Light- or heat-curing method and curable resin composition

Patent metadata

Field	Value
Publication number	US-11548984-B2
Application number	US-201816622132-A
Country	US
Kind code	B2
Filing date	Jun 12, 2018
Priority date	Jun 12, 2017
Publication date	Jan 10, 2023
Grant date	Jan 10, 2023

Abstract

An object of the present invention is to provide a light- or heat-curing method by which a cured product (crosslinked product or resin) can be prepared in a simple method even in a case where filler is contained in a large amount; a curable resin composition which is used in the curing method; and the like.
The present invention provides a light- or heat-curing method containing a step 1 of obtaining (E) a condensate having constitutional units of Si—O—Al and/or Si—O—Si, obtained from aluminum derived from an aluminum alkoxide and a silane derived from a silane coupling agent having a mercapto group, from (A) a compound that is formed of a salt of a carboxylic acid and an amine and has a carbonyl group generating a radical and a carboxylate group generating a base through decarboxylation by irradiation with light or heating, the (B) aluminum alkoxide, the (C) silane coupling agent having a mercapto group, and (D) water, and a step 2 of performing a reaction among the (E) condensate, (H) a compound having two or more polymerizable unsaturated groups, and (I) filler under the conditions of irradiation with light or heating in the presence of the (A) compound; a curable resin composition which is used in the curing method; and the like.

First claim

The invention claimed is:

1. A light- or heat-curing method comprising:
a step 1 of obtaining (E) a condensate having constitutional units of Si—O—Al and optionally Si—O—Si, obtained from aluminum derived from an aluminum alkoxide and a silane derived from a silane coupling agent having a mercapto group, from (A) a compound that is formed of a salt of a carboxylic acid and an amine and has a carbonyl group generating a radical and a carboxylate group generating a base through decarboxylation by irradiation with light or heating, the (B) aluminum alkoxide, the (C) silane coupling agent having a mercapto group, and (D) water; and
a step 2 of performing a reaction among the (E) condensate, (H) a compound having two or more polymerizable unsaturated groups, and (I) filler under the conditions of irradiation with light or heating in the presence of the (A) compound.

2. A light- or heat-curing method comprising:
a step 1 of obtaining (E) a sol by performing a reaction among (A) a compound that is formed of a salt of a carboxylic acid and an amine and has a carbonyl group generating a radical and a carboxylate group generating a base through decarboxylation by irradiation with light or heating, (B) an aluminum alkoxide, (C) a silane coupling agent having a mercapto group, and (D) water; and
a step 2 of obtaining a cured product from the (E) sol, (H) a compound having two or more polymerizable unsaturated groups, and (I) filler by irradiation with light or heating in the presence of the (A) compound.

3. The curing method according to claim 1 , wherein the step 1 is a step of obtaining (E) a condensate having constitutional units of Si—O—Al and optionally Si—O—Si, obtaining (E) a condensate having constitutional units of Si—O—Al and/or Si—O—Si, obtained from aluminum derived from an aluminum alkoxide and a silane derived from a silane coupling agent having a mercapto group, from the (A) compound, the (B) aluminum alkoxide, the (C) silane coupling agent, (D) water, and (F) a chelating agent.

4. The curing method according to claim 2 , wherein the step 1 is a step of obtaining (E) a sol by performing a reaction among the (A) compound, the (B) aluminum alkoxide, the (C) silane coupling agent, (D) water, and (F) a chelating agent.

5. The curing method according to claim 1 , wherein the step 2 is a step of performing a reaction among the (E) condensate, the (H) compound having two or more polymerizable unsaturated groups, (I) filler, and (J) a compound having two or more epoxy groups under the conditions of irradiation with light or heating in the presence of the (A) compound.

6. The curing method according to claim 2 , wherein the step 2 is a step of obtaining a cured product from the (E) sol, the (H) compound having two or more polymerizable unsaturated groups, (I) filler, and (J) a compound having two or more epoxy groups by irradiation with light or heating in the presence of the (A) compound.

