JPS61218578A - Novel imidazoline-isocyanuric acid adduct, synthesis of said adduct, and curing of polyepoxy resin containing said adduct as essential component - Google Patents

Abstract

NEW MATERIAL:The imidazoline-isocyanuric acid adduct of formula I (R2 is alkyl or aryl; R4 is H or methyl). EXAMPLE:2-Undecylimidazoline-isocyanuric acid adduct. USE:A hardener for epoxy resin for the production of epoxy resin powder coating having excellent storage stability, insulation property, heat-resistance, low- temperature curability, yellowing resistance and self-extinguishing property, and a cure accelerator or co-hardener of an acid anhydride and dicyandiamide. PREPARATION:The compound of formula I can be produced easily in high yield by reacting isocyanuric acid with imidazoline of formula II in hot water at a molar ratio of about 1:1, and filtering the crystal precipitated by cooling.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a novel imidazoline isocyanuric acid adduct,
The present invention relates to a method for synthesizing the adduct and a method for curing a polyepoxy resin containing the adduct as an essential component.

The polyepoxy resin powder coating using the compound of the present invention is
It is used as an insulating film for electronic components such as ceramic capacitors, film capacitors, carbon film fixed resistors, varistors, and hybrid ICs, and as an exterior coating for products such as metal plates, metal containers, and metal tubes.

(Prior art) A polyepoxy resin powder coating using an imidacillin compound represented by the following formula as a curing agent has a relatively low curing temperature (120°C
) is known to provide a cured product that can be baked in a short time and is resistant to yellowing (for example, Japanese Patent Publication No. 57-369).
(See Publication No. 45).

(Problems to be Solved by the Invention) However, during storage, the above-mentioned imidacilline compound causes the following side reactions due to the action of moisture in the system or in the outside air. . ] When the monoamide of the corresponding diamine is prepared and is therefore used in formulations such as powder coatings, it has the disadvantage of reducing storage stability and the heat resistance and water resistance of the coating film. Especially in the case of electrically insulating coatings, such drawbacks are extremely disadvantageous.

(Means for Solving the Problems) As a result of intensive research to overcome these drawbacks, the present inventors have found that these drawbacks can be overcome by using the following imidazoline-isocyanuric acid adduct in place of the corresponding imidacillin. found that it can be overcome. Note that this imidazoline/isocyanuric acid adduct is a new compound.

Imidazoline-isocyanuric acid adduct [However, R2 and R4 are as described above. ] Each imidacilline, which is a starting material for the imidazoline-isocyanuric acid adduct (hereinafter referred to as adduct) used in the present invention, is prepared from diamine and nitrile, for example, by Japanese Patent Publication No. 39-249.
65, Japanese Patent Publication No. 42-1548, or West German Published Patent Application No. 3236598.

Similarly, isocyanuric acid is an industrial chemical produced in large quantities by thermal decomposition of urea.

The present inventors have demonstrated that the adduct can be easily produced in high yield by reacting isocyanuric acid and imidacillin in hot water at a molar ratio of 1 or around 1, and then filtering and drying the crystals that precipitate when cold. The present invention was developed based on the discovery that the present invention can be obtained.

The properties of the adduct of the present invention are as follows.

2-ethylimidazoline isocyanuric acid adduct CH,
.

Properties: Colorless crystal Melting point: >250°C TLC (Silica G, ethanol, Iz Total color development: Rf
O,00~0.1O NMR(DzO): δ 3.89. S, 4H (methylene group); 2.56
．． q (J=7.8Hz), 2H (methylene group of ethyl group); 1.21. t(J=7.8Hz), 3H(
Methyl group) M S: m/e 129 (isocyanuric acid), 98 (imidacillin), so-called! I: 1780.1755 (4th absorption), 1725 (1st absorption), 1680, 1612 (2nd absorption), 1580 in the fingerprint area
(3rd absorption), 1476 (5th absorption), 1460
(7th absorption), 1418.1400 (6th absorption)
, 1380.1302.1248.1087.10
72.1053, 979, 870. 760, 6982
- Kundecylimidazoline isocyanuric acid 4-f Additive υ Properties: Colorless crystal Melting point: 172°C (decomposition) TLC (Silica G, ethanol +, h color development): Rf
O, 00-0.15 M S: m/e 224 (imidacillin), 139 (224-C6H13), 129 (isocyanuric acid), 97 (224-C9HI 9), 84
(224-C,.H2°), 43 (-CONH-)ν
First: e# in the fingerprint area! 1735 (6th absorption), 1720.1687.1
695 (7th absorption), 1675 (5th absorption), 1
594 (first absorption), 1480 (second absorption), 1
412 (3rd absorption), 1377 (4th absorption),
13511280. 1242.1189.1164.
1070.1039970, 862, 780, 7
57,712,695.2-Heptadecyl imidazoline/isocyanuric acid Form: Colorless crystal Melting point: 187°C (decomposition) TLC (Silica G, ethanol + RZ photochromic: Rf
O, 00-0.12 M S: m/e 30B (imidacillin), 139,129 (isocyanuric acid) 97.84.4
3. tic' in the two fingerprint areas 1735 (3rd absorption), 1713 (7th absorption)
, 1,690° 1648 (5th absorption) , 1595
(first absorption), 1481 (second absorption), 1413
(4th absorption), 1379 (6th absorption), 1285
．． 1242.1170.1078.975.863,7
82, 758, 712, 6992-ethy3-4-methylimidazoline isocyanuric acid Properties: Colorless crystal Melting point: 220°C (decomposition) TLC (Silica G, ethanol + IZ color development): Rf
O,00~0.12 NMR(DtO): δ4.6~4.1. m, IH; 3.9B, dd
, 18; 3.45°d-d, 18; 2.54. g
, 2)1;1.31. d, 3H; 1.19. t
.

H M S: m/e 129 (Isocyanuric acid), 112 (Imidacillin), 97.83.69 ν/It"'In the fingerprint region 1780.1730 (2nd absorption), 1680 (7th absorption), 1625 ( 3rd absorption'), 1595 (
1st absorption), 1478 (5th absorption), 1460.1
414 (6th absorption), 1380 (4th absorption), 1
280.1245.1110.1070.998.86
5, 835, 775, 760. 7002-7 Enylimidazoline/Isocyanuric Acid Condition: Colorless crystal Melting point: 196°C (decomposed) TLC (Silica G, ethanol + Ig photocoloring: [?f
o, oo ~ 0.12 NMR (DgO): δ 7.8"'7,4.m, 5H; 4.0B, S
, 4H (z tyrene group) M S : ale 146 (purine), 1
29 (ICA), C::2. , 1730 (5th absorption), 1685 (6th absorption) in the fingerprint area
, 1600 (first absorption) , 1570 (second absorption)
, 1482 (4th absorption) , 1415 (7th absorption)
, 1375 (3rd absorption) , 1282.1250.1
184.1033, 875, 838, 785, 6832
-Phenyl-4-methylimidazoline/isocyanuric acid properties: Colorless crystal Melting point: 214°C (decomposition) TLC (Silica G, ethanol, I2 color development): Rf
O, 00~0.22 NMR(DzO): δ 769~7.5. m, 5H; 4.8-4.4.
m, IH (methine group of imidacillin); 4.22. d
-d, IH (methylene group): 3-6ELd-d, IH (
methylene group); 1.50. d, 3H (Mef+c group) M S: ale 160 (imidazolyte)
), 145,132,129 (isocyanuric acid), 1
17.77 KBh, C in the fingerprint area 1775.1730 (3rd absorption), 1685 (6th absorption), 1590 (1st absorption), 1480 (4th absorption), 1410 (5th absorption') , 1392 (
7th absorption), 1373 (2nd absorption), 126B
, 1240.1043.860. 832.78069
5,680 Next, a method for curing a polyepoxy resin containing an adduct as an essential component will be explained in detail.

In the method of the present invention, in addition to using the adduct alone as a curing agent, it can also be used, for example, as a curing accelerator or co-curing agent for acid anhydride or dicyandiamide.

Furthermore, it can accelerate the curing of aliphatic polyamines, aromatic polyamines, amine salts, quaternary ammonium salts, urea, melamine, polycarboxylic acids, addition condensates of phenol and aldehyde, polyhydric phenols, polycarboxylic acid hydrazides, imidazole compounds, etc. It can also be used as an agent or co-curing agent.

When the adduct is used alone as a curing agent, the blending ratio is 5 to 30 phr (i.e., 100 phr of polyepoxy resin).
5 to 30 parts by weight of additives are added to each part by weight)
It is.

When an adduct is used as a curing accelerator or co-curing agent for an acid anhydride, the blending ratio is 85 to 100% of the stoichiometric amount to the acid anhydride polyepoxy resin, and 0.0% of the adduct.
1 to 10 phr. When an adduct of dicyandiamide is used as a curing accelerator or co-curing agent, the blending ratio of dicyandiamide is the same as that of general polyepoxy resins currently commercially available in Japan. Among them, the most desirable are bisphenol A1, bisphenol F1, bisphenol S, and polyglycidyl ether of phenol-formaldehyde resin.

In the method of the present invention, coloring pigments, extender pigments, plasticizers, organic solvents, monoepoxy-based reactive diluents, etc. may be added as required.The following examples illustrate the method of the present invention. Explain.

Example 1 0.1 mol (12.9 g) of isocyanuric acid, 0.1 mol (22.4 g) of 2-undecylimidacillin and 4 mol of water
5 (1 ml of the system consisting of the three components was boiled for about 5 minutes, the homogeneous hot aqueous solution thus obtained was cooled, the precipitated crystals were filtered and dried, and 2-undecylimidazoline-isocyanuric acid adduct 0.09 mole (32.0g yield 90.
5%).

Example 2 A system consisting of 0.1 mol (12.9 g) of isocyanuric acid, 0.1 mol (30.8 g) of 2-heptadecyl imidacillin and 450 mf of water is boiled for about 5 minutes, and thus obtained By cooling the homogeneous hot aqueous solution and filtering and drying the precipitated crystals, 0.096 mol (42°0 g yield of 2-heptadecyl imidazoline isocyanuric acid adduct) was obtained.
5.9%).

Example 3 0.1 mol (12.9 g) of isocyanuric acid, 0.1 mol (14.6 g) of 2-phenylimidacillin and 10 mol of water
ml of the three-part system was boiled for about 5 minutes, the homogeneous hot aqueous solution thus obtained was cooled, and the precipitated crystals were filtered and dried to obtain 14 g of 2-phenylimidazoline isocyanuric acid adduct. 5+ after treating the filtrate with activated carbon
By concentrating to wjt, filtering and drying the precipitated crystals,
An additional 8.5 g of the desired adduct was obtained. Thus, the former and the latter were combined to obtain 0.009 mol (25.1 g, yield 91.3%) of 2-phenylimidazoline isocyanuric acid adduct.

Example 4 A system in which 8 phr of 2-ethyl-4-methylimidazoline/isocyanuric acid adduct was added to Epicote 1004 (trade name, epoxy resin manufactured by Yuka Shell Epoxy KK) was 15
It gelated in 150 seconds on a hot iron plate at 0°C and could be used as a powder coating.

For comparison, the gelation time of a system in which the adduct was replaced with 2-ethyl-4-methylimidacyline was 196 seconds, and the gelation itself only showed storage stability to the extent that it gelled within 14 days at room temperature. Therefore, it was difficult to use it as a powder coating composition.

Example 5 A system in which 8 phr of 2-undecylimidazoline/isocyanuric acid adduct was added to Epicote 1004 gelled in 103 seconds on a hot iron plate at 150° C., and could be used as a powder coating.

For comparison, the gelation time of a system in which the adduct was replaced with 2-undecylimidacillin was 185 seconds, but the irritating odor during heat curing was so pronounced that this system could not be used as a paint. It turned out that.

Example 6 A system in which 12 phr of 2-heptadecyl imidazoline/isocyanuric acid adduct was added to Epicote 1004 was 150
It gelatinized in 140 seconds on a hot iron plate and could be used as a powder coating.

On the other hand, the system in which the adduct was replaced with 2-heptadecyl imidacillin gelled in 200 seconds.

Example 7 A system in which 8 phr of 2-phenylimidazoline-isocyanuric acid adduct was added to Epicote 1004 gelled in 107 seconds on a hot iron plate at 150° C., and could be used as a powder coating.

On the other hand, the system in which the adduct was replaced with 2-phenylimidacillin gelled in 178 seconds.

Example 8 The 150°C gelation time of a system in which 8 phr of 2-phenyl-4-methylimidazoline/isocyanuric acid adduct was added to Epicote 1004 was 112 seconds.

Example 9 The 150°C gelation time of a system in which 17 phr of 2-ethylimidazoline/isocyanuric acid adduct was added to Epicote 1004 was 81 seconds.

Example 10 This example is an example in which a 2-phenylimidazoline/isocyanuric acid adduct is blended into an epoxy resin as a sole curing agent, and by selecting appropriate fillers, pigments, flow control agents, and leveling agents, hot melt Casting material (
Examples of possible applications include E-pellets (an epoxy resin usage form known as Nitto Electric Industry KK product name), powder coatings, etc.

To a polyepoxy compound (trade name: Epicoat 1004, manufactured by Yuka Shell Epoxy KK) that has been ground in advance to a mesh size of 80 or less, a 2-phenylimidazoline isocyanuric acid adduct that has been ground to a mesh size of <150 or less is added, and heated. After passing through a two-roll machine to make a homogeneous system and quenching,
An epoxy powder lacquer was obtained by pulverizing the powder to a size of 80 mesh or less. Storage stability of this lacquer, gelling time (
The results of measuring the hardenability) and the performance of the cured product are shown in the table below.

The physical properties of the coating film were measured using a coating film formed by a fluidized dipping method.

For comparison, an example in which the adduct was replaced with 2-phenylimidacillin is also described.

(Formulation) Comparative Example Epicor) 1004
100 1002-Phenylimidacillin
daily budget
108 108 (Properties of the formulation) Appearance, visual inspection White powder Apparent specific gravity 0.42 0.42 Storage stability, day/25℃ 〉120 Approx. 60 (
Cured coating performance) Curing conditions: 15 minutes at 7150°C appearance,
Visual observation: Light yellow and transparent Same pencil hardness on the left
38 3H engineering Riksen steel ball indentation test, mm >10 >10 ManF
Reel bending test, IIIφ Ku2
2 (cured product performance) Curing conditions: 3
0 min 7150℃ bending strength, kg/mw”
14 14 Flexural modulus, pupil/mm”
320 312 dielectric constant, 5oz
3 3 Breakdown voltage, KV/mm
>20 >20 Volume resistivity, Ω-mouth
> l Q I S > I Q I S Regarding storage stability, the lacquer was stored at 25°C, the change in fluidity was measured, and the end point was when the flow reached the initial level of 172. 1 g of the sample was placed in a tablet molding die with a diameter of lca, and the resulting tablet was placed on a hot iron plate adjusted to 150 ± 0.5°C in advance to catalyze and harden the tablet. Then measure its average diameter,
Expressed as flow rate %.

Flow rate % = (average diameter after curing - 1)
Spread the sample to a size of 30+ am and knead it by evenly pressing the sample back and forth once every 2 hours, then lift the spatula from time to time to measure the time until no thread is drawn between the sample and the spatula. This is what I was looking for.

Example 11 This example is an example of an adhesive formulation in which a 2-ethyl-4-methylimidazoline/isocyanuric acid adduct was used to accelerate the curing of dicyandiamide.

70 parts of polyepoxy compound A (product name: Epicoat 828, manufactured by Yuka Shell KK), 30 parts of polyepoxy compound B (product name: Epicoat 834, same), thixotropy additive (product name: Bentone 38, National Red) (manufactured by Nippon Carbide), 30 parts of an extender pigment (product name: Mantaru P, manufactured by Ueya Kaolin KK), 6 parts of dicyandiamide (manufactured by Nippon Carbide), and 2 parts of the adduct were uniformly kneaded using a three-roll machine and bonded. A drug composition was obtained.

This adhesive has a shelf life of more than 2 months at room temperature and has a shelf life of 120
It cured rapidly by heat treatment at temperatures above ℃ and exhibited strong adhesive strength.

Storage stability, day/25℃〉60 shear adhesive strength, kg/mm” (curing condition 0.5hr/150℃
) Rope-Steel/20℃ 24081-
Al/20℃
105 volume resistivity, Ω-am/20℃
>IQIs breakdown voltage, KV/mm
>20 Example 12 This example is a formulation example of a powder coating using a 2-undecylimidazoline/isocyanuric acid adduct as a sole curing agent and an acid anhydride curing accelerator.

The ingredients listed in the table are melt-kneaded in a two-roll machine preheated to 85-95°C, and the resulting mixture is rapidly cooled, pulverized, and then classified to produce a powder in the range of 80-270 mesh. Obtained as a powder coating for fluidized dipping.

The coating is useful for coating ceramic components such as film resistors, varistors, capacitors, and hybrid ICs.

(Formulation) Epicote 1004 (Note 1)
100 100S H-
6018 (Note 2) 0゜50.52-undacylimidazoline isocyanuric acid (on the verge of 12
1 Trimeliftic anhydride

8 Silica powder (Note 3)
50 80 Iron oxide (Note 4
) 2 2 total
164.5 191 (cured resin properties) Curing conditions, min/150°C 2060 appearance,
Visual observation Red red powder Same as left gelation time, seconds/150℃ 85 216 specific gravity
1,51.8 Heat distortion temperature, ℃
98115 Corner force l (-rate, %
42 45 Volume resistivity, Ω-
cm > IQIs > IQI5 breakdown voltage, KV/mm >20 >
20 dielectric constant, 60Hz/25℃ 3.8
3.2 Note 1: Poly I Zoxy compound, oily shell KK layer 2 = flow control agent, east + shi IJ: I-shi K K layer 3
: Body 1tR material, Crystallite AA Note 42 color pigment manufactured by Kutumori KK, Benga 9R-10 manufactured by Toda Kogyo KK
0 (Effect of the invention) The present invention makes it possible to provide a polyepoxy resin powder coating with excellent storage stability, insulation, heat resistance, water resistance, low-temperature fast curing, non-yellowing, and self-extinguishing properties. Spontaneous) April 2.3, 1985 Patent Application No. 58792 2, Title of Invention: Novel imidazoline-isocyanuric acid adduct, method for synthesizing the adduct, and polyepoxy containing the adduct as an essential component Resin curing method 3, person making the amendment 43 Detailed description of the invention column 5 of the specification to be amended, content of the amendment (1) The structural formula on page 7, line 4 of the specification is amended as shown in the attached sheet. .

(2) The structural formula on page 11, line 7 of the specification is amended as shown in the attached sheet.

Claims (6)

[Claims] (1) General formulas: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas,
There are tables etc.▼ [In the formula, R_2 represents an alkyl group or an aryl group, and R_4 represents a hydrogen atom or a methyl group. ] An imidazoline-isocyanuric acid adduct represented by. (2) Isocyanuric acid and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_2 represents an alkyl group or an aryl group, and R_4 represents a hydrogen atom or a methyl group. ] A general formula characterized by reacting imidazoline shown by in hot water at a molar ratio of 1 or around 1, and then filtering out the crystals that precipitate when cooled: ▲Contains mathematical formulas, chemical formulas, tables, etc. ▼ ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ [In the formula, R_2 and R_4 are the same as above. ] A method for synthesizing an imidazoline-isocyanuric acid adduct. (3) General formulas: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas,
There are tables etc. ▼ [However, in the formula, R_2 is an alkyl group or an aryl group, R
_4 represents a hydrogen atom or a methyl group. ] A method for curing a polyepoxy resin, characterized in that the imidazoline/isocyanuric acid adduct represented by the following is an essential component. (4) A claim in which a system containing 5 to 30 parts by weight of an imidazoline-isocyanuric acid adduct to 100 parts by weight of a polyepoxy resin is cured under heating conditions of 120°C for 60 minutes to 200°C for 5 minutes. The method for curing a polyepoxy resin according to item 3. (5) A system in which 0.1 to 10 parts by weight of an imidazoline-isocyanuric acid adduct and 85 to 100% of the stoichiometric amount of the acid anhydride to the polyepoxy resin is blended into 100 parts by weight of the polyepoxy resin is heated at 150°C. The method for curing a polyepoxy resin according to claim 3, wherein the polyepoxy resin is cured under heating conditions of 60 minutes to 200° C. for 15 minutes. (6) A system in which 0.1 to 10 parts by weight of an imidazoline/isocyanuric acid adduct and 4 to 10 parts by weight of dicyandiamide are blended into 100 parts by weight of a polyepoxy resin is 150 parts by weight.
4. The method of curing a polyepoxy resin according to claim 3, wherein the polyepoxy resin is cured under heating conditions of 30 minutes at 0.degree. C. to 10 minutes at 200.degree.