JPH01161012A - Epoxy resin containing zwitterionic phosphate group - Google Patents

Abstract

PURPOSE:To produce the subject epoxy resin which has surface active performance and biocompatibility, by modifying hydroxyl groups of a polyhydroxylated epoxy resin with zwitterionic phosphate groups. CONSTITUTION:Alcoholic hydroxyl groups of a polyhydroxylated epoxy resin are reacted with 2-chloro-2-oxo-1,2,3-dioxaphosphorane at 0-10 deg.C. The reaction product is reacted with an amine (e.g., methylamine) in a solvent (e.g., dimethylformamide) at 50-80 deg.C to obtain an epoxy resin containing zwitterionic phosphate groups which has a zwitterionic phosphate equivalent of 50-3,000 and wherein at least 2 of the hydroxy groups of the polyhydroxylated epoxy resin is modified by zwitterionic phosphate groups of the formula (wherein R<1-3> are each H, 1-20C alkyl, alkenyl, aryl, or an alicyclic hydrocarbon group).

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to adding at least a phosphoric acid Zvitter group formed from phosphoric acid and an amine to a polyhydroxy compound (having two or more hydroxyl groups) modified from an epoxy resin. This invention relates to a modified epoxy resin obtained by introducing two or more epoxy resins.

(Prior Art and its Problems) Phosphate Zwitter groups have the formula: %Formula% and have various properties such as surfactant ability and biocompatibility. Various compounds having such a phosphate Zvitter group have been obtained naturally and synthetically, but it is sometimes difficult to impart one of the various properties of the phosphate Zvitter group.

For example, in JP-A-61-205291 and JP-A-61-207395, one
Compounds having one or two are disclosed. The former is a monomer having a polymerization active group, and the latter is a diol that is a constituent of a polyurethane polymer. All of these can be used as film-forming materials, but their functionality as surfactants is poor.

(Means for solving the problem) The present inventors have discovered not only film-forming ability but also surface-active ability,
Furthermore, as a result of studies to obtain a phosphoric acid zwitter material that is also biocompatible, the present invention has been completed.

That is, the present invention provides a phosphoric acid Zwitter group-containing epoxy resin in which at least a portion of the hydroxyl groups of the multihydroxylated epoxy resin are modified with phosphoric acid Zwitter groups.

As the multi-hydroxylated epoxy resin, an epoxy resin that is linear, has epoxy groups at both ends, and has an alcoholic hydroxyl group in the main chain can be used. Examples of these are Bisphenol A1 Bisphenol S1 Bisphenol F
Diglylenol ethers of glycols (e.g., butanediol, hexanediol, hydrogenated bisphenol A, etc.) are typical; glycols (e.g., polyethylene glycol, polypropylene glycol, polyethylene glycol, bisphenol) Diglycidyl ether of polyokine alkylene glycols, which is an adduct of polyoxene and alkylene oxide; diglycidyl ester of dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, adipic acid, etc.), hydroxycarboxylic acids (e.g., paraoxobenzoic acid) acids, metahydroxybenzoic acid, etc.), or esters.

Epoxy compounds that do not have an alcoholic hydroxyl group in their main chain are extended in chain length by reaction with a bifunctional active hydrogen-containing compound, and are preformed with an alcoholic hydroxyl group in their main chain that is generated by ring-opening of the epoxy group. It can be used by making it into a modified epoxy resin. The bifunctional active hydrogen-containing compound used for chain lengthening is a compound having at least two amino groups, imino groups, hydroxyl groups, or carboxyl groups in the molecule as active hydrogen-containing groups. Examples of these include ethylene glycol, trimethylene glycol, tetramethylene glycol, l.

Alkylene glycols such as 6-hexanediol; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; n moles of adipic acid and n+1
Polyester diols such as reaction products with moles of ethylene gelcol; bisphenol A, l, 1-bis(
4-hydroxyphenyl)ethane, 2-methyl-t,i
-bis(4-hydroxyphenyl)propane, 2,2-
Bis(4-hydroxy-3-t-butylphenyl)propane, bis(2-hydroxynaphthyl)methane, I, 5
- dihydric phenols such as dihydroxynaphthalene; dicarboxylic acids and their anhydrides such as adipic acid, azelaic acid, maleic anhydride, phthalic anhydride; reaction products of n moles of ethylene glycol and n+1 moles of phthalic anhydride; Polyester dicarboxylic acids; alkanolamines such as N-methylethanolamine, N-methylpropanolamine, jetanolamine, dibrobanolamine; N,N'-trimethylethylenediamine, N,N'
-Diamines such as dimethyltrimethyldiamine.

Furthermore, in addition to epoxy resins that are linear or have side chains in a linear chain, there are, for example, novolac type, evoquinated polybutadiene, epoxidized natural oil, or Resilson type epoxy resin.

The method for introducing phosphate Zvitter groups into the above-mentioned multi-hydroxylated epoxy resin is to first introduce 2-chloro-2-oxo-1,2,
A preferred method is to react 3-dioxaphosporane at 0 to 10°C, and then react the resulting reaction product with an amine in a predetermined solvent (eg, dimethylformamide, acetonitrile, methanol, etc.). Typical examples of amines that can be used include aliphatic amines such as ammonia, -grade amines such as methylamine, edylamine,
n-propylamine, isopropylamine), secondary amines (e.g. diethylamine, diethylamine, etc.), tertiary amines (e.g. trimethylamine, triethylamine,
dimethyllaurylamine, etc.), or amino alcohols (eg, jetanolamine, methylethanolamine, etc.); aromatic amines, such as aniline, toluidine, etc.; or alicyclic amines, such as cyclohexylamine, cyclopentylamine, etc. The reaction with the amine is carried out at a temperature range of 50-80°C. The end point of the reaction is confirmed by NMR.

The phosphoric acid Zvitter group-containing epoxy resin of the present invention has a phosphoric acid Zvitter equivalent, expressed as a molecular weight per one phosphoric acid Zvitter group, of 50 to 3,000, preferably 200 to 20.
00 is preferred. If the molecular weight per phosphoric acid Zvitter group is less than 50, the surfactant ability and water dispersion stability will decrease, and if it exceeds 3,000, the surfactant ability will be poor. The phosphoric acid Zwitter group-containing epoxy resins of the present invention are classified into linear type and main chain side chain type. Since the linear type has a phosphoric acid Zvitter group introduced at both ends, it has better surface activity than one at one end or where the position is not controlled. In addition, in the case of the main chain side chain type, the surfactant ability becomes good due to the balance between the molecular weight of the hydrophobic part of the main chain side chain and the number of phosphoric acid Zvitter groups. In addition, regarding the relationship between the hydrophobic group of the amine part of the phosphoric acid Zvitter group and the surfactant ability, there is a deep relationship between the amine hydrophobic group and the surfactant ability. The surfactant ability increases in the order of alicyclic hydrocarbons and alicyclic hydrocarbons. The phosphoric acid Zwitter group-containing epoxy resin of the present invention forms a tough film through the reaction of active hydrogen-containing groups (e.g., hydroxyl, amino, carboxyl groups) in the resin with a curing agent such as melamine resin or blocked isocyanate. can do. Moreover, a blocked isocyanate group can be introduced by the reaction between an active hydrogen-containing group and a half-blocked isocyanate compound, thereby making it possible to impart curability to the epoxy resin itself.

The phosphoric acid Zwitter group-containing epoxy resin of the present invention may exhibit biocompatibility if necessary.

The epoxy resin of the present invention may exhibit a buffering effect. Phosphate Zvitter resin, which has strong hydrophilicity, is preferred in order to exhibit a buffer effect. Therefore, the buffer effect is enhanced by using a modified epoxy resin with a small epoxy equivalent (specifically, 1000 or less). Furthermore, the epoxy resin of the present invention may have antistatic ability. Resins containing phosphoric acid zwitter are hygroscopic and ionic and can be used as antistatic agents.