7. The curing method according to claim 1 , wherein the (A) compound is represented by the general formula [1],

in the formula [1], R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a nitro group, or a group represented by the general formula [2], R 9 and R 10 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, or a nitro group, or R 9 and R 10 are bonded to each other through an oxygen atom, a sulfur atom, or a carbonyl group, provided that at least one of groups represented by R 1 to R 8 represents a group represented by the general formula [2],

in the formula [2], R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms and Z 1 + represents an amidinium cation, a guanidinium cation, or a biguanidinium cation.

8. The curing method according to claim 1 , wherein the (B) aluminum alkoxide is represented by the general formula [6],
Al(OR 32 ) 3   [6]

in the formula [6], three R 32 's each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that at least one of groups represented by R 32 represents an alkyl group having 1 to 4 carbon atoms.

9. The curing method according to claim 1 , wherein the (B) aluminum alkoxide is aluminum tri-sec-butoxide.

10. The curing method according to claim 1 or 2 , wherein the (C) silane coupling agent is represented by the general formula [7],
(R 33 ) 3 Si—R 34   [7]

in the formula [7], three R 33 's each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, R 34 represents an alkyl group having 1 to 8 carbon atoms, which has at least one mercapto group, provided that at least one of groups represented by R 33 represents an alkoxy group having 1 to 4 carbon atoms.

11. The curing method according to claim 1 , wherein the (C) silane coupling agent is selected from (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, and 3-mercaptopropyl(dimethoxy)methylsilane.

12. The curing method according to claim 1 , wherein a ratio of the molar ratios of the (B) aluminum alkoxide and the (C) silane coupling agent is 1:10 to 9:1.

13. The curing method according to claim 3 , wherein the (F) chelating agent is selected from methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, 2-(2-thioxanthenyl)diethyl malonic acid, acetylacetone, diacetone alcohol, and ethyl lactate.

14. The curing method according to claim 1 , wherein (I) filler is thermally conductive filler.

15. The curing method according to claim 14 , wherein the thermally conductive filler is aluminum nitride.

16. A curable resin composition comprising:
(A) a compound that is formed of a salt of a carboxylic acid and an amine and has a carbonyl group generating a radical and a carboxylate group generating a base through decarboxylation by irradiation with light or heating;
(B) an aluminum alkoxide;
(C) a silane coupling agent having a mercapto group;
(H) a compound having two or more polymerizable unsaturated groups; and
(I) filler.

17. A curable resin composition comprising:
(A) a compound that is formed of a salt of a carboxylic acid and an amine and has a carbonyl group generating a radical and a carboxylate group generating a base through decarboxylation by irradiation with light or heating;
(E) a condensate having constitutional units of Si—O—Al and optionally Si—O—Si, obtained from aluminum derived from an aluminum alkoxide and a silane derived from a silane coupling agent having a mercapto group;
(H) a compound having two or more polymerizable unsaturated groups; and
(I) filler.

18. The resin composition according to claim 16 , further comprising: (J) a compound having two or more epoxy groups.

19. A thermally conductive substrate for forming an electronic circuit, comprising:
a cured product obtained from the curable resin composition according to claim 16 .

20. A method for prep

Assignees

• Fujifilm Wako Pure Chemical Corp

Inventors

• Nakano Tadashi
• Sakai Nobuhiko
• YANABA Kosuke
• Imazeki Shigeaki

Classifications

• C08G75/045 Primary

  from mercapto compounds and unsaturated compounds · CPC title

• C08K2003/282

  Binary compounds of nitrogen with aluminium · CPC title

• C08F2/44 Primary

  Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers · CPC title

• C09K5/14

  Solid materials, e.g. powdery or granular · CPC title

• C08K5/0025

  Crosslinking or vulcanising agents; including accelerators · CPC title