JP2000319267A - Tris(2-carboxyethyl)isocyanurate derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound excellent in solubility to organic solvents and compatibility with various resins, and useful as e.g. a curing agent for one-part curable compositions by modifying with a specific vinyl ether compound the carboxyl group of tris(2-carboxyethyl)isocyanurate. SOLUTION: This new compound is a compound of formula I (R1 to R3 are each H or a 1-18C organic group; R4 is a 1-18C organic group; R3 and R4 may be bound to each other to form a heterocyclic ring with Y1 as heteroatom; Y1 is O or S), e.g. a compound of formula II. The compound of formula I is obtained by reaction between tris(2-carboxyethyl)isocyanurate and a vinyl ether compound of formula III (e.g. n-propylvinyl ether) in the equivalent ratio of the carboxyl group of the former to the vinyl ether group of the latter of pref. (1:1) to (1:1.2) pref. at 50-100 deg.C normally for 1-100 h, optionally in the presence of an acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel tris (2)
-Carboxyethyl) isocyanurate derivative,
More specifically, as a thermosetting composition having excellent solubility in organic solvents and compatibility with various resins, and having good chemical and physical properties, a thermosetting composition suitable for a paint, an ink, an adhesive, a molded product, and a photoresist. The present invention relates to a tris (2-carboxyethyl) isocyanurate derivative capable of providing a contrast enhancer realizing high resolution.

[0002]

2. Description of the Related Art Conventionally, tris (2-carboxyethyl) isocyanurate has been used in terms of chemical performance and physical performance.
It has been considered useful as a curing agent for various thermosetting compositions. However, tris (2-carboxyethyl) isocyanurate has high crystallinity and a high melting point due to high hydrogen bonding of the carboxyl group, and has low solubility in general organic solvents and low compatibility with various resins, and is difficult to handle. There was a problem. When tris (2-carboxyethyl) isocyanurate is used in the form of a mixture with another compound, a carboxyl group and an epoxy group, a silanol group, an alkoxysilane group, a hydroxyl group, an amino group, an imino group, Since it has high reactivity with reactive functional groups such as isocyanate group, blocked isocyanate group, cyclocarbonate group, vinyl ether group, vinyl thioether group, aminomethylol group, alkylated aminomethylol group, acetal group and ketal group, carboxyl group In a composition in which the compound to be contained and the compound having the reactive functional group coexist, stability has been a problem, for example, gelation occurs during storage or the pot life is shortened. As a method for solving such a problem, for example, a carboxyl group is blocked as t-butyl ester,
A method of regenerating a free carboxyl group by isobutene elimination decomposition by heating has been proposed (JP-A-1-104646). However, this method requires 170-200 ° C. for the thermal decomposition of the t-butyl ester group.
This method requires a high temperature, which is not always satisfactory from the viewpoint of saving resources and energy. In addition, traces of foaming due to isobutene generated by decomposition also become a problem.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a method for modifying tris (2-carboxyethyl) isocyanurate, which has poor solubility, with a specific vinyl ether compound.
By increasing the solubility in general organic solvents and the compatibility with various resins, and combining it with various curable resins, it can be used as a curing agent for one-part curable compositions. The purpose of the present invention is to obtain a tris (2-carboxyethyl) isocyanurate derivative which can be used as a contrast enhancer for realizing image properties.

[0004]

The present inventors have conducted intensive studies to develop a tris (2-carboxyethyl) isocyanurate derivative having the above-mentioned preferable properties. It has been found that a novel tris (2-carboxyethyl) isocyanurate derivative obtained by reacting a carboxyl group of a nurate with a vinyl ether compound can achieve the object, and based on these findings, the present invention has been completed. Reached. That is, the present invention provides a compound represented by the general formula (1):

[0005]

Embedded image

(Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a carbon atom having 1 to 18 carbon atoms)
18 an organic group, R ³ and R ⁴ may form a heterocyclic structure which comprises Y ¹ as the hetero atom bonded with each other,
Y ¹ is an oxygen atom or a sulfur atom), and is a tris (2-carboxyethyl) isocyanurate derivative. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The tris (2-carboxyethyl) isocyanurate derivative of the present invention can be obtained by reacting tris (2-carboxyethyl) isocyanurate with a vinyl ether compound. The vinyl ether compound used for synthesizing the tris (2-carboxyethyl) isocyanurate derivative of the present invention includes the following general formula (2)

