Fine powder-coated amine and composition containing same

Abstract

This invention relates to a fine powder-coated amine comprising a solid amine having a melting point equal to or higher than 50 C. and a mean particle size equal to or smaller than 20 m. The fine powder-coated amine has an amount of heat in the second absorption peak measured by a differential scanning calorimeter equal to or less than 220 J/g, and the surface of the solid amine is coated with fine powder having a mean particle size equal to or smaller than 2 m.

Claims

1. A fine powder-coated amine comprising a solid amine having a melting point equal to or higher than 50 C. and a mean particle size equal to or smaller than 20 m, wherein the fine powder-coated amine has an amount of heat in the second absorption peak measured by a differential scanning calorimeter equal to or less than 220 J/g, and the surface of the solid amine is coated with fine particles having a mean particle size equal to or smaller than 2 m.

2. The fine powder-coated amine according to claim 1, wherein the solid amine is an aromatic or aliphatic amine compound.

3. The fine powder-coated amine according to claim 1, wherein the solid amine has a mean particle size of 1 m to 20 m.

4. The fine powder-coated amine according to claim 1, wherein a weight ratio of the solid amine to the fine particles is from 1/0.001 to 1/0.5.

5. The fine powder-coated amine according to claim 1, wherein the fine particles are at least one selected from the group consisting of a polyvinyl chloride, titanium oxide, calcium carbonate, clay, carbon, alumina, talc, zinc oxide and silica.

6. A one-pack heat curable composition comprising the fine powder-coated amine according to claim 1.

7. The one-pack heat curable composition according to claim 6, comprising an isocyanate component.

Description

EXAMPLES

(1) [Second Absorption Peak Heat Amount]

(2) The second absorption peak heat amount was measured by using a differential scanning calorimeter (DSC). As the DSC, model Q2000 DSC manufactured by TA Instruments Japan Inc. was used. According to the temperature program, the temperature was increased from the room temperature to 200 C. at a rate of 5 C./min and the measurement of the second absorption peak was conducted during the increase of the temperature.

(3) [Mean Particle Size]

(4) To measure the particle size and the particle size distribution of the solid amine particles and the fine particles, a laser diffraction-scattering particle size distribution measuring apparatus LA-950V2 manufactured by Horiba Ltd., was used and the measurement was conducted according to a dry method. The particle size with which the resulting passing substance cumulative distribution was 50% was taken as the mean particle size.

(5) [Breaking Strength]

(6) The compositions under test were applied with a thickness of 2 mm onto a release coated paper sheet, and were heated at 100 C. for 10 minutes to be cured. The breaking strength thereof was thereafter obtained according to JIS K 6251 Vulcanized Rubber and Thermoplastic Rubber-How to Acquire Value of Tensile Property and the measurement result was judged according to the following criteria.

(7) : Breaking strength equal to or higher than 2 MPa

(8) x: Breaking strength lower than 2 MPa

(9) [Tackiness]

(10) The compositions under test were each applied with a thickness of 2 mm onto a release coated paper sheet, and were each heated at 100 C. for 10 minutes to be cured. The state of the surface of each hardened material was checked by digital examination and was evaluated according to the following criteria.

(11) : No component of the hardened material adhered to the finger.

(12) x: A component of the hardened material adhered to the finger.

(13) [Reactive Property]

(14) To evaluate the hardenability of the one-pack type heat curable composition, presence or absence of an absorption peak (2,260 cm.sup.1) of the isocyanate group remaining in the one-pack type heat curable composition after the curing was checked using an FT-IR (Nicolet iS10 manufactured by Thermo Fisher Scientific K.K.).

Example 1 (Production of Fine Particles-Coated Amine According to Present Invention)

(15) A solid amine (76.9 g of 1,12-dodecanediamine whose melting point was 71 C.) and 23.1 g of titanium oxide fine particles having a mean particle size of about 0.02 m were put in a jet mill in an atmosphere whose temperature was 29 C. and whose relative humidity was 69% to conduct pulverizing and coating for the content. The solid amine was pulverized to particles having a mean particle size of 13 m. A fine particles-coated amine having a second absorption peak heat amount of 71 J/g was obtained.

Example 2 (Production of Fine Particles-Coated Amine According to Present Invention)

(16) A solid amine (76.9 g of 1,12-dodecanediamine whose melting point was 71 C.) and 23.1 g of titanium oxide fine particles having a mean particle size of about 0.02 m were put in a jet mill in an atmosphere whose temperature was 28 C. and whose relative humidity was 65% to conduct pulverizing and coating for the content. The solid amine was pulverized to particles having a mean particle size of 8 m. A fine particles-coated amine having a second absorption peak heat amount of 120 J/g was acquired.

