JPS59501166A - Stable aqueous dispersions of curable resin compositions - 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] Stable aqueous dispersions of curable resin compositions and adhesives made therefrom and Coating Compositions It has been said that many vinyl ester resins are polymerizable. child This is U.S. Patent No. 8,560,287 CRE27.656); 3,66 1,576; 3,673,140 and the disclosure of British Patent 1,375,177 has been revealed by. U.S. Patent No. 3,560,237 CRE27,65 6) and No. 3,661,576 disclose that the invention is based on resinous epoxides (such as -r). In the case of non-inventiveness and special characteristics regarding vinyl ester resin derived from Nigeki resin, is related to. These vinyl ester trees derived from resinous epoxide groups Many of the fats are commercially available, and have excellent physical and chemical properties. have and It is particularly useful as a protective coating for various substrates. For this purpose, the vinyl The ester resin is dissolved in a normal organic solvent or reactive diluent and applied to the substrate using conventional techniques. (spray, dipping, etc.) and then actinic light or pond catalyst Hardened by steps.

The need to use all organic solvents is a drawback for using the compositions shown above. . Organic solvents should not be recovered, recycled or recycled for safety, environmental pollution and/or economic reasons. will be discarded. Recovery is often difficult and/or costly. Ru. These problems can be reduced if the organic solvent reacts within the coating. . Studies to consider include vinyl monomers 8 and low viscosity vinyl resins as reactive diluents. Regarding the use of However, many of the useful reactive diluents are e.g. - Hydroquinoethyl acrylate is toxic and health and environmental considerations 2 8 times the problem.

Many resin systems include 1, such as sulfonium, phosphonium, and ammonium. Various onium groups can be attached to the resin matrix or used as a dispersion vehicle. By adding an onium surfactant to the resin, it becomes water-soluble or water-dispersible (oil-in-water type). Dispersion) K and rice. Many of these onium compounds are electroreducible; And in particular, sulfonium 2 and inothiuronium compounds are ε is used as rice. Thorough measurement of stiffness (unnecessary) ) et al. U.S. Patent No. 3,793.27s; 3.936,405; 3,937 ,679; 3.959,1068 and 3,894,922 are onium-modified We present a series of cases in which poxide groups have been asserted to be useful as electrolytically deposited compositions. It shows. Onium-modified epoxy resin is a third party to epoxy resin in the presence of acid. made by reacting with tertiary amines or sulfides.

The acids used in this series of experiments exhibited dissociation constants greater than 1X10-'; Including organic and inorganic ek. Although alkenoic acids meet the requirements for a dissociation constant, was not mentioned or used in these specific references.

The present invention is a semi-esterification of dicarboxylic acid and secondary hydroxyl of vinyl ester resin. 711). The first half The carboxylic acid group of the ester) is alkali metal hydroxide, ammonium hydroxide or At least partially neutralized by a tertiary amine. The dispersion is 2500 The vinyl ester resin has an average particle size of less than i (25, olm). can be cured through the vinyl group of

The vinyl ester YHIW useful in the present invention is a polyepoxide all-ethylenic non-polyester. The dicarboxylic acid is reacted with a monocarboxylic acid to form a half ester. or its reaction product with an anhydride. Vinyl ester wood like this It is disclosed in U.S. Pat. No. 3,564,074.

Any of the known polyepoxides) may be used in the production of vinyl ester resins. Can be used. Useful polyepoxides include polyhydric alcohols S and polyhydric phenols. LY/ZIL POLYATE/L= is a mixture of epoxy novolak or epoxy.

Many polyepoxide modifications can be readily made within the scope of this invention. So methods such as reacting with the epoxide groups of and adding these diepoxide molecules serves to bond two or more polyepoxide molecules together, and further connects the terminal epoxide molecules. Bisphenols, dicarboxylic acids or carboxyl-terminated polydicarboxylic acids bearing oxide groups. The molecular weight of polyepoxides can be overridden by polyfunctional reactants such as enzymatic rubbers. Is possible.

When polyhydric phenols are selected to make the polyepoxide, many constructions are possible. Mr. @ is possible. Polyepoxide made from polyhydric phenol (general formula Divalent hydrocarbons like! i　S-1-S-S-1 also works. that novolac There are different, well-recognized types of epoxy novolacs available for selection. I'll guide you.