[0008]

Embedded image

(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹
Has the same meaning as described above. ) Can be used. The compound of the general formula (2) is preferably a monovinyl ether compound, and specific examples thereof include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, secondary butyl vinyl ether, and tertiary butyl. Aliphatic vinyl ether compounds such as vinyl ether, isoamyl vinyl ether, cyclohexyl vinyl ether, and 2-ethylhexyl vinyl ether, and the corresponding aliphatic vinyl thioether compounds; furthermore, 2,3-dihydrofuran, 3,4-dihydrofuran, and 2,3-dihydrofuran; -2H-pyran, 3,4-dihydro-2H-pyran,
3,4-dihydro-2-methoxy-2H-pyran, 3,
4-dihydro-4,4-dimethyl-2H-pyran-2-
Cyclic vinyl ether compounds such as on, 3,4-dihydro-2-ethoxy-2H-pyran and sodium 3,4-dihydro-2H-pyran-2-carboxylate; and cyclic vinyl thioether compounds corresponding thereto. These vinyl ether compounds can be used alone or in combination of two or more.

The reaction ratio when reacting the above tris (2-carboxyethyl) isocyanurate and the above vinyl ether compound is such that the equivalent ratio of the former carboxyl group to the latter vinyl ether group is usually about 1: 1 to 1: 2. The ratio is preferably 1: 1 to 1: 1.5, particularly preferably 1: 1 to 1: 1.2. The reaction temperature of this reaction may be generally in the range of room temperature to 150 ° C, and preferably 50 to 100 ° C. The reaction time of this reaction may be appropriately selected according to the progress of the reaction, and is usually 1 to 100 hours. At this time, an acid catalyst can be used for the purpose of accelerating the reaction. As such an acid catalyst, for example, the general formula (3)

[0011]

Embedded image (R ⁵ —O—) _m —P (O) — (OH) _3-m (3)

(Wherein R ⁵ is an alkyl group, cycloalkyl group or aryl group having 3 to 10 carbon atoms, and m is 1 or 2).
More specifically, n-propanol, n-butanol,
Phosphoric acid monoesters or phosphorus of primary alcohols such as n-hexanol, n-octanol and 2-ethylhexanol, and secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol and cyclohexanol Acid diesters. These acid catalysts can be used alone or in combination of two or more. Although the amount of the acid catalyst used is not particularly limited, tris (2-carboxyethyl)
Total amount of isocyanurate and vinyl ether compound 10
Usually, 0.0005 to 0.05 part by weight, particularly preferably 0.001 to 0.01 part by weight, relative to 0 part by weight is preferable.

An organic solvent can also be used for the purpose of making the reaction system uniform and facilitating the reaction. Examples of such an organic solvent include benzene, toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine, Solvesso # 100 (registered trademark of Exxon Chemical Co., Ltd.), Solvesso # 150 (registered with Exxon Chemical Co., Ltd.) Trademark) and the like, ethers such as dioxane and tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-acetate.
Esters and ether esters such as butyl, isobutyl acetate, sec-butyl acetate, amyl acetate, monomethyl ether, methoxybutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone, mesityl oxide, methyl isoamyl ketone , Ethyl positive butyl ketone,
Examples thereof include ketones such as ethyl amyl ketone, diisobutyl ketone, diethyl ketone, methyl propyl ketone, and diisopropyl ketone; phosphates such as trimethyl phosphate, triethyl phosphate, and tributyl phosphate; dimethyl sulfoxide; and N, N-dimethylformamide. One or more organic solvents can be used in combination.

