JP2009292979A - Siloxane compound and curable composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a siloxane compound which is markedly improved in characteristics of heat resistance, solvent resistance, etc., while satisfying basic characteristics such as mechanical strength, is suitably usable as a curable composition formable into a cured product causing less deterioration of various physical properties even under a high temperature environment, especially for an insulation material for a power module, an adhesive for assemblies, an adhesive for aerospace industries, or the like; and a curable composition containing the siloxane compound. <P>SOLUTION: The siloxane compound (I) having an imide bond and a siloxane bond has imide bonds in the molecular skeleton and also at the molecular terminals. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a siloxane compound and a curable composition containing the siloxane compound. More specifically, the present invention relates to a siloxane compound and a curable composition containing a siloxane compound that are useful for insulating materials for power modules, adhesives for assemblies, adhesives for aerospace industry, and the like.

A siloxane compound is a compound having at least one Si-O bond (siloxane bond), including polysiloxane (commonly known as silicone), polysilsesquioxane, etc., and has been widely used as a raw material for various industrial products. Has been. And nowadays, it has been applied to various uