JPS5871960A - Aqueous resin dispersion composition - Google Patents

Abstract

PURPOSE:The titled composition, prepared by mixing an oily component with a polyhydric alcohol, a mono(poly)basic acid, polyoxyethylene glycol, petroleum resin, etc., in a specific proportion, having improved water and alkali resistance, and suitable for resource saving and low pollution aqueous coating materials with a small amount of organic solvents to be used. CONSTITUTION:A composition prepared by mixing (A) 0-60wt% oil or fatty acid with (B) 10-60wt% polyhydric alcohol[except the component (E)]having 2-6 hydroxyl groups in one molecule, (C) 0-30wt% monobasic acid[except the component (A)]having 6-18 carbon atoms in one molecule, (D) 10-50wt% polybasic acid and anhydride having 4-10 carbon atoms in one molecule, (E) 2-15wt% polyoxyethylene glycol having 600-20,000 molecular weight and (F) 5-40wt% petroleum resin and/or modified petroleum resin at (2/1)-(1.6/1) ratio between the numbers of the hydroxyl groups and the carboxyl groups in the components (A)-(E), neutralizing the resultant mixture, and emulsifying and dispersing the neutralized mixture in water.

Description

[Detailed description of the invention] The present invention relates to a water-dispersed resin composition. recent years.

Water-based paints are attracting attention from the viewpoint of resource saving and low pollution.

In particular, water-dispersed paints generally use less organic solvents, organic amines, etc. than water-soluble paints, and are therefore preferable from the viewpoint of resource saving and low pollution.

The paint film dries quickly because the dissolved solvent evaporates quickly.

It has the advantage of being easy to paint, and the cured coating film has good water resistance and corrosion resistance. First, we filed a patent application No. 116447/1983, and we investigated the drying properties of the coating film,
7 The present invention C1- provides a water-dispersed resin composition of alkyd resin having good properties of water resistance and alkali resistance.
Furthermore, the present invention provides a water-dispersed resin composition f of an alkyd resin that has improved water resistance and alkali resistance.

That is, the present invention.

(A) Oil or fatty acid 0 to 60 hydroxyl group (B1. Polyhydric alcohol containing 2 to 6 hydroxyl groups in one molecule [below (excluding J=:j component)] 10 to 60 hydroxyl group ( C) -4-basic acid having 6 to 1,8 carbon atoms in one molecule (excluding component (A) above) 0 to 30 double atoms (1)) 4 to 10 in one molecule A polybasic acid having 10 carbon atoms -!fr:, is its anhydride 10=50 i!
'%(E) Molecule 411゛600~20.000 polyoxyethylene glycol 2~15 weight-φ O'': and (F) Petroleum resin and/Amatakehen 1 1・Petroleum resin 5 to 40 heavy building (1) (A3-(Fl components are mixed and reacted so that the number of hydroxyl groups/number of carboxyl groups is 1/1 to 16/1, or (Ill(A) to (E) components are mixed and reacted in a ratio of hydroxyl groups/carboxyl groups of 1/1 to 16/1. An alkyd resin with an acid value of 30 or less obtained by mixing the resin and component (F) by blending and reacting so that the number of carboxyl groups is 1/1 to 16/1 is mixed with one of the carboxyl groups in the resin. Part 1 relates to a water-dispersed resin composition obtained by emulsifying and dispersing in water a neutralized resin obtained by neutralizing all of the components. - The total amount of components (A) to (E) is 100% by weight.

Can be used in the present invention (drying oil as a light component).

There are semi-drying oils, non-drying oils, fatty acids derived from these and synthetic fatty acids, such as tung oil, dehydrated and mustard oil, linseed oil, safflower oil, soybean oil.

These include castor oil, cottonseed oil, coconut oil, palm oil, etc., and versatile acid obtained by synthesizing fatty acids 1 obtained from these. One or more of these components (A) can be selected and used depending on the desired coating performance. iA
If the amount of the components (fA1 to (IC)) exceeds 60% by weight, which is used in a downwind environment, the drying properties and fragility of the coating film will be poor and practical performance will not be exhibited. (Bl ingredients include ethylene glycol, phlopylene gellicol, /
Ethylene glycol, neopentyl glycol, 1.
4-butanediol, 1,6-hegizanediol.