(Effects of the Invention) The phosphoric acid Zwitter group-containing epoxy resin of the present invention not only has film-forming ability, but also has various other properties due to the phosphoric acid Zwitter group, such as surfactant ability, biocompatibility, buffer effect, antistatic ability, etc. can be granted. The epoxy resin of the present invention is the first to have this film-forming ability and to exhibit various film performances.

(Example) The present invention will be explained in more detail with reference to Examples. The present invention is not limited to these examples.

Example 1 A flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser was charged with 94 parts of an epoxy resin with an epoxy equivalent weight of 189 obtained by the reaction of bisphenol and evil rohydrin, and 70 parts of xylene. After the temperature was raised to 80°C under a nitrogen stream, 67 parts of dimedylolpivalic acid and 1.61 parts of dimethylbenzylamine were added and reacted at 140°C for 6 hours. After the reaction was completed, the temperature was raised to 80°C under reduced pressure. xylene was removed. The reactants and 20 parts of triethylamine were dissolved in 170 parts of acetone, and after cooling to 5°C, 2-chloro-2-oxo-1,3,2-dioxaphosphorane 2
9 parts were added dropwise while maintaining the reaction temperature at 5°C. Stirring was continued for 1 hour after the dropwise addition, but the hydroxyl group of the hydroxy compound and the 2
As the reaction with -chloro-2-ox/-1,3,2-nooxaphosporane progresses, triethylamine hydrochloride precipitates out.

The reaction was further carried out at room temperature for 2 hours, and after the reaction was completed, triethylamine hydrochloride was removed by filtration, and acetone was removed under reduced pressure. The yield in this reaction was calculated from the weight of filtered triethylamine hydrochloride and was 95%.

Next, the above reactant, 13 parts of trimethylamine, and 180 parts of dimethylformamide were placed in a pressure-resistant reactor, and reacted at 60° C. for 62 hours. After the reaction is completed, concentrate under reduced pressure,
The desired resin was obtained. When the obtained resin was analyzed by NMR, the methylene proton signal of phosphorane that had been observed at around δ3, 5 ppm disappeared, and due to the reaction of the above reactant with triethylamine, the signal was reduced to 64 ppm.
A new methylene proton signal due to ring opening of phosphorane was confirmed nearby. Also IR measurement l O40
Absorption of shear -0 at cm-' and absorption of shear 8 at 1240 cm-' were observed. The resin obtained from these things has four phosphoric acid Zvitter groups in one molecule as shown in soil, and the phosphoric acid Zvitter equivalent is 23.
0 modified epoxy resin l was obtained.

■ Example 2 Using the same reaction apparatus as in Example 1, 198 parts of an epoxy resin with an epoxy equivalent of 975 obtained by the reaction of bisphenol and evil rohydrin were charged, and 56 parts of xylene was added.
After heating to 80°C under a nitrogen stream, 24 parts of hydroxybivalic acid and 2.23 parts of dimethylbenzylamine were added and reacted at 140°C for 1 hour. After the reaction was completed, the temperature was raised to 80°C under reduced pressure. Removed xylene. After dissolving the reactant and 10 parts of triethylamine in 356 parts of methyl ethyl ketone and cooling to 0°C, 2-chloro-2-oxo-1,3,
14.3 parts of 2-dioxaphosphorane was added dropwise while maintaining the reaction temperature at 0°C. After the dropwise addition was completed, the mixture was allowed to react for 1 hour under cooling.
The reaction was further carried out at room temperature for 2 hours, and after the reaction was completed, triethylamine hydrochloride was removed and methyl ethyl ketone was removed under reduced pressure.

Next, the above reactant, 21.3 parts of dimethyllaurylamine, and 230 parts of dimethylformamide were placed in a flask.
The reaction was carried out at 57°C for 15 hours.

After the reaction is completed, it is concentrated under reduced pressure to obtain a resin with two phosphoric acid Zvitter groups in one molecule and a phosphoric acid Zvitter equivalent of 12
A modified epoxy resin flame of 90 was obtained.

The structure of the resin was confirmed by NMR and I in the same manner as in Example 1.
It was done in R.

? Example 3 Using the same reactor as in Example 1, 198 parts of the same epoxy resin as used in Example 2 was charged, and 57 parts of xylene was added.
After heating to 80°C under a nitrogen stream, 28 parts of dimethylolpinocrylic acid and 2.26 parts of dimethylbenzylamine were added and reacted at 140°C for 1.3 hours to complete the reaction. Thereafter, xylene was removed under reduced pressure to obtain a hydroxy compound. Then 2-chloro-2-oxo-1,3,
57 parts of 2-dioxaphosphorane and 85 parts of dimethyllaurylamine were introduced in the same manner as in Example 2 to obtain resin 1.
A modified epoxy resin 3 having 4 g of phosphoric acid Zvitter groups in the molecule and having a phosphoric acid Zvitter equivalent of 920 was obtained.

The structure of the resin was confirmed by NMR and I in the same manner as in Example 1.
It was done in R.

Example 4 Using the same reaction apparatus as in Example 1, 236 parts of the same epoxy resin as used in Example 2, 2 parts of hydroxybivalylic acid
9.5 parts and 2.66 parts of dimethylbenzylamine were reacted in the same manner as in Example 2 to obtain a hydroxy compound,
Further, 35.5 parts of 2-chloro-2-oxo-1,3,2-dioxaphosphorane was introduced in the same manner as in Example 2.

Next, put the above reactant, 218.8 parts of methylethanolamide and 300 parts of dimethylformamide into a flask,
The reaction was carried out at 70°C for 20 hours.

After the reaction, it was concentrated under reduced pressure to obtain a modified epoxy resin ± having two phosphoric acid Zvitter groups in which the terminal amine is methylethanolamine in each resin molecule and having a phosphoric acid Zvitter equivalent of 1280. Ta. The structure of the resin was confirmed by NMR and IR in the same manner as in Example 1.

Example 5 Using the same reactor as in Example 1, 1940 epoxy
200 parts of polyglycol ether type epoxy resin,
28 parts of dimethylolpivalic acid and 22.28 parts of dimethylbenzylamine were reacted in the same manner as in Example 3 to obtain a hydroxy compound, and further 2-chloro-2-oxo-
56 parts of 1,3,2-dioxaphosphorane were introduced in the same manner as in Example 2.

Next, the above reactant and 29.5 parts of methylethanolamine were reacted in the same manner as in Example 4, and each molecule of the resin contained four phosphoric acid Zvitter groups whose terminal amine was methylethanolamine. A modified epoxy resin having a phosphoric acid Zwitter equivalent weight of 780 was obtained.

The structure of the resin was confirmed using NMR and IR in the same manner as in Example 1.
It was done in

Example 6 Using the same reaction apparatus as in Example 1, 189 parts of the same epoxy resin as used in Example 2 was charged, 52 parts of xylene was added and dissolved, and the temperature was raised to 80°C under a nitrogen stream, followed by dipropyl. Add 20 parts of amine and react at 100°C for 2 hours.
Thereafter, the mixture was cooled, and 300 parts of ε-caprolactam and 1.01 parts of dibutyltin oxide were added thereto and reacted at 120° C. for 6 hours. After the reaction was completed, xylene was removed under reduced pressure to obtain a hydroxy compound. Furthermore, 2-chloro-2-oxo-1,
57 parts of 3,2-dioxaphosphorane were introduced in the same manner as in Example 2.

Next, the above reactant and 30 parts of methylethanolamine were reacted in the same manner as in Example 4, and the resin had an average of 4.5 phosphate Zvitter groups in its side chain per molecule of resin. - Modified epoxy resin 1 having an equivalent weight of 1320 was obtained.

The structure of the resin was confirmed by NMR and IR in the same manner as in Example I.
It was done in

X δ 1″ 碕＼〜−y ＼−−／ Niji Brother Example 7 Using the same reactor as in Example 1, 189 parts of Evoquin resin similar to that used in Example 2 was charged, and 53 parts of xylene was added. After adding and dissolving, the temperature was raised to 800 C under a nitrogen stream, 21 parts of jetanolamine was added, and the mixture was reacted at 100 C for 1.5 hours, after which it was cooled and xylene was removed under reduced pressure to obtain a hydroxy compound.Furthermore, 2 -chloro-2-oxo-
57 parts of 1,3,2-dioxaphosphorane were introduced in the same manner as in Example 2.

Next, the above reactant and 30 parts of methylethanolamine were reacted in the same manner as in Example 4, so that the resin had four phosphoric acid Zvitter groups in one molecule, and the phosphoric acid Zvitter equivalent was 740.
A modified epoxy resin was obtained. The structure of the resin was confirmed by NMR and IR in the same manner as in Example 1.

Example 8 Using the same reactor as in Example 1, the epoxy equivalent was 15
8 Noholak type Evokin resin 711i1, 531 parts of hydroxybivalic acid and dimethylbenzylamine 5.
One part was reacted in the same manner as in Example 2 to obtain a hydroxy compound, and further 2-chloro-2-oxo-1,3,2-
429 parts of dioxaphosphorane were introduced in the same manner as in Example 2.

Next, put the above reaction product, 225 parts of methylethanolamine and 300 parts of dimethylformamide into a flask, and
The reaction was carried out at 0°C for 20 hours. After the reaction is completed, it is concentrated under reduced pressure to obtain a resin having two phosphoric acid Zvitter groups in one molecule,
A modified epoxy resin having a phosphoric acid Zwitter equivalent of 590 was obtained.

The structure of the resin was confirmed by NMR and IR in the same manner as in Example I.
It was done in

Example 9 Using the same reaction apparatus as in Example 1, 1492 parts of an epoxy resin of fi 3000 obtained by the reaction of bisphenol and epichlorohydrin was charged, and one molecule of resin was prepared using the same reagents and operations as in Example 1. inside 2
A modified epoxy resin having 3,280 phosphoric acid Zvitter groups and a phosphoric acid Zvitter equivalent weight of 3,280 was obtained.

Application Example 1 1.5 parts of phosphoric acid Zvitter resin obtained in Example 1 was dissolved in 6 parts of deionized water, the pH of this aqueous solution was adjusted to 7.3, and 1% dihydroxyethyl taurine aqueous solution was dissolved in 1.5 parts of phosphoric acid Zvitter resin obtained in Example 1.
Added 0 copies. Furthermore, 2 parts of phospholipase C (enzyme activity includes I 25 units) aqueous solution was added, and 4
It was left at room temperature for several days. The resulting resin dispersion was cloudy compared to before the start of the experiment, and when comparing the average particle size, it was found that the average particle size had increased from 189 mμ to 646 mμ before the start of the experiment. This was thought to be due to decomposition and agglomeration.

Application Example 2 1.5 parts of the phosphate Zvitter resin obtained in Example 1 was dissolved in deionized water and titrated with a 1/10 normal aqueous sodium hydroxide solution. van S lyke's buffer value β (
β = number of equivalents of strong acid or strong base added to 1 g of solution / pH change) was calculated and found to be β - 0,015,
Sufficient buffering capacity was observed.

Application Example 3 In a reaction vessel, the phosphoric acid zwitter obtained in Example 3 was placed.
172 parts of a group-containing epoxy resin was taken, and the solvent was removed at 70° C. by adding a pressure reduction device. After removing the solvent, add 4.5 parts of triethylamine, stir well, and add 1 part of deionized water.
150 parts of the solution were added and dissolved while stirring while maintaining the temperature at 80° C., and to this was added a solution prepared by dissolving 12 parts of azobiscyanovaleric acid in 124 parts of deionized water and 7.5 parts of triedylamine. Then 179 parts of methyl methacrylate, n-
248 parts of butyl acrylate, 193 parts of styrene, 2-
60 parts of a mixed solution consisting of 14 parts of hydroxyethyl acrylate and 42 parts of ethylene glycol dimethacrylate
It took several minutes to drip. After dropping, 4.1 parts of azobiscyanovaleric acid was added to 41 parts of deionized water and 2.1 parts of triethylamine.
Add the solution dissolved in 5 parts and continue stirring at 80°C for 60 minutes to obtain a mixture with an average particle size of 87 parts and a heating residue of 39.6%.
An aqueous dispersion of internally crosslinked fine resin particles was obtained. This fine resin particle dispersion was stable and did not cause aggregation or sedimentation even after being left for one month.