Other modifications were known to those skilled in the art.

Although the present invention is applicable to polyepoxides, the most advantageous polyepoxides in general Oxide has a weight of 150 to 2000 per epoxy group (-t).Epoxy equivalent weight of a polyhydric alcohol or of a polyhydric phenol having an amount of be. These bo1j ehosonodos are epihalohydrin or dalicerol dihalohydrin. At least about 2 moles of polyhydric alcohol or 1 mole of polyhydric phenol 2 and 10 moles React with a certain amount of alkali metal to combine the halogen and hydroxyl group of the halohydrin. It is usually made by saletto and shiteyo. The product contains more than one epoxide group.

5 That is, it is characterized by the presence of more than 1 1,2-epoxy equivalent.

Preferred polyepoxides are methylene bisphenol or 2,2'-inopropylene. It is a polyepoxide derived from Denbisphenol 711).

Suitable α,β-ethylenically unsaturated monocarboxylic acids include, for example, acrylic acid, methacrylic acid, acid, crotonic acid and cinnamic acid.

Hydroxyalkyl acrylate or methacrylate as other unsaturated carboxylic acids using a half ester formed by the reaction of one molecule of ester with a cyclic acid anhydride. Can be done.

The above reactants have a virtually stoichiometric ratio of carhoki/functionality with the oki/ran groups present. 8 are included in the composition to provide the desired equivalent weight. It is polyepoxide each 0.8 to 1.15 equivalents of carboxylic acid component per equivalent, and preferably carboxylic acid component This means that 0.9 to 1.05 equivalents are present.

The esterification reaction is preferable (macarboxyl group and oki/ran group and this esterification reaction). catalyzed with known catalysts for fluorination. Such a catalyst is tris(dimethylamino Contains tertiary amines such as methyl)phenol and also contains chromium.

The composition is prepared by mixing the components mentioned above and preferably in the presence of a catalyst. to produce a curable product by reacting the mixture at 0-120°C. It can be used to The reaction is very slow if temperatures above 80°C are used. stomach. If temperatures above 120° are used, side reactions occur and the desired product The product yield is reduced and an exotherm occurs that is difficult to control.

1 cg in the reaction mixture, and due to the presence of reactive ethylenically unsaturated groups, the reaction Mixtures and their resulting compositions should maintain a suitable residual amount of vinyl polymerization inhibitor. It is necessary to・Idoquinones and any of the quinones belong to this order. Although it was found to be suitable for the purpose.

However, the hydroquinones enter the reaction with the epoxy groups of the starting material. Quinones because of the tendency? It is generally preferred to use tolquinone or tol When hydroquinone is used as a polymerization inhibitor, the reaction product appears transparent. Therefore, tolquinone S and toluhydroquinone are preferred vinyl polymerization inhibitors.

Other preferred inhibitors (p-quinone, 2,5-2 methyl-p-benzoquinone, I +4-natsutaquinone, anthraquinone, 2 and chloranil )f included. A preferred inhibitor in the product composition is 2-chloro-2-nitroph. phenothiazine 8 and/or oxic anhydride.

Ethylenically unsaturated monocarboxylic acid-polyepoxy containing its secondary hydroxyl groups The sid reaction product may further be treated as disclosed in U.S. Pat. No. 8,564,074. reacted with 0.1 to 1.2 mol of dicarboxylic acid anhydride per equivalent of epoxide in the process Ru. The dicarboxylic acid anhydride has a phosphorescent or fusogenic anhydride as disclosed in the patent. It can be selected from carboxylic acid anhydrides or mixtures thereof. For example, hydroquinone Vinyl polymerization inhibitors such as methyl ether or +-1 hydroquinone can be added. Ru. After completion of the reaction, the reaction mixture is cooled and the polymerizable monomer is removed. Mar can be mixed with it.

'-c = (A wide selection of polymerizable monomers containing JH2 groups is available in many public It is possible from known vinyl monomers. Alternatives are styrene and vinyltoluene. , )・Contains monomers such as logogenated styrene and divinylbenzene.