Cyclohegyzanedimethanol, trimetherpentanediol, dipropylene glycol, glycerin, trimethylolethane, l-rimethylolpropane, 1-IJ (2-hydroxyethyl) isocyanurate, tris(
Hydroxymethyl) isocyanurate, pentaerythritol, dipentaerythritol, etc. can be used.

(IJ) component is 10 to 10% of the total amount of components (A) to (E)
It is used between 60 wt%.

To obtain a quick-drying resin, tris(2-hydroxyethercine cyanurate and/or tris(hydroxymethyl)in cyanurate (based on the total amount of Al-(E) component) should be added to ≠ or more 5- It is preferable to use.

Component (C) is benzoic acid and methylbenzoic acid.

9. Carboxylic acids such as para-tert-butylbenzoic acid, isodecanoic acid, cyclohexanoic acid, isooctanoic acid, etc. These ester-forming derivatives can be used. fc) component is used in an amount of 30% or less by weight relative to the amount of fA, 1 to +E+component a.

Component (D) is isophthalic acid and phthalic acid.

Terephthalic acid, dimethyl terephthalate, tetrahydrophthalic acid, hymic acid, maleic acid.

Fumaric acid, adipic acid, sepacic acid, dimic acid, trimellitic acid, het's acid, dodecanedioic acid or their acid anhydrides and other ester-forming derivatives can be used. You can use it selectively depending on your point of view. (]
) l component is 10 to 5 with respect to the total amount of (A, i to fE) components.
Used at 0 weight i%.

For fE) component and 7, one molecule of polyethylene glycol [600 to 20,000] can be used. It is possible to use not only one type but also a combination of two or more types. (The El component is used in an amount of 2 to 15% by weight based on the (Al-(IC) component at), but in order to obtain particularly excellent water dispersibility and coating film performance, it is necessary to It is preferably 4 to 10% by weight with respect to the component line k.

As the petroleum resin of component (F), commonly known petroleum resins can be used. For example, for petroleum decomposition and refining, petroleum resins obtained by combining 1-C distillate with a boiling point range of -10 to +280°C with a catalyst-1, such as a Friedel-Crafts catalyst, etc. There are aliphatic petroleum resins whose main components are fractions of C. and aromatic petroleum resins whose main components are aromatic compound fractions. Petroleum resins that incorporate vinyl acetate, unsaturated carboxylic acids, etc., hydrogenation, oxidation, and evolving.

Esterified petroleum resin (< 1 petroleum side j fingers can be used.

(1") component is aliphatic petroleum resin V" and its modified petroleum resin is Wine I-L/L-5 (10°A
-1000, A-2000, [L-1000゜, etc. (all trade names from Nippon Zeon Industries) Azocabriol LP
H-31, LPHX-51, LP) iX-530, LP
HX-2030, LPHX-2060, LPHX210
0th grade (both Asahi Denka Kogyo product names), Wineton A-
100, B-170, C-100, D-100゜U-1
85,200S, 0302.1300.1325.13
45゜1500.1525.1700 etc. (all Nippon Zeon Kogyo product names), Escorets 1102.120
2゜1260.1291,1304,1315,210
1,2201゜5300.5380,8190.810
0, Escoball, Escoball R-020, etc. (all of which are trade names of Esso Chemical Industries). In addition, as aromatic petroleum resins or modified petroleum resins, Escorets 3102 (Esso Chemical Industry ■ trade name), Vetrozin ◆ 80. ÷100゜≠120. ÷13
0. ≠140. 150. It is commercially available as K, etc. (all trade names of Mikata Petrochemical Industries ■).

