having the same composition as Example 3, but the maninated resin was simply mixed after its acid anhydride group was ring-opened in advance.

Comparative Example 2 A maleated resin synthesized in the same manner as in Example 1 except that the amount of maleic anhydride was changed to 60% (22f) in the production of the maleated resin was opened in the same manner as in Example 1. I made a circle.

Comparative Example 3 A dehydration condensation reaction was carried out in the same manner as in Example 1 using 5087 g of RJ-101, 470 g of linseed oil fatty acid, and 412 g of 7-talic anhydride, and then 38 g of maleic anhydride was carried out. Kazuyuki added and performed the maleation reaction.

Then, the acid anhydride groups of the maleated resin obtained were ring-opened with water.

Comparative Example 4 The same formulation as in Comparative Example 3 was used except that the amount of maleic anhydride was changed to 272.

The compositions obtained in the above Examples and Comparative Examples were neutralized in equivalent amounts with triethylamine, dispersed in water, and their properties and coating performance were examined. The results are shown in Table 1 below.

(Note 1) It shows the pencil hardness after curing at room temperature a desiccant (Dicknate, manufactured by Dainippon Ink Co., Ltd., trade name) I PHR.

(Note 2) After drying for one week, the coating film was immersed in water for 5 hours and the state of the coating surface was examined.

Claims (1)

[Scope of Claims] A maleated addition polymer having a drying oil fatty acid residue and/or a semi-drying oil fatty acid residue connected to the main chain by an ester bond as a side chain; An oxidation-curable water-dispersible resin composition obtained by neutralizing a reaction product with an addition polymerization polymer and dispersing it in water.