Other valent II monomers include, for example, methyl, ethyl, inopropyl, octyne, etc. , esters of acrylic or methacrylic acid, vinyl acetate, diallyl maleate , dimethallyl fumarate, acrylic acid, methacrylic acid, and crotonic acid. acidic monomers such as 3 and acrylamide 2 and N-alkylacrylamide. Contains a mixture of amide monomers ε and 12.

; Clever polymerizable monomers containing c=cu2 groups include styrene, vinyltoluene, N, Ornow, Memeo and para-halostyrene, vinylnaphthalenes, various α-substituted styrene, S and acrylic, methacrylic S and crotonic acid ester. Ru.

A non-reactive solvent can be used to replace all or a portion of the reactive solvent.

Non-reactive solvents such as ethers; alcohols such as butanol ; Ketone 2 and methylene chloride gold.

The resulting acid-functionalized vinyl ester then makes the resin water-dispersible. Amounts of alkali metal hydroxide, ammonium hydroxide or tertiary amine. Make it react.

Although all alkali metal hydroxides are useful, 1JaOH2 and KOH is preferred.

Suitable tertiary amines include, for example, trimethylamine, triethylamine, triethylamine, Contains alcoholamine, dimethylethanolamine and methyljethanolamine .

The neutralization/residue is preferably carried out at a temperature of 20 to 80°C, most preferably 20 to 75°C. It is given. After neutralization, the resin; It can be dispersed by

7) Inventiveness; go 1-13 weight section, preferably 1 go 1, 5-7 weight section Boxill? include. Advantageously (Goso Dispersion 1 Go2500 Augerstrom Mono It has an average particle size of less than or equal to The polymers of the particles are liberated at somewhat higher temperatures. Curable by group catalysts and/or by pendant carboxyl groups can. Its dispersion (for 1π, or melamine or (gourea-formal Amino blasts such as dehyde (or phenol blasts) can be mixed. Since the dispersion can be water-based, problems caused by organic solvents in coatings are eliminated. or becomes the minimum.

The dispersion may contain colorants, fillers, waxes or other materials for its desired effect. Can be mixed with common additives.

The dispersions are useful in adhesives and coatings.

For example, dispersions thereof (botyer cord adhesives, glass sizing agents 3 and wood products) It is useful as an adhesive for As a coating, the dispersion is used as a metallic cosmetic primer 2. and finishes, internal and external can coatings, drum linings and other industrial applications. It is a commercially available covering.

This tire cord adhesive is suitable for bonding the tire cord and rubber. Dispersions of the invention and e.g. styrene/butadiene/vinyl, pyridine (15/70/ (15% by weight) in a mixture with a suitable latex, such as a free radical initiator. made by Suitable free radical initiators are, for example, tertiary butyl perbenzoic acid. Contains salt. The mixture of dispersion and latex of this invention is catalyzed by an acid. Can also be cured with phenolprost or aminoblast resins.

Suitable coating compositions include dispersion 8 of this invention and aminoblast or phenolblast. It is made with an acid catalyst.

Suitable aminoplus resins include hexamethoquinomethylmelamine 3 and methylated resins. Contains ramine formaldehyde m fat. Suitable acids as catalysts are carboxylic acids or For example, para-toluenesulfonic acid or an amine salt of para-toluenesulfonic acid. Contains sulfonic acid.

The concept of the present invention (= Clarifying the best method to reduce the production and utilization of the dispersion to zero) More clarification is provided in the following non-limiting examples.

Example 1 14 five neck round bottom flask with condenser, calorimeter, air sparge tube, S and stirrer Epoxy equivalent weight (EEW) of methacrylic acid and 361 'f! ：＊Surupo 273 g of reaction product with epoxide were added. The polyepoxide C Gobisfu The diglyphyl ether of phenol A and the diglyphyl ether produced from the reaction with bisphenol A It was glyphzyl ether. The vinyl ester base resin is at 10°C. 7JO was heated and 26.80 g of maleic anhydride and hydroquinone o , o 3 g were added. The mixture was heated for 1-2 hours or until its acid content was 4.0%. The reaction was allowed to occur until the reaction occurred. Add styrene (44°97g) and to the mixture Cooled down to 0n. Phenothiazine (0,ogy)g and hydroquinone mono methyl ether Stirring was continued until Fat 8 and styrene were completely mixed.

Then the temperature drops to 40°C and triethylamine 32.46.9= Add 372.6g of water at a rate of 15 parts/min and stir for 30 minutes. I got so angry. This dispersion contained a solids content of 35% and 17ooA (17%).

particle size (nm) and viscosity of 250 cps (0.22 pa-s) at 25 °C It had

1 The vinyl ester of Example 1 was added to a 215-necked round bottom flask equipped as in Example 1. I used base resin 501e710.

The resin was heated to 1,10'C and hydroquinone 0,06F'j 6 and 49.05 g of maleic anhydride and 1.5 hours (acid ratio = 4.4). react, then styrene j0 9.9 Lj was added, and the mixture was heated to 70 Cooled to 'C. So 3″L to hydroquinone monomethyl ether 0,15 710 g of phenothiazine and 0.20 g of phenothiazine were added and stirred for 1 hour. 40℃ 83g2 of triethanolamine and diethylene glycol monobutyl ether 10 jj k. and mixed thoroughly for 30 minutes.

That's water 1079. ! It was added at a rate of 110-201 HA/min. This dispersion is 30% solid volume, 22,700 cps at 25℃ (22.7 pa・s) viscosity 1f. E and particle size of 134oA (1 3 4 nm) had. The gel time at 77”F (25°C) is 50.9’i1% for the dispersion. Cured with benzoyl peroxide S and 0.2% trimethylaniline to form a white solid. Measured by obtaining body mass. The gel time was 117 minutes.

49 gE of this dispersion and tert-butyl perbenzoate o. 2sg. I agreed. So The pHk of the system was adjusted to above 10 using triethylamine. Then the The dispersion contains 41% solids styrene/butadiene/vinylpyridine latex ( 15/'7 0/1 5% by weight) was reduced to zero while stirring normally.

Untreated polyester cord 2 12 inches (305mm) is the measurement size.1. And the weight Jll was determined. That code The container was dipped a little into the above mixture for 3''L and hung from the clamp.

The cord was placed at 190°C for 2 minutes and then removed. The board was weighed and the resin coverage was determined and then 1.5 in. Four control coats of the fragments were cut into 44 pieces of length (38 m + i). (commercially available polyester tire cord) and place it on top of a piece of loose rubber. . Another piece of uncured rubber was placed on top of the cord. Then remove the rubber from 160 Cure for 10 minutes at 2°C and 8000 psi (5.52, I4Pα). Ta. Its adhesion (= test it as shown below.) The insertion point of the tire cord is just deep enough to cut the I4 inch (6.35mm)<Accurate cutting friend. That mat is 30 minutes. 110℃ Let it dry in the oven with 7 tons, and then remove the cord from the rubber from the 3 tons and pull it out to dry. The required tensioning load was added 111 for the hustle cord. Adhesive lba38 , 4 bonds/inch (6 7 2 ON/m.), and the adhesion of Kawase is 4 0.3 2 bond/I7chi (70611V/m) Vinyl ester base resin S Filled with ulk light. The vinyl ester resin is 208EE with up to 4.7% acid content. W resin (bisphenol A epoxy / epoxy resin 8 and epoxy resin), methacrylate The reaction product of maleic acid and maleic anhydride was used. The soil is heated to 70℃ And phenothiazine 0.12g8 and styrene 58! jk added. Its・'mixture The mixture was stirred for 1 hour and cooled to 40°C.

Then 48.9 g of triethanolamine and diethylenetalicol monomer were added. “Chill ether and mixed outside for 30 minutes. Add 15 to 20 ml of water 589I from the pot at a rate of 1 minute. Added in degrees. The dispersion has a solids content of 30% and a temperature of 27,500 c at 25°C. Viscosity S of ps (2 7,5 Pa-s) U6 8 5i (6 8.5 　nm)　　　fJ3+”lS　J:　H6　8　5　A according to Example 2. Measured with a dispersion of l'1. Ta.

The gel time was 17 minutes.

Central side example 20 Tire cord closure according to Ill1M (1 made from this dispersion) Ta. Its cutting performance was 32.4 bonds/inch (5 6 7 4 N/inch) compared to the control. rn) and measured 34.6 bonds/inch (6059N/m). determined.

Example 4 The vinyl ester of Example 1 was added to a 2p 5-neck round bottom flask equipped as in Example 1. 500 g of base resin was added.

The resin was heated to 110°C and treated with maleic anhydride 27,9.98 and hydride. Rokinone 0.04. i- added. The reaction continues for 1 hour up to an acid concentration of 3.25%. Then add 75,5 7 g’Th of styrene and heat the mixture to 70°C. Cooled. Then 0.15 gg of monomethyl ether of hydroquinone and Added 0.12 gi of notiazine and stirred for 1 hour and cooled to 40°C.

From So4z, triethanolamine 50.75,? ．． F:? and butanol 1o g and mixed outside for 30 minutes. Then water 863gk15~20k/ Added at a rate of 1 minute. This dispersion (with a solids content of 30% and 1680 It had a particle size of A (168 nm). At 77”F (25C) The gel time was determined for the dispersion according to the procedure of Example 2.

The gel time was 21 minutes.

Example 5 A 2J 5-piece pressure flask equipped as in Example 1 was filled with a 1" L vinyl evaporator. Stellbase resin 455.8. ! 7. The resin can be heated up to 110℃. 0 heat and add hydroquinone u. o5g. b and anhydrous maleic lees 4475,97 i: added and allowed to react for 1.5 hours 1 hour (acid ratio=4.60). 7 of the mixture Cool to 0°C and add 0.13 g of phenothiazine and hydroxyl. Non's monomethyl ether o- 1 3 g f. Triethylamine ( 62.13y) and mixed outside for 30 minutes. So, flJ) Rasui 970 ．． 2, L) r7II] at a speed of 15-20 mi/min. This obtained hole size (9 ．． It had a viscosity of 0.75 Pa·S).

Example 6 3, 6, and 1 of Example 1 in a 11, five-necked round-bottomed flask equipped as in Example 1. EEW Bisphenol-A Ehoki/5 Base Juzuki's dimethacrylate 273g'e sword 0. The resin was heated to 110℃1 Heat the sword to 0, then add 1.9 g of anhydrous maleic e 1 and 0.0 hydrosonone. 8! The reaction was continued for 1 hour to an acid concentration of 2.2%. then nothing 0.06g of water and oxalic acid = 42.74.9g of styrene. the mixture Cool to 70°C and add phenothiazine o. 06g gained 710. 50℃ After cooling to Mix thoroughly for a minute.

While stirring, 472 g of water was added at a rate of 15 to 20 ml per minute. its dispersion The body has a solid content of 35% and a particle diameter of 2240A (2240 nm). It had .

The above dispersion 22.87.9i hemisametoki/methylmelamine (/mil R803) 1.29, mixed with 50% solids para-toluenesulfonic acid solution, which Neutralized with 2 methylethanolamine and 35.6 g of deionized water. of this mixture pHi! Lo with triethylamine. I was able to adjust it with 5-t. This dispersion (Go Jintong 41% solids of styrene/butadiene/vinylpyrinone (7'J) without stirring. 15/70/15+at%) latex 1 2.9 3 g.

Coat it by first soaking it slightly in water to saturate it and then adding the adhesive mixture described above. I soaked it in a little bit. Place that cord in the oven and glue it to the cord The agent was fixed. The curing time and temperature are shown in Table 1. That code has a thousand adhesives The amount of coating was 4 to 5 wt%. The code + = rubber as described in Example 2. ・6 on top of Gunodo placed. The results are shown in Table I. Polyester Example 6 60 375 45.6 (191) (7990) 6 60 410 50, 5 (210) (88i)) Polyester commercially available’45 300 (149) - 60 475 49, 5 (246) (8670) Nylon 6, 6 Example 6 60 875 52.9 (191) (9260) Nylon 6 Example 6 60 375 47.0 (191) (8230) Commercially available - 53% Reso/Nol, Formaldehyde, Triallyl/Amerate 47% styrene/butadiene/vinylvinyl latenox (15/70/15) Use commercially available adhesive II300”F (149°C) for 45 seconds. It was a two-step cure at 75"F (246°C) for 60 seconds.

Example 7 Epoxy resin ( Diglycidyl ether of bisphenol A CEEW=182-190))85 0gl7 (1,8460 equivalents)? added. Heat it to 110°C and add 1 ml of ice methacrylic acid. 58.76,! 11.8460 equivalents) 8 and hydroquinone 0.11.9 were added. Ta. Thoroughly combine 7jL of these ingredients for 15 minutes, 2, 4, 6-) II Add 0.53 g of (dimethylamiculum) fluor (DMP-80), Then, it was slowly heated to 118°C (30 to 60 minutes). coog percent The reaction continued in the trenches where the value was below 1.0. Then 23.20 g of maleic anhydride (0,2367 mol) and reacted for 1.5 hours, C0 equal to 2.40 The OH percent was obtained. Then 0.11 g of 4-chloro-2-nitrophenol was added and the mixture was cooled to 85°C. Then phenothiazine o, Add ogg, cool the mixture in a 55℃ trench, and add dimethyl ethanol solution. Add Min 30.41.1 (13417 equivalents) and mix thoroughly for 15 minutes. Ta. While stirring, water was added at a rate of 621 g'i15-20111 g/min.

Example 8 Following the same procedure as in Example 7, a dispersion having the following composition was synthesized. Example 7 Sono green/green ether (350L 1.8460 equivalents), hydroquinone (0,12g), glacial methacrylic acid (158,76!j, 1.8460 equivalents), DMP-30 (0,53g), 4.58 C (JOH% TF Maleic anhydride (48.62g, 0.4961%), phenothianone (0.4961g), 08g), 4-chloro-2-ditrophenol (o, 1tl, dimethyl ethanol 2 and water (1150.5 g).

Solid chi was 29.0. Blockfield viscosity at 25°C is 1600c ps (1,6 Pa-5).

Example 9 A 21.5-day round-bottomed flask was equipped as in Example 1 with the evo key of Example 11. Resin 228.6.9 (1,2057 equivalents), bisphenol-A 23.88 g (0,2095 equivalent) Jiyoto Hiker (BF Danodorinochi Chemical) Kanhoney's quotient i) 1aooxtg (butanene/a 23.88 g (0.2095 equivalents) of crylonitrile polymer) were added. the tree The fat mixture was heated to 80°C, and the resin molecular weight Umu Acetate IJ, 44.1 - I lost strength while doing Muroshi Bano. then 1 Heat to 50°C with stirring and hold for 1.5 hours. The mixture is 110 Cool to ℃ and start air purge. -Idoquinone 0.121b and Add glacial methacrylic acid 79.02,9 (0,9188 equivalents) and the mixture was stirred for 15 minutes and 710 DA4F-3o (o, +s, l) was added. The material was slowly heated to 118°C for 60 minutes and the acid percentage was 1.0. The reaction was continued until the following. Then maleic anhydride 18.2 & (0,185 6 mol) and reacted for 1.5 hours, cooH percent equal to 2.79. I got it. SorL7:l) Add Lastyrene 73.70.9 and the mixture 9 Cooled to 85°C. 1.711) Phenothianone 0.05 g? The mixture was cooled to 60°C. Then dimethylethanolamine 27.65 g (0.3107 eq.) was added and thoroughly vc mixed for 30 minutes. stirring Meanwhile, 1538 g of water was added at a rate of 15 to 2017 minutes. Its final solid par Cent is 20.3 and the Brookfield viscosity at 25°C is 16Cp s (0,016 Pα・S), and its particle size was 1950 A (195 nwL). Epoxy Mogetsuji of Example 2 (228.6g, 1.2057 equivalents) amount), bisphenol-A (23.9g, 0.2095 equivalent), No. squid-13 UOX18 (67g, 0.0944eq), tetrabutylphosphonium acetate (0.44 g), hydroquinone (0.13 g), glacial methacrylic acid (79.2 g) 2 g, 0.9212 equivalents), DMP-30 (0,36 g), C equal to 4.80 Maleic anhydride (38.13g, 0.3891 to give 0OH percent mole), phenothiazine (0,05l), styrene (77,3!j), dimethyzate ethanolamine (49,88,9,0,5604 equivalents) and deionized water ( 1186I). The final product is 15% solids 2 and 805A (80,5n The following fraction field was made using all the same procedures as in Example 9 with a particle size of m). ゛Epoxy/resin of Example 7 (254 g, 1.3417 equivalents), bisphenol- A (55 &, 0.4822 equivalents), tetrabutylphosphonium acetate (0, (22g), hydroquinone (0, (19g), methacrylic acid (72,4 41,0,8423 equivalents), DMP-30 (0,46 &), 2.5 equivalents C 0OH%H- Maleic anhydride (17.4.3g, 0.177 8 mol), phenothiazine (0,07 g), 4-chloro-2-ditrophenol (o, o 9 g), styrene (70,61), dimethylethanolamine (2 3,73Lj, 0.2666 eq): F6 and water (1486g). 20.2%1 This raw soup C type 25℃ T3 cps (U, U O3Pa・S) bull field viscosity. Particle size is 228 o, Z (228 lm )Met.

Example 12 Using the same procedure as Example 9, the following dispersion was made using the epoxy of Example 7. Antigreasing <2549.1.3417 equivalents), bisphenol-A, (55g, 0. 4822 equivalents), tetrabutylphosphonium acetate (0.22g), No. Doroquinone (0.09g>, glacial methacrylic acid (72.44y, 0.8423) 1), DMP -30 (0,46g), C0OH parameter equal to 2.5 Anhydrous mackerel/inic acid (17.43g, 0.1778mol) , phenothiazine (0,0?, l, 4-chloro-2-go, trophenol 21 (0,09g) styrene (44,4,9), dimethylethanolamine (23, 73 g, 0.2666 eq) ε and water (x513.l. This at 20.2% solids The product has a Brookfield viscosity of 3 cps (0°003Pα・S) at 25°C. He had great powers. The particle size was 228 OA (228 nm).

The above dispersion was made to 15% solids with water. To this], 5wt%cyme#(' Cyme t)R and 0.5% para-toluenesulfonic acid were added. untreated A 2-inch x 4-inch (102 mm x 3Q5 mm) piece of cleaned cold-rolled steel. The panel (go) is immersed in an electrolytic coating bath consisting of 2p of the above composition and the electrolytic bath A 2-inch (51mm) panel as a carbon cathode D. et al. Use electricity Decoated. An overpressure of 50V was applied for 2 minutes. Remove the panel from the bath D) The mixture was washed with deionized water and baked at 150° C. for 30 minutes. The obtained parameter The flannel is a smooth, hard, even texture that has been subjected to 10 to 15 methyl ethyl ketone double friction. Using the same procedure as in the example and using a 51.5-necked round-bottomed flask, do the following: A dispersion was made. Epoxy resin of Example 7 (411.9 g, 2.18.8 equivalents) , bisphenol-A, (819.4g, 0.7.84 equivalents), tetrabutylene Phosphonium acetate (10:8.5 g), Hydroquinone ( ・0.14g'), glacial methanolic acid, (11,9,, 9'8', 1.3・9 51 equivalents), DMP-30 (0,75 g), percent COOH equal to 4.57 Maleic anhydride (59.61L, 0.6083 mol), phenol Thiazine (o, 11), 4-chloro-2-ditrophenol (0,15p), and 1'1730 cp of water and 15% solids, the product was 3040 cp at 25°C. It had a Brookfield viscosity of s (3,04Pα·S).

Example 14 Using the same procedure as in Example 1, the following dispersions were made: Stell (273g), anhydrous malay giving a COOH percentage of 4.55 monoethyl ether of hydroquinone (0,1'1.9 ), phenothiazine (o, osy), dimethylethanolamine (32, 4,9) 8 and water (480g).

Using the procedure of Example 6, the following tire cord adhesive composition was applied to the above dispersion. (21,15g) The hole made using 'r: Cynor R303 (1,11,1, De-ionized On water (32,92g) and styrene/butadiene/vinylpyridine latex (15/70/15wt%) (12,02, l. Polyester cord is not coated. and tested by the method of Example 6. The adhesive is 375” for 60 seconds Cured at F (191°C). The resulting adhesion was 42.0 lb/in ( 7360N/rn).

Example 15 The following dispersions were made using the same procedure as in Example 6. Ta. Vinyl ester base resin of Example 1 (2'73g1, maleic anhydride ( 41,・Og), / oxic acid dihydrate (0, (06g), phenothiazine (0,0 6g), dimethylethanolamine (43,47g) & water (678,1° Using the procedure of Example 6, the following tire coat adhesive composition was prepared using the above dispersion (2). 7,5'#).

Cymel 8303 (-1,2,9), deionized water (30,8,12 and styrene /butadiene/vinylpyridine latex (15/70/15wt%) (t 2,939). The polyester cord was coated and processed by the method of Example 6. tested. The adhesive was cured at 375"F (191C) for 60 seconds. Obtained adhesion i:! It was 48.3 bonds/inch (846 ON/m).

Example 16 27.0 g of the reaction product used in Example 3 in a 50QmJ round bottom flask Ta. Then, 710 g of styrene was added. Add 5% NaOH solution to this mixture. Added to liquid 7.8'# with stirring. After stirring for 30 minutes deionized water 339.29 The sword was fired at a rate of 17 mIV/min. The product was a good stable dispersion.

The above dispersion 40. ! i’ffi Cymel R325 (methylated melamine formal Dehyde resin) 3. Mixed with Op. Next time.

10% 7)-Toluenesulfonic acid 0.4 neutralized with dimethylethanolamine 4g to 17.83g of deionized water? -I got bored. The resulting dispersion is While stirring normally 41% styrene/butadiene/vinylpyridine (15/70/15 wt% ) An adhesive was made by adding 12.93 g of latex.

Polyester cords were coated and tested according to the method of Example 6. Contact The amount of adhesive adhered was 5%.

The adhesive was cured for 10 minutes at 175°C. The resulting adhesive was 40 lbs/ inch (7000N/m, ).

The polymers of Examples 1 to 15 contained ammonium hydroxide in place of the amine mentioned in the present invention. , similar results were obtained when neutralized with sodium hydroxide or potassium hydroxide. Ta.

international metrology report

Claims (1)

[Claims] 1. Consists of half ester of dicarboxylic acid and secondary hydroxyl group of vinyl ester resin , the carboxylic acid group of the half ester is an alkali metal hydroxide, ammonium hydroxide or at least partially neutralized with a tertiary amine. A stable aqueous dispersion of a resin composition. 2. The dispersion according to claim 1, wherein the half ester contains 1 to 13 wt% of carboxylic acid. body. 3. The vinyl ester resin is composed of a monounsaturated monocarboxylic acid and a polyhydric alcohol or The claimed product is an esterification product of polyhydric phenol with polygly/dyl ether. The dispersion in the first term. 4. The vinyl ester resin (or diglyndyl ether of bisphenol A) The dispersion of claim 1 which is an ester. 5. Diglyphyl ether of la hibinyl ester resin bisphenol-A and a combination of an undissolved monocarboxylic acid 8 and a liquid carboxyne-terminated polydiene rubber; reaction product, in which at least 80% of the acid equivalents are the monocarboxylic acid and the balance of 0.01 to 20% is at least 4wt of the polydiene rubber. % of said polydiene. 6. The polydiene rubber is a copolymer of acrylonitrile and butadiene. The dispersion according to claim 10. 7. The polyglyc/dyl ether is novolac polyg6 5. The dispersion of claim 4 which is a water/dyl ether. 8. The dispersion of claim 1 and styrene/butadiene/vinylpyridine latte. Tire cord made by curing a mixture with a free radical initiator Value fiber-rubber adhesive composition. 9. Dispersion styrene/butadiene/vinylpyridine latte according to claim 1 Phenol blast or (=tire cord fiber made by curing with amineplast resin) Rubber adhesive composition. 10. Dispersion 8 of Claim 1 and an aminoblast extract containing a carboxylic acid catalyst Coatings made from oil or phenol blast resin or Bochenol blast resin D. Covering composition. l