The tris (2-carboxyethyl) isocyanurate derivative of the present invention is accompanied by elimination of vinyl ethers by heating or irradiation with actinic rays such as ultraviolet rays and electron beams, and the original tris (2-carboxyethyl) derivative Regenerate isocyanurate. This free acid regeneration reaction is
Assisted by an acid catalyst. Such acid catalysts include:
For example, protonic acids such as halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters, phosphoric acid mono- and diesters, polyphosphate esters, boric acid mono- and diesters, BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ ,
Organometallic compounds such as ZnCl ₂ , trialkylboron, trialkylaluminum, dialkylaluminum halide, monoalkylaluminum halide, tetraalkyltin, aluminum diisopropoxyethyl acetoacetate, aluminum tris (ethylacetoacetate), isopropoxybis (Ethyl acetoacetate) aluminum, monoacetylacetonato
Bis (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (n-butylacetoacetate) aluminum, monoethylacetoacetate bis (acetylacetonate)
Aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum, acetylacetonatobis (propionylacetonato) aluminum, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetoacetate) Nato) titanium, tetrakis (n-
Propyl acetoacetate) zirconium, tetrakis (acetylacetonato) zirconium, tetrakis (ethylacetoacetate) zirconium, dichlorobis (acetylacetonato) tin, dibutylbis (acetylacetonato) tin, tris (acetylacetonato)
Metal chelates such as iron, tris (acetylacetonato) chromium, tris (acetylacetonato) rhodium, bis (acetylacetonato) zinc, tris (acetylacetonato) cobalt, dibutyltin dilaurate, dioctyltin ester malate, naphthenic acid Magnesium, calcium naphthenate, manganese naphthenate, iron naphthenate, cobalt naphthenate, copper naphthenate, zinc naphthenate, zirconium naphthenate, lead naphthenate, calcium octylate, manganese octylate, iron octylate, cobalt octylate, Zinc octylate, zirconium octylate, tin octoate, lead octylate, zinc laurate, magnesium stearate, aluminum stearate, calcium stearate, cobalt stearate, stearie Zinc, and the like Lewis acids such as metal soaps such as lead stearate and the like. As the photoacid catalyst, Adeka Optomer SP series (trade name, manufactured by Asahi Denka Kogyo KK) or the like can be used. These acid catalysts can be used alone or in combination of two or more.

The tris (2-carboxyethyl) isocyanurate derivative of the present invention is used as a curing agent for a resin having various reactive functional groups. Examples of such a reactive functional group include an epoxy group and a silanol. Group, alkoxysilane group, hydroxyl group, amino group, imino group, isocyanate group, blocked isocyanate group,
Examples include a cyclocarbonate group, a vinyl ether group, a vinyl thioether group, an aminomethylol group, an alkylated aminomethylol group, an acetal group, and a ketal group.

Examples of the resin having such a reactive functional group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin, and glycidyl. Homopolymers or copolymers such as (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate; epoxy group-containing compounds such as polyglycidyl compounds obtained by reacting polycarboxylic acids or polyols with epichlorohydrin; Equation (4)

[0017]

Embedded image (R ⁶ ) _n Si (OR ⁷ ) _4-n (4)

Wherein R ⁶ and R ⁷ are alkyl or aryl groups having 1 to 18 carbon atoms, and n is 0, 1 or 2. acryloyloxypropyl Homopolymers or copolymers of α, β-unsaturated silane compounds such as trimethoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltri-n-butoxysilane, and hydrolysis products of these compounds. Compounds containing silanol groups or alkoxysilane groups; aliphatic polyols, phenols, polyalkyleneoxy glycols, α, β-unsaturated compounds such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Homopolymer or copolymer, and ε-caprolase of these polyols A hydroxyl group-containing compound such as a ton adduct; an amino group-containing compound such as an aliphatic or aromatic diamino compound or polyamino compound and a polyamino compound obtained by reducing a cyanoethylation reaction product of the polyol; Imino group-containing compounds such as polyimino compounds; p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2, 2,4
-Trimethylhexane-1,6-diisocyanate, methylenebis (phenylisocyanate), lysine methylester diisocyanate, bis (isocyanateethyl) fumarate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 2-isocyanatoethyl-2,6-diisocyanate hexanoate and the like Burettes and isocyanurates, and isocyanate-containing compounds such as adducts of these isocyanates with the polyol; phenols and lactams of the isocyanate-containing compounds;
Blocked isocyanate group-containing compounds such as blocks with active methylenes, alcohols, acid amides, imides, amines, imidazoles, ureas, imines, oximes; 3- (meth) acryloyloxypropylene carbonate Homopolymers or copolymers, cyclocarbonate group-containing compounds such as polyvalent cyclocarbonate group-containing compounds obtained by reacting the epoxy group-containing compound with carbon dioxide; the polyvalent hydroxyl group-containing compound and halogenated alkyl vinyl ethers A vinyl ether compound obtained by reacting a hydroxyalkyl vinyl ether with a compound containing a polyvalent carboxyl group or the above-mentioned polyisocyanate compound; Vinyl ether compounds such as copolymers of acrylates and α, β-unsaturated compounds, and corresponding compounds containing vinyl ether groups and vinyl thioether groups such as vinyl thioether compounds; melamine formaldehyde resin, glycolyl formaldehyde resin, urea formaldehyde Resin, aminomethylol group or alkylated aminomethylol group-containing compound such as homopolymer or copolymer of aminomethylol group or alkylated aminomethylol group-containing α, β-unsaturated compound; polyhydric ketone, polyhydric aldehyde compound, A polyacetal compound obtained by reacting the polyvalent vinyl ether compound or the like with an alcohol or an orthoacid ester, a condensate of the polyacetal compound with a polyol compound, and a vinyloxyalkyl (meth) acrylate and an alcohol; Acetal group- and ketal-group-containing compounds such as homopolymers or copolymers of adducts with carboxylic acids and orthoacid esters. These resins can be used alone or in combination of two or more.

The amount of the acid catalyst used is based on 100 parts by weight of the total amount of the tris (2-carboxyethyl) isocyanurate derivative and the resin having a reactive functional group.
Usually, 0.01 to 10 parts by weight is preferable, and especially 0.1 to 1 part by weight.
Parts by weight are preferred. In the curable composition containing the tris (2-carboxyethyl) isocyanurate derivative of the present invention and a resin having a reactive functional group, the composition ratio of both is equivalent to the equivalent of the former carboxyl group and the latter reactive functional group. The ratio may usually be in the range of 0.2: 1.0 to 1.0: 0.2. In addition, the curable composition, in addition to the acid catalyst, a coloring pigment, a filler, a solvent, an ultraviolet absorber, an antioxidant, a flow regulator, a surfactant, a leveling agent, a thixotropic agent, an antifoaming agent, and the like. Various additives can be contained.

The curing of the curable composition can be performed in various temperature ranges from a low temperature to a high temperature, for example, in a range from room temperature to 300 ° C. Thus, the curable composition can be a low temperature curable composition, a thermosetting composition, and the like. The curing time of the curable composition may be appropriately selected, and is usually 0.01 to 24 hours. Further, the tris (2-carboxyethyl) isocyanurate derivative of the present invention can be used as a photoresist as a contrast enhancer for realizing high resolution.

[0021]

Next, the present invention will be described more specifically with reference to examples. The present invention is not limited by these examples.

Example 1 (1) Preparation of Tris (2-carboxyethyl) isocyanurate Derivative A Solution Tris (2-carboxyethyl) isocyanurate was placed in a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer. 345.3 parts by weight, n-propyl vinyl ether 25
8.4 parts by weight, 134.7 parts by weight of trimethyl phosphate, A
0.26 parts by weight of P-8 (produced by Daihachi Chemical Industry Co., Ltd., phosphoric acid catalyst, acidic phosphoric acid ester) was charged and stirred at 50 ° C. The reaction was terminated when the acid value of the mixture became 5 or less, and a solution of tris (2-carboxyethyl) isocyanurate derivative A having an effective content of 46.7% by weight was obtained.