Example 3 (Production of Fine Particles-Coated Amine According to Present Invention)

(17) 76.9 g of a solid amine (1,12-dodecanediamine whose melting point was 71 C.) was put in a jet mill (a counter jet mill manufactured by Hosokawa Micron Corporation) in an atmosphere whose temperature was 28 C. and whose relative humidity was 68% to be pulverized to particles having a mean particle size of 4 m. The pulverized solid amine particles and 23.1 g of titanium oxide fine particles having a mean particle size of about 0.02 m were put in a Henschel mixer (a model FM20 manufactured by Nippon Coke Co., Ltd.). After mixing the components with each other for 5 minutes, a fine particles-coated amine was obtained. The second absorption peak heat amount of the obtained fine particles-coated amine was 187 J/g.

Example 4 (Production of Fine Particles-Coated Amine According to Present Invention)

(18) A solid amine (76.9 g of 1,12-dodecanediamine whose melting point was 71 C.) and 23.1 g of titanium oxide fine particles having a mean particle size of about 0.02 m were put in a jet mill in an atmosphere whose temperature was 23 C. and whose relative humidity was 63% to conduct pulverizing and coating for the content. The solid amine was pulverized to particles having a mean particle size of 5 m. A fine particles-coated amine having a second absorption peak heat amount of 120 J/g was acquired.

Example 5 (Production of Fine Particles-Coated Amine According to Present Invention)

(19) A solid amine (76.9 g of 1,12-dodecanediamine whose melting point was 71 C.) and 23.1 g of titanium oxide fine particles having a mean particle size of about 0.02 m were put in a jet mill in an atmosphere whose temperature was 25 C. and whose relative humidity was 63% to conduct pulverizing and coating for the content. The solid amine was pulverized to particles having a mean particle size of 15 m. A fine particles-coated amine having a second absorption peak heat amount of 37 J/g was obtained.

Example 6 (Production of Fine Particles-Coated Amine According to Present Invention)

(20) A solid amine (76.9 g of 1,12-dodecanediamine whose melting point was 71 C.) and 23.1 g of titanium oxide fine particles having a mean particle size of about 0.02 m were put in a jet mill in an atmosphere whose temperature was 15 C. and whose relative humidity was 52% to conduct pulverizing and coating for the content. The solid amine was pulverized to particles having the mean particle size of 4 m. A fine particles-coated amine whose second absorption peak heat amount was 63 J/g was obtained.

Example 7 (Production of Fine Particles-Coated Amine According to Present Invention)

(21) A solid amine (76.9 g of 1,12-dodecanediamine whose melting point was 71 C.) and 23.1 g of titanium oxide fine particles having a mean particle size of about 0.02 m were put in a jet mill in an atmosphere whose temperature was 28 C. and whose relative humidity was 72% to conduct pulverizing and coating for the content. The solid amine was pulverized to particles having the mean particle size of 10 m. A fine particles-coated amine having a second absorption peak heat amount of 209 J/g was obtained.

Comparative Example 1 (Production of Fine Particles-Coated Amine not According to Present Invention)

(22) 76.9 g of a solid amine (1,12-dodecanediamine whose melting point was 71 C.) and 23.1 g of titanium oxide fine particles having a mean particle size of about 0.02 m were put in a jet mill in an atmosphere whose temperature was 35 C. and whose relative humidity was 85% to conduct pulverizing and coating for the content. The solid amine was pulverized to particles having the mean particle size of 15 m. A fine particles-coated amine having a second absorption peak heat amount of 263 J/g was obtained.

Comparative Example 2 (Production of Fine Particles-Coated Amine not According to Present Invention)

(23) 76.9 g of a solid amine (1,12-dodecanediamine whose melting point was 71 C.) was put in a jet mill (a counter jet mill manufactured by Hosokawa Micron Corporation) in an atmosphere whose temperature was 32 C. and whose relative humidity was 73% to be pulverized to particles having a mean particle size of 5 m. The pulverized solid amine particles and 23.1 g of titanium oxide fine particles having a mean particle size of about 0.02 m were put in a Henschel mixer (a model FM20 manufactured by Nippon Coke Co., Ltd.) to be mixed with each other for 5 minutes to obtain a fine particles-coated amine. The second absorption peak heat amount of the obtained fine particles-coated amine was 374 J/g.

Comparative Example 3 (Production of Fine Particles-Coated Amine not According to Present Invention)

(24) A solid amine (76.9 g of 1,12-dodecanediamine whose melting point was 71 C.) and 23.1 g of titanium oxide fine particles having the mean particle size of about 0.02 m were put in a jet mill in an atmosphere whose temperature was 31 C. and whose relative humidity was 71% to conduct pulverizing and coating for the content. The solid amine was pulverized to particles having a mean particle size of 4 m. A fine particles-coated amine having a second absorption peak heat amount of 275 J/g was obtained.

Examples 8 to 14 (Production of One-Pack Type Heat Curable Composition According to Present Invention) and Comparative Examples 4 to 6 (Production of One-Pack Type Heat Curable Composition not According to Present Invention)

(25) The components having each of the compositions shown in Table 1 below were mixed and dispersed at the room temperature using a mixing stirrer to obtain a one-pack type heat curable composition. The obtained one-pack type heat curable composition was cured at 100 C. for 10 minutes. The breaking strength, the tackiness, and the reactive property of the one-pack type heat curable composition after the curing were evaluated according to the above evaluation methods. The result is shown in Table 2.

(26) TABLE-US-00001 TABLE 1 Example Example Example Example 8 Example 9 10 11 12 Fine Particles- 9.1 Coated Amine 1 Fine Particles- 9.1 Coated Amine 2 Fine Particles- 9.1 Coated Amine 3 Fine Particles- 9.1 Coated Amine 4 Fine Particles- 9.1 Coated Amine 5 Fine Particles- Coated Amine 6 Fine Particles- Coated Amine 7 Fine Particles- Coated Amine 8 Fine Particles- Coated Amine 9 Fine Particles- Coated Amine 10 Isocyanate 90.9 90.9 90.9 90.9 90.9 Component Example Example Comparative Comparative Comparative 13 14 Example 4 Example 5 Example 6 Fine Particles- Coated Amine 1 Fine Particles- Coated Amine 2 Fine Particles- Coated Amine 3 Fine Particles- Coated Amine 4 Fine Particles- Coated Amine 5 Fine Particles- 9.1 Coated Amine 6 Fine Particles- 9.1 Coated Amine 7 Fine Particles- 9.1 Coated Amine 8 Fine Particles- 9.1 Coated Amine 9 Fine Particles- 9.1 Coated Amine 10 Isocyanate 90.9 90.9 90.9 90.9 90.9 Component Unit: Parts by weight
[Fine Particles-Coated Amines 1 to 7]

(27) The fine particles-coated amines 1 to 7 were the fine particles-coated amines respectively obtained in Examples 1 to 7.

(28) [Fine Particles-Coated Amines 8 to 10]

(29) The fine particles-coated amines 8 to 10 were the fine particles-coated amines respectively obtained in Comparative Examples 1 to 3.

(30) [Isocyanate Component]

(31) A terminal NCO prepolymer having a terminal NCO content rate of 3.5% and a viscosity of 20,000 mPa.Math.s at 20 C. The terminal NCO prepolymer was obtained by reacting 79.3 g of polyether polyol having an average molecular weight of 2,000 (Excenol 2020 produced by Asahi Glass Co., Ltd.) and 20.7 g of diphenylmethanediisocyanate with each other at a reaction temperature of 80 C. for 2 hours.

(32) TABLE-US-00002 TABLE 2 Example Example Example Example Example 8 Example 9 10 11 12 13 Mean Particle 13 8 4 5 15 4 Size of Solid Amine Second Absorption 71 120 187 120 37 63 Peak Heat Amount of Fine Particles-Coated Amine (J/g) Breaking Strength Tackiness Absorption at None None None None None None 2,260 cm.sup.1 of FT- IR Example Comparative Comparative Comparative 14 Example 4 Example 5 Example 6 Mean Particle 10 15 5 4 Size of Solid Amine Second Absorption 209 263 374 275 Peak Heat Amount of Fine Particles-Coated Amine (J/g) Breaking Strength x x x Tackiness x x x Absorption at None Present Present Present 2,260 cm.sup.1 of FT- IR

(33) From the result shown in Table 2, as to Examples 8 to 14 each using the fine particles-coated amine of the invention, an excellent breaking strength, excellent tackiness, and an excellent reactive property were obtained after the curing even at a relatively low curing temperature such as 100 C. In contrast, as to Comparative Examples 4 to 6 each using the fine particles-coated amine not according to the present invention, no excellent result was obtained for any one of the breaking strength, the tackiness, and the reactive property after the curing.