JPS5943050A - Aqueous dispersant for epoxy resin and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compounds useful in preparing aqueous dispersions of water-insoluble compounds. More specifically, the present invention relates to urethane dispersants used in the production of aqueous dispersions of resinous or high molecular weight compounds containing epoxy groups.

In recent years, there has been a great deal of emphasis in the paint and plastics industry on converting organic solvents to aqueous systems. Reasons for this conversion include the increasing cost of these organic solvents as well as pollution problems caused by the escape of organic-containing compounds such as hydrocarbons into the atmosphere.

It has long been known that epoxy group-containing materials have highly desirable properties when used in coatings and plastic formulations. Epoxy resins impart unique strength and chemical resistance to paints and plastic formulations.

For these reasons, the use of epoxy resins, and in particular the use of aqueous emulsions or dispersions of epoxy group-containing materials, has increased recently. However, since epoxy group-containing materials have extremely high reactivity and relatively high molecular weights, it may be difficult to produce stable, low-viscosity epoxy resin dispersions with relatively high solids content. many.

Therefore, there remains a need for dispersants that enable the production of epoxy resin dispersions with small particle size, low viscosity, and high solids content. One example of a conventional method of making such a dispersion is to prepare a hydroxy-terminated polyethylene glycol 2
The method is to use an epoxy surfactant obtained by reacting 1 mole of diepoxide with 1 mole of diepoxide. However, it is difficult to fully react these materials without causing excessive chain elongation.

Another problem that hinders the production of epoxy resin dispersions is the difficulty in producing satisfactory dispersants that are compatible with epoxy resins.

The above and other problems are caused by small particle size, low viscosity,
This problem is overcome by providing compounds of the present invention that can be used to prepare stable epoxy resin dispersions with high solids content.

The compounds of the present invention are particularly useful in that they can be produced without excessive chain elongation.

British Patent No. 1,069,735 discloses a process for the preparation of surface-active reaction products, which consists of reacting 2 moles of diisocyanate, 1 mole of dihydroxy polyether and 2 moles of monophenol. However, this patent does not disclose the use of such reaction products as epoxy resin dispersants.

U.S. Pat. No. 3,549,543 discloses a combination of materials useful as low foam agents, detergents and cleaning agents.

This includes certain ethylene oxide adduct dimers made with aliphatic or aromatic diisocyanates. However, this patent does not disclose the specific compounds of the present invention, nor does it disclose the use of such materials as dispersants for polyepoxides.

US Pat. No. 4,079,028 discloses the production of certain polyurethane-based materials using polyhydroxy compounds such as di- and trihydroxybenzenes. The hydroxy-terminated P172 repolymers produced in this patent are generally endcapped with either monoisocyanates or monoisocyanate/diisocyanate mixtures. This patent... There is no disclosure of the use of bisphenol A type compounds or of their use with aliphatic polyether glycol monoethers.

The present invention relates to the production of surfactants or dispersants for use in epoxy resin materials that are not originally water-soluble or water-dispersible. The dispersants of the present invention contain approximately n moles of aromatic, aromatic origin or cycloaliphatic diol, n+1
It is produced by reacting mol of diisocyanate and 2 mol of long chain aliphatic polyether glycol monoether.

This dispersant is represented by the following general formula.

In the above formula, n is 1 to 10, D is a residue of an aliphatic polyether glycol, G is an aromatic, residue of an aromatic origin or alicyclic diol, F is a residue of a diisocyanate, and E is a residue of C1 to The diisocyanate compounds useful in the present invention, each meaning a C4 alkyl group, have the general formula 〇C
can be represented by N−F NCO, □where i
? is a residue of an aliphatic, aromatic, aromatic origin or alicyclic compound having about 6 to about 20 carbon atoms per molecule.

Substantially any type of diisocyanate-containing material can be used in the present invention; the only requirement is that the diisocyanate backbone is compatible with this and the diols and long chain aliphatic polyether glycol monoethers described below. This means that it does not contain any groups that would interfere with the reaction with.

Isocyanates are substances known in the art, and those suitable for the present invention are those which can be referred to as aromatic, aromatic origin or cycloaliphatic diisocyanates. The term "aromatic origin" refers to aromatic isocyanates or precursors thereof that have been partially or fully hydrogenated to form cycloalkyl or cycloalkene isocyanates. The same applies to the diol used in the present invention, but the isocyanate is preferably one that is structurally similar to the polyepoxide that will ultimately be dispersed with the obtained dispersant. Therefore, when a long-chain aliphatic epoxy resin is used, it is preferable to use a long-chain aliphatic isocyanate such as hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, etc.). However, in most cases, the polyepoxide used is preferably aromatic, of aromatic origin, or of cycloaliphatic diisoleanate, so long as the polyepoxide used has an aromatic donor, such as bisphenols. Particularly preferred diisocyanates include isophorone diisocyanate, bis(p-phenylisocyanate), bis(p-phenyl)methylene diisocyanate, bis(p-phetrilycyclohexyl)methylene diisocyanate, 2,4-toluene diisocyanate-1-, 2
．． 6'-1-ruene diisocyanate, 1.4-phenylene diisocyanate, 1.3-phenylene diisocyanate, 4,4"-diphenylmethane diisocyanate, 4.4"-diphenyldimethylmelane diisocyanate, 1.5-naphthalene diisocyanate, ■ , 4-cyclohexane diisocyanate-1, etc.

The second main component of the present invention is an aromatic, aromatic origin or cycloaliphatic diol. However, the term "aromatic origin" used here refers to partially or completely hydrogenated aromatic diols. Examples of diols useful in the present invention include resorcinol, hydroquinone, p+p'
-dihydroxybenzophenone, p, p'-dihydroxybiphenyl, I) IP'-dihydroxydiphenylethane, bis, (2-hydroxynaphthylmethane) mi 1,
5-dihydroxynaphthalene, and p+ p'-dihydroxydiphenylpropane (commonly known as bisphenol A)
). Furthermore, hydrogenated bisphenonyl A, 1,4-
Also included are cyclohexanedioneyl, 1,3-cyclobentanediol ζcypolyhexane dimethanol, and the like.

Other useful compounds are halogenated derivatives of each of the above substances, such as borivalogenated bisphenols, including tetrabromobisphenol A. -1- The third component of the present invention has the general formula B'
It is a long chain aliphatic polyether glycol monoether represented by -0-I'320-■. However, in the above formula,
・E is 'C, [:'~C-alkyl group, D is molecular weight approximately 1
11000-: each means a residue of 1.5,000 aliphatic polyether glycols. • Preferred materials for use in the present invention are C,;C2 mono-alkyl ethers of polyoxyethylene glycol. Polyether products include: polyethylene glycol polyethers, polyethylene dioxide 9 adducts, and engineered dioxyde and propylene containing about 50-90% by weight ethylene oxide and about 10-50% by weight propylene oxide. Block copolymers with oxides are included. □The polyether glycol monoether used in the present invention is produced using a method well known in the field. □ In the above description, the terms diisocyanates, diols or glycols are used, but this is not meant to exclude materials consisting of mixtures of monofunctional and polyfunctional substances. In the case of such mixtures, the materials used need only contain on average approximately two functional groups. For the purposes of this invention, the terms □ diisocyanates, glycols and diols mean on average about 1.5-2.
Includes materials with 8 functional groups.

To prepare the compositions of the present invention, about 2 moles of the long chain monoalconyl' (i.e., glycol monoether)
Then, 'n moles of di-J and n+1 moles of diisocyanate are added. Preferably or □n is! tlo1
．． ．． -FvAJr, +ltKa<,:t+J:6'*J
<i=, -1□ Kudzu has reduced effectiveness as an engineered poxy tree subdividing agent. Specially.

0 Preferably, n is from 1 to about 5.

There are many methods for co-reacting the above three types of materials, but the preferred reaction method is to first add ()ol and long-chain monoanosyph-11 to the reactor.

This mixture is then dissolved under heat (usually about 60 to 8
within the range of 0°C). At time 49, the reaction catalyst may now be added.

Examples of reaction catalysts include virtually any type of catalyst that catalyzes the reaction between isocyanates, alcohols, and diols. Such catalysts include tertiary amines and various enriched metal compounds and carboxylic acid salts of metals such as tin, mercury, and mercury. Specific examples of such catalysts include trialkylamines and sialgyltin dialkoxylates I, including dibutyltin dilaurate and the like. , the amount of catalyst added to the diagrammatic mixture depends on the desired reaction rate and the type of reactants used.1 Wide range: JIJ13
L Wow. Just 2, general. For example, about 0.1-5% by weight of the reaction catalyst, based on the total amount of reactants, is added to the reaction mixture.

Following the addition of the catalyst, add 1.
The mixture is held at the reaction temperature until all incyane I groups have disappeared. For the reaction of isocyanate-1, take a sample of the reaction mixture, add dibutylamine, and:! ] c, β, by back titration with an acid such as Monitored using standard testing methods. Normally, heating for about 2 to 2 hours is required for all isocyanates to react. .

The products thus obtained can then be used as dispersants or surfactants in various epoxy resins. Although the present invention can be used to disperse virtually all types of epoxy resins in water, the dispersants of the present invention are particularly useful for aromatic polyepoxide resins. (Because this type of epoxy resin has good hydrolytic stability).

Such polyphenols are well known in the art and include reacting diphenols of the type described above with at least an equivalent amount, preferably an excess, of epihaphahydrin, preferably shrimp chlorohydrin, relative to the phenolic hydrogen. Manufactured by Preferred epoxy resins are 2.・About 1
80. It is a glycidyl polyether of bisphenol Δ with a reboxy equivalent weight of ~1000.

Dispersion of epoxy resins with dispersants thus produced can be coupled by any of several methods well known in the art. The preferred dispersion method is to place the epoxy tree lIy together with the dispersant in a reactor.
It depends on how you put it in. These two types of fees are
If necessary, the polyepoxides are then heated together to melt and obtain a compatible mixture.

At this point, it may be desirable to add up to about 30% by weight of a cosolvent, based on the total amount of polythousandboxide and dispersant. Examples of such co-solvents include glycols, glycol ethers and glyco□ −
The esters include: This ring is the ethyl ester (
A wide variety of separators, such as monoethyl re-ether of ethylene glycol), monomethyl ether of ethylene glycol, and cellosolve acetate (acetic ester of monoethyl ether of ethylene glycol, kono, and monoethyl ester) Axialosolve, which also contains substances such as oxidation, is a registered trademark of Union Carbide Co.),...

A predetermined amount of water is added to the resulting mixture together with the divine aid solvent. The amount of water present and the temperature of the phase inversion point are.

Small and uniform particle size is an important factor in producing thousands of emulsions. 80～? At 5°C, the amount of water required is usually 7. ? This is the amount required to form a ~77% emulsion. After this combination, the mixture is maintained under stirring at the desired temperature until a stable dispersion is obtained. In some cases, it may be necessary to slightly increase the temperature to form a stable dispersion. Dispersion stability can be evaluated by monitoring its viscosity and holding the temperature until a stable viscosity is obtained. .

To achieve dispersion of the epoxy resin, at least about 2% dispersant should be used. The maximum amount of dispersant should be the minimum amount necessary to form a turf stable dispersion. The amount of water in which the epoxy resin is dispersed is generally sufficient to be about 15% or less based on the total weight of dispersed solids.
It varies widely depending on the epoxy resin and dispersant used. However, the typical solids content of the final product is approximately 35.
-70% by weight.・ ・
・：、１・：、Kasumi.

Another method of achieving dispersion of the epoxy resin is to mix the surfactant and water and then slowly add the epoxy resin to the mixture over a period of minutes to hours.・・・
If the epoxy resin used is a solid, it is necessary to heat this material to its melting point.

The products produced according to the invention may be modified with conventional fillers - pigments, reinforcing agents and other conventional aqueous binders, modifying agents, extenders, etc. l-,'11. ', 111'
The obtained epoxy resin 1 dispersion is □blended into a one-liquid or two-liquid type system for 7 seconds. 21 liquid type element □
Now, an epoxy curing agent such as an amine or amide/amide is added to the dispersion □ just before use. On the other hand, −
In the acid type system □, the epoxy resin and the hardened resin are mixed from the beginning. In any of these systems, final curing is achieved at 100 to 2'00°C at 5°C.
Baking up to an hour is required.

The dispersed acids obtained according to the present invention are preferred as protective coatings, but are also used in a variety of plastic end uses. This, togade, is celebrated.・The most common use of this type of paint is in the field of maintenance paint for positive electric currents using a two-component system. The dispersion of the present invention can also be used as a coating for printing circuits.

In the examples set forth below, all parts and percentages are by weight unless otherwise specified.

Practical Separation 1 629.3 parts of MPEG-5000 and 28.7 parts of bisphenol A were added to a reactor equipped with a mechanical stirrer and a temperature needle.

:15 (MPEG-5000 is a frozen, point 59.2°02 methoxy-terminated polyethylene with a molecular weight of about 5000, manufactured by Union Carbide.

'Sigly□Cole polyether. ) The reactor was gassed with nitrogen, and the mixture was stirred and heated at 60 to 80°C. At this time, 0.7 parts of dibutyltin silica and urate were added in Jc. Next, set the altitude to 82℃ and
2 parts of isoporone diisocyanate (equivalent weight 111
) was added and the resulting reaction mixture was maintained at a temperature ranging up to about 100'C for 2.5 hours. The resulting dispersant exhibited a Gardner-Bolt viscosity of 0 to P at 25° C. at 10% solids in water. .

Next side” Tadai machine tl! In a reactor equipped with a stirrer and a thermometer, add 1.164
．． 1 part of 1Epi-Rez 520 and 36.0 parts of the single □ dispersant prepared in Example 1 were added.

(Epi-Rez 520 Lt, a bisphenol A glycidyl polyether with a weight of approximately 502 kg per epoxy, Ce1anese 5specialty Re
It is commercially available from Sins Company. )This 2
The various materials were heated together for about 20 minutes at temperatures ranging up to 115°C. Then, at a reactor temperature of about 95°C, 168
．． 0 parts of ethyl cellosolve and 232.0 parts of water were added to the reactor. (Ethyl cellosolve is the monoethyl ether of ethylene glycol and is commercially available from Union Karpai I'6.) This mixture was then heated to about 85'C for 1 hour.
'0 minutes 1' (!t*L, -t+7) fie lz
&:15B2. . ,. 5. The 'L' mixture was held at a temperature ranging from 85°C to 65°C for 1 hour and 15 minutes. The epoxy resin dispersion thus obtained was
I, 840 cp! Using a Brookfield viscosity of <2 m'i-ndle and a rotation speed of 20 rpIll), the i-degree was within the range of 1.0-1.5μ.

Example 1 Side 1 Using essentially the same procedures as in Example 1, the dispersants shown in the following table were prepared. In Table 1, the "Type" column indicates the polyether used in the reaction, and the "Mole" column indicates the number of moles of the polyether. The column ``Poly (NGO)'' shows the type and malt of the diisocyanate used, and the number 4.
-7187"/-)b A (71%) kfll'
Ii: * The column "911, ji" indicates the temperature used in the preparation of the polymer in °C, and the column "Viscosity" indicates the temperature in °C, unless otherwise specified. i 1 Gardner-Holdt viscosity at 25°C at 4'0% solids in water is shown.

1□、Car 6o 7、Eng. , Dゎ and □No.

MPEG-5M is MPHG-5000, a 1.:'1''17 nidoxy-terminated polyethylene glycol manufactured by Union-Carbide with a molecular weight of about 5000 and a freezing point of 59.2°C.

? pro G-2M is M'PU! :G-2006, which is the same as M'PIEG-"45M except that the portion size is approximately 1":b60 Myogae condensation furnace 51.9℃.
1 is a similar substance □.

"MR"s'-to" means isocyanate functionality □2
．． B. Isocyanate calorific value 132 m polystylene polyphenyl isocyanate t, Mobay Chem
ica'I C'company'ct: commercially availableb
'). ' Des, W is D'e'smo'dur W, which means 4.4'・-Reiso □shi”
rurine = "+-", and it is "Q"M'ob'9'C
"hemi" cat. Ompiny or 5 cities, Kiwa 7 Io.

``'''I P'l)'I'bi Isophorone diisocy7nenit etc. 1 1ha: 1, , ,,,. 111 , / , , , , , ,
,,l, ,, , ,', '1. ．． ．． l,,
,,, ・1'l.

1'1・ 1.

11.

18
・□Table 1...

■1: ', ', I11. ”,',,I,,”',”,
``,' l, bi, field, ・According to the procedure described in Example 2, Experiments E-K in Table 1.
A small liquid solution of l1pi-Rez52.0,000 boxy resin was prepared using Ftl. Result: 2nd result.
,Table ,shows. In this table, "', dispersant (%)" refers to the dispersant 1. % by weight of 1. “′Solid content (%)
, ゛ is the solid in water of the dispersion, minute: F,! , :%, ma: voice, ゛viscosity 2. Bus, Bindle, all flights 1+i2
2 measured at 5'C! The pull and viscosity at rpm is expressed in the unit CpS, and the "particle size" is the dispersion, material, quality included within each of the three viscosity ranges expressed in the unit μ. The ratio, sum, is 1% and is Q. ,,.

20,, 1 kaku! In Experiment E of Table 2, 22.6 parts of a dispersion of 55% solids in water (Q, 024 etemoxy equivalent) was added to a polyamide amine with half the amount of hydrogen at 324. Mixed with 15.2 parts of system curing agent (0.02!8 effective amine hydrogen equivalents). Cejan, eS5p13c, 1
This curing agent Epi-Cu+7e□°”-6 is commercially available from Alty Re5ins Company.
0-85364; t:・Shuttle t, Lb>7 i・V7. '
16% of the available amine nitrogen of <i[Ll)"- is salted,
(Butyl cellosolve/ethyl cellosolve/
Diluted to 60% solids with f30/20/20 (weight ratio) mixed solvent of , toluene, and n! Aya. The solids content of the blend of 1i4(jJ+) was 43.7%.
8n+m) coating with bondericin? It was prepared on a treated steel plate. The coating was dry to the touch after standing at room temperature for 2-3 hours. The film after being left at room temperature for 6 days has a pencil hardness of B-HB and a good surface:
Exhibited with abrasion resistance and excellent gloss and adhesion.

1 The principles, preferred embodiments, and implementation methods of the present invention have been shown above. However, the specific embodiments disclosed above are: 1) The present invention is not limited to these embodiments because they are merely examples and are not intended to be limiting.

□ 1. It is prohibited to make various modifications by those skilled in the art without departing from the scope of this book. , .

, ■ , ・ ,,'1ui6. ．．
, Needs Corporation, Kazuharu Nshiro, Patent Attorney Akira Hirose -, Ll
: □ , 1 □ ■ □ 11 □111 1
1 11□.

,− 2

Claims (1)

[Scope of Claims] (1) 1 mole of diisocyanate, n moles of aromatic, aromatic origin or alicyclic di-ol and 2 moles of long-chain aliphatic polyester methyl glycol monomer; Reaction product of ether (where n' is 1 to 1o)'
Dispersant for free-flowing epoxy resins. , ・□(2
) The dispersant according to claim 1, wherein n is 1 to 5. (3) The dispersant according to claim 1, wherein the diisocyanate is an aromatic diisocyanate, the diol is a diphenol, and the polyether glycol monoether is a 01-C4 monoalcohol ether of polyethylene glycol. . 1(4) General formula:
: (where n is 1 to 10, D is a residue of aliphatic polyether glycol polyglycol ether, E is C', 1
~C, alkyl group, F is the remaining one group of diisocyanate, and G is aromatic, aromatic, aromatic, group origin, □ or alicyclic diol group, respectively). Dispersant. (5) A patent claim in which D is a polyethylene glycol polyether residue, E is an 01-C2 alkyl group, F is an aromatic diisocyanate residue, and G is I) ip''-dihydroxydiphenylpropane. Range□Claim 4・
dispersant. ′ □(6)(al
about n+1 moles of diisocyanate, aromatic,
□ or cycloaliphatic □ diols of aromatic origin, and about 2
Mole long/chain aliphatic □ group polyether group □ Reaction pressure of recall monoether: ・Acid: is formed, (blThe resulting reaction product is used to form an aqueous dispersion of epoxy resin □ ■ □: Method for producing an epoxy resin, a dispersion comprising: □' (7) The reaction product is used in an amount of about 2 to 15% sodium bicarbonate based on the total weight of the epoxy resin and the reaction product. and the solids content of the aqueous dispersion formed is from about 2'o to 35% by weight. □(8)
isocyanate, f-t is an aromatic diisocyanate, the diol is a diphenol, the polyether glycol is derived from ethylene glycol, and the epoxy resin is bisphenol A diglycidyl ether with a weight per epoxy group of about 180 to 1000. A method according to certain claim 6. 9. The method of claim 6, wherein up to about 30% by weight of cosolvent is used, based on the total content of epoxy resin and reaction product.