(2) Tris (2-carboxyethyl) i
Purification of Socyanurate Derivative A Tris (2-carboxyethyl) obtained by the above method
50.0 parts by weight of the isocyanurate derivative A solution was
Sun / toluene (weight ratio = 7/3) mixed solution 100.0
Parts by weight and then ice-cooled 5% by weight aqueous sodium carbonate
The solution was washed 5 times with 200.0 parts by weight. Next, sulfuric acid
After drying the organic layer with gnesium, it was concentrated under reduced pressure at a bath temperature of 35 ° C.
did. Furthermore, the residue is dried with a vacuum pump,
Tris (2-carboxyethyl) isocyanurate induction
Body A was obtained. In addition, tris (2-cal
Boxyethyl) isocyanurate and the resulting tris
(2-carboxyethyl) isocyanurate derivative A
The infrared absorption spectrum measurement
The absorption charts shown in FIGS. 1 and 2, respectively, were obtained. This figure
From Tris (2-carboxyethyl) isocyanurate
In the infrared absorption spectrum of the derivative A,
0-3500cm^-1 Due to absorption of nearby carboxyl groups
Since the peaks disappeared, it is expressed by equation (5).
Tris (2-carboxyethyl) isocyanurate
It can be seen that the derivative A was obtained.

[0024]

Embedded image

Example 2 10 g of the tris (2-carboxyethyl) isocyanurate derivative A obtained in Example 1 and 90 g of an organic solvent, and 10 g of the isocyanurate derivative A and 9.86 g of a bisphenol A type epoxy resin were collected in a glass bottle. Stir well. By further observing the state after standing for 3 hours, the solubility of the tris (2-carboxyethyl) isocyanurate derivative A obtained in the example in an organic solvent and the compatibility with a bisphenol A type epoxy resin were examined. Table 1 shows the results. Also, a tris (2-carboxyethyl) isocyanurate derivative as a curing agent and an epicoat 828 of a bisphenol A type epoxy resin are used.
Are mixed so that the molar ratio of the former carboxyl group to the latter epoxy group is 0.9: 1, and zinc octylate is used as a catalyst in an amount of 0 to 100 parts by weight of the curing agent and the total nonvolatile components of the resin. .16 parts by weight were added and mixed to prepare a coating composition. This paint is applied to a glass plate with a dry coating thickness of 30
It was applied by air spray to a thickness of μm, baked at 150 ° C. for 30 minutes, and cured. The characteristics of the obtained coating film were examined. Table 1 shows the results.

Comparative Example 1 The procedure of Example 2 was repeated, except that the tris (2-carboxyethyl) isocyanurate used as a starting material in Example 1 was used instead of the tris (2-carboxyethyl) isocyanurate derivative A. In the same manner as in Example 2, the solubility, compatibility and coating film properties were examined. Table 1 shows the results.

[0027]

[Table 1]

Notes on Table 1 (* 1) Compatibility was evaluated according to the following criteria. ：: Uniform solution ×: Insoluble (* 2) Bisphenol A type epoxy resin solution (trade name of Yuka Shell Epoxy Co., Ltd.)

From the results in Table 1, all of the tris (2-carboxyethyl) isocyanurate derivatives obtained in the examples have excellent solubility in organic solvents and resins as compared with the raw material tris (2-carboxyethyl) isocyanurate. You can see that it is. In addition, a uniform coating film was obtained with respect to the coating film characteristics, and sufficient hardness was also obtained.

[0030]

Industrial Applicability The novel tris (2-carboxyethyl) isocyanurate derivative of the present invention has excellent solubility in general organic solvents and compatibility with various resins. Achieves high resolution as a cured product excellent in weather resistance, for example, a thermosetting composition suitably used for paints, inks, adhesives, molded articles, etc., particularly a one-pack type thermosetting composition, and a photoresist. It is possible to provide a contrast-enhancing agent.

[0031]

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum chart of tris (2-carboxyethyl) isocyanurate used in Example 1.

FIG. 2 is an infrared absorption spectrum chart of a tris (2-carboxyethyl) isocyanurate derivative obtained in Example 1 (2).

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CG001 CG002 DA001 DA002 DB001 DB002 DB061 DB062 DB221 DB222 DE001 DE002 DF001 DF002 DG231 DG232 DL001 DL002 EA011 EA012 JB36 JC02 KA03

Claims (1)

[Claims] [Claim 1] The following general formula (1) (Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic group having 1 to 18 carbon atoms, and R ³ and R ⁴ are bonded to each other. To form a heterocyclic ring having Y ¹ as a hetero atom, wherein Y ¹ is an oxygen atom or a sulfur atom. (Carboxyethyl) isocyanurate derivative.