It was confirmed that the phosphoric acid Zwitter group-containing resin used in this experiment had sufficient emulsifying ability as an emulsifier in emulsion polymerization.

Application Example 4 40 parts of the phosphoric acid Zvitter group-containing epoxy resin obtained in Example 3 was placed in a container, and 1.9 parts of helimethylethanolamine, with an average molecular weight of 4500 and a hydroxyl value of 50, was placed in a container.
30 parts of acrylic resin and 30 parts of methylated butylated modified melamine resin were added and thoroughly stirred. Then gradually 5
An aqueous dispersion was obtained by adding 67 parts of deionized water and removing the solvent at 70°C by adding a pressure reduction device.

The nonvolatile content of this resin dispersion was 15%, the l) I-1 was 84, and the conductivity was 2.76 m5/cm. Using this resin dispersion, anionic electrodeposition was carried out at a coating voltage of 150 cm for 2 minutes. This resin dispersion had sufficient film resistance and throwability, and the resulting electrodeposition coating was smooth.

The pencil strength of the coating film obtained by baking at 1508C for 30 minutes was 2H, and it had a hardenability of 50 times or more of xylol rubbing.

Application Example 5 In a stainless steel beaker, 100 parts of the Zvitter phosphate resin obtained in Example 6, 12 parts of dimethylethanolamine, and 150 parts of deionized water were charged, and after thorough stirring, hexamethoxymethylolmelamine (American Cyanamid Co., Ltd.) was added. 15 parts of ethylene glycol monobutyl ether (manufactured by Cyme JL, 303) and 5 parts of ethylene glycol monobutyl ether were gradually added to obtain a resin composition having phosphoric acid zwitter.

This composition was coated on the inside of a glass Petri dish with a dry film thickness of 10
A glass petri dish coated with a resin composition having a phosphoric acid Zvitter group was obtained by coating the sample so as to have a phosphoric acid Zvitter group and baking it for 20 minutes at 170°C. Next, in a glass Petri dish, add benzyladenine (
Hanakirin cultured cells (0,59) were transferred to a liquid medium (10 mC) containing 10-@M) and naphthylacetic acid (10-'M), and cultured statically. After 10 days, 62μ
It was filtered with a nylon filter and washed with sterile water to obtain cultured cells (4 g). It was found that the glass Petri dish coated with the resin composition having a phosphoric acid Zvitter group is a good container for cell culture in which culture is not inhibited.

Application Example 6 The phosphoric acid Zvitter group-containing epoxy resin obtained in Example 9 was desolventized under reduced pressure, and triethylamine was used to
0% neutralization was performed. Further deionized water was added, but an aqueous dispersion could not be obtained.

Patent applicant Nippon Paint Co., Ltd.

Claims (1)

[Scope of Claims] 1. A phosphoric acid Zvitter group-containing epoxy resin in which at least a portion of the hydroxyl groups of a multi-hydroxylated epoxy resin are modified with a phosphoric acid Zvitter group. 2. At least two or more of the hydroxyl groups of the multi-hydroxylated epoxy resin have the formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1, R^2 and R^3 are the same or different, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
Indicates an alkenyl group, an aryl group, or an alicyclic hydrocarbon group. ] The phosphoric acid Zvitter group-containing epoxy resin according to item 1, which is modified to a phosphoric acid Zvitter group represented by the following. 3. The phosphoric acid Zvitter group-containing epoxy resin according to item 1, which has a phosphoric acid Zvitter equivalent weight of 50 to 3,000.