Component (F) that is reactive with oil, carboxyl groups, hydroxyl groups, etc. can be reacted with components (3) to (E), or alkyds obtained by reacting components (A) to (E). The alkyd resin of the present invention can be obtained by mixing the compatible component (F) with the alkyd. Incidentally, a component (1") that is not reactive with oil, carboxyl group, hydroxyl group, etc. can also be present in the reaction system during the reaction of components (A) to (F).
A (Fl component that is reactive with hydroxyl groups, etc.) can also be mixed with the above alkyd to form the alkyd resin of the present invention.
) ingredients, it has alkali resistance and water resistance (<
L: A water-dispersible resin with excellent adhesion can be obtained.

If the (F) component is less than 5% by weight with respect to (3) to (El component ail), such an effect is small, and 4 (l
If it exceeds 1 qjli, the hardness and removability of the coating film will be poor.

Note that components (A) to (E) may be functional derivatives thereof. (3) to (F'l component [(3) to (E) component when component (F) has no reactive group)] is the number of hydroxyl groups/
The number of carboxyl groups is preferably 1/1 to 1.6/I
rj: , 1/1 to 1.4/1. The number of hydroxyl groups/the number of carboxyl groups is less than 1/1 and t
J, if the acid value becomes too high and exceeds 1.6/1, the molecule-
9- Too low. When using a monofunctional derivative, the number of hydroxyl groups and the number of carboxyl groups are counted by replacing the functional groups with hydroxyl groups and carboxyl groups. The reaction is carried out by a condensation reaction according to a conventional alkyd resin synthesis method. i.e. 1 for example (
3) When using oil as an ingredient, the first step is (
A) Components (part or whole amount of Bl component and fc)
Part or all of the components are heated and stirred at 170 to 270°C under nitrogen to perform transesterification or esterification.

Then, as a second step, (Bl and the remainder of component (C) and fE) and component (F) were added, and the mixture was heated again under nitrogen at 170°C.
This can be carried out by proceeding with the condensation while heating to ~270°C with stirring, reaching the end point at an appropriate acid value and viscosity, and cooling. In addition, component (F) can be added in a newly provided third step as needed, and the desired resin can be obtained in the same manner. (When a fatty acid is used as the Al component or when not used, (3) to fF) The components can be mixed at once to perform one reaction.

When mixing component (F) with resin obtained by reacting (3) to (El component), +A) to (E) components are subjected to a condensation reaction in the same manner as above, and an appropriate acid value and viscosity are obtained. This can be carried out by adding the component (F) to a resin having the following properties and cooling it as it is.

The acid value of the above alkyd resin is 11i in terms of coating nIA performance.
-1 It is preferably 30 or less in order to maintain aqueous and alkali resistance.

Before neutralizing and emulsifying the alkyd resin and dispersing it in water, adding 50 parts by weight or less of a water-soluble solvent to 100 parts by weight of the alkyd resin may affect the water dispersibility of the resin, or
It is preferable in terms of improving the IL slipperiness of the coating film. If the amount of the water-soluble solvent exceeds 50 parts by weight, the viscosity of the aqueous dispersion may become high or the water dispersibility may become poor.

As the water-soluble solvent, a solvent that dissolves in water at 20° C. by 5 tnL% or more can be used.

For example, methanol, ethanol, ingropanol,
n-propertool, n-butanol.

Alcohols such as inbutanol, 5ec-butanol, 1erl-butanol, 3-methyl 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, etc. Alkyl ethers, diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol heptanoisopropyl ether, diethylene glycol heptanobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, etc. Dipropylene glycol monoalkyl ethers, such as cyfropylene glycol monoisopropyl ether 1, acetone, ketones such as methyl ethyl ketone, ethers such as tetrahydrofuran, methyl acetate , ethylene glycol acetite, ethylene glycol acetite.

Examples include esters such as ethylene glycol monomethyl acetate and diethylene glycol monomethyl acetate. When preparing a water-dispersed resin composition that can be dried at room temperature, it is preferable that the boiling point is 200°C or less.

Part or all of the carboxyl groups of the alkyd resin are neutralized. As a neutralizing agent, ammonia, triethylamine, dimethylamine ethanol, morpholine, N-methylmorpholine.

Amines such as 2-amine and 2-methylpropanol; hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide A'Q; carbonates of bases such as anhydride carbonate; and bases such as sodium bicarbonate; There is a large amount of bicarbonate.

The thus obtained neutralized resin 1d, , It can be easily made into a water-dispersed resin composition by mixing it with water while stirring.

The water-dispersed resin composition according to the present invention can be used as is, but it can be used by adding pigments, plasticizers, solvent 1 colorants, etc., or by reacting formaldehyde with amine compounds such as melamine, urea, pendiguan-13-mine, etc. ,
Modified amino resins, epoxy resins, and alkyd resins obtained by etherification with partial alcohols such as methanol, ethanol, and butanol.

It is also possible to incorporate a wide range of water-soluble resins such as polyester resins and acrylic resins, as well as water-dispersible resins. For example, it can be used as a baking paint by combining with modified amino resins, epoxy resins, etc. In particular, when a drying oil, a semi-drying oil or a fatty acid thereof is used in the water-dispersed resin composition according to the present invention, metals such as Co, Mn, Pb, Zn, etc. of aliphatic carboxylic acids such as naphthenic acid and octenoic acid are used. By adding about 0.001 to 0.5% by weight of the salt to the alkyd resin as a metal dryer, it exhibits excellent properties as a room temperature drying paint. These compositions can be made into paints by further using commonly used pigment 9 surface treating agents, organic solvents and the like. The paint composition can be applied by dipping or brushing.

It is possible to apply the coating by methods such as spray coating and roll coating.

14- Next, examples will be given to specifically explain the present invention.

Example 1 A 1-ton glass flask equipped with a stirrer, thermometer, reflux dehydrator, and inert gas introduction tube.

Linseed oil fatty acid 198fF, isophthalic acid 115.8i
, pentaerythritol 46.2P, tris(2hydroxyethyl)incyanure-1-118,87° polyethylene glycol (molecules: lt 2,000) 362 were added, heated to 230°C, and condensation proceeded when the acid value reached 20. 1
Petroleum resin (Vetroginna 80. Mitsui Petrochemical Industries ■ trade name) 120 i was added and cooled. To 100 g of the resin thus obtained was added 10 f of butyl cellosolve and t-
Butyl cellosolve 15i plus triethylamine 1.8
Then, 124 i of water was added at 50 to 60° C. to obtain an aqueous dispersion with a heating residue of 40 i.

Example 2 Using the same equipment as in Example 1, dehydrated mustard oil fatty acid 60
? , linseed oil fatty acids 10254. Inphthalic acid 143%
, Pentaerythritol 19.2F, Tris(2-
Hydroxyethyl) isocyanurate 211.2fi'
, polyethylene glycol (molecular weight a, ooo) + 2F
, petroleum resin (Quinton 0302 Nippon Zeon Kogyo ■ trade name) 6ofP was added and heated to 230°C to proceed with condensation until the acid value reached 16 〇 1oof of the resin thus obtained
f, 3-methyl-3-methoxybutanol 15f, Impropatool 14? , further added 1.4 i of ammonia (25% aqueous solution), and heated to 120 °C of water at 60°C. An aqueous dispersion with a heating residue of 40% was obtained.

Example 3 Using the same equipment as in Example 1, linseed oil fatty acid 210i, isophthalic acid 12ifP, pentaerythritol 40.8
P,) Lis(2-hydroxyethyl)isocyanurate, polyethylene glycol (molecular weight 5,000) 30i
Add and heat at 230℃.

Condensation is continued until the acid value reaches 40, resulting in petroleum resin (Azocabriol LPHX-2060, Asahi Denka Kogyo ■trade name) 90f.
! - was added, and the reaction was further advanced at 210°C until the acid value reached 16. Resin 1007, ethyl carpitol 101. Inglovir Cellosolve 19?
Furthermore, add 1.4P of ammonia (25% aqueous solution) and
Water was added for 120 y at 0° C. to obtain an aqueous dispersion with a heating residue of 40%.

Comparative Example 1 Using the same equipment as in Example 1, linseed oil fatty acid 222? ,
Isophthalic acid 171P, glycerin 35P, I-lith(2-hydroxyethyl), isocyanurate 1507
．． Pentaerythritol 28.2P and polyethylene glycol (molecular M: 3,000) 421 were added and heated at 230°C, and condensation proceeded to an acid value of 161. To the resin 1001 obtained in this way, 154% of ethyl selonlupe,
Bujiruse ``1 Solv 10y-Additionally 1 triethylamine
．． 8y- was added and 124y- of water was added at 60°C to obtain an aqueous dispersion with a heating residue of 40%.

Comparative Example 2 Using the same equipment as in Example 1, linseed oil fatty acid 1981, isophthalic acid 145.5F, pentaerythritol 17--17.9fP, tris(2-hydroxyethyl)isocyanurate 118, sfF, glycerin 40.21
Add and heat to 230°C, and when the acid value reaches 25, add trimellitic acid 39y- and heat to 170'.

The reaction proceeded until the acid value reached 60, and Vetrozin ◆80 (Mikata Petrochemical Industries KK) 12ON was added and cooled. Butyl cellosolve 50i was added to the resin 1001 thus obtained.
Further, 10 parts of triethylamine and 90 parts of water were added to obtain a water-soluble resin with a heating residue of 40 parts.

The water dispersions or water-soluble resins obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were made into paints in the following manner.

Titanium white (rutile type) 200 parts by weight Butyl cellosolve 20 〃 Water dispersion or water-soluble resin 500 // (Solid content) 5% Cobalt naphthenate 2 〃 Water Appropriate amount Disperse the pigment in the mixture blended as above using a sand mill. I let it happen. Next, each paint was diluted with an appropriate amount of water and adjusted to 18-30 seconds using a Ford Cubner 4 for 30 to 35 seconds.

[Coating film test]

Test plate preparation conditions Drying: Table 1 shows the test results over 3 days (other than the drying test) at 22-24°C.

Note 1) Press hard on the paint film with two fingers when it is hardened and dry, and indicate when there are no fingerprint marks left.

2) Gloss: 60° specular reflectance 3) Pencil hardness: Mitsubishi lead wire used 4) The coating surface was observed with the naked eye. The plan was rated as ``good'' if there were no abnormalities, and 1 poor if there was any shine, shrinkage, blisters, etc.

The water-dispersed resin composition according to the present invention has excellent alkali resistance, water resistance, and corrosion resistance when formed into a coating film.

21-

Claims (1)

[Scope of Claims] 1. Polyhydric alcohol having 2 to 6 hydroxyl groups in one molecule (B) 0 to 60% by weight of oil or fatty acid [the following (E
(Excluding component (3) above) 10 to 60% by weight (C) Monobasic acid having 6 to 18 carbon atoms in one molecule [Excluding component (3) above] O to 30% by weight (D) 1 molecule Polybasic acid having 4 to 10 carbon atoms or its anhydride 10 to 50% by weight (E) Molecular weight 600 to 20,0 OOf7) Polyoxyethylene glycol 2 to 15% by weight and FF) Petroleum resin and/ or modified petroleum resin 5-4
0% by weight (NXA) ~ (Fl component is mixed and reacted so that the number of hydroxyl groups/number of carboxyl groups is 1/1 ~ 1.6/1, or +l1l (A) ~ (El component is mixed with the number of hydroxyl groups / number of carboxyl groups / An alkyd resin with an acid value of 30 or less obtained by mixing the resin obtained by blending and reacting so that the number of carboxyl groups is 1/1 to 16/1 and the (F') component is added to the carboxyl group in the resin. A water-dispersed resin composition obtained by emulsifying and dispersing in water a neutralized resin obtained by neutralizing some or all of The total amount of components (A) to (E) is 100% by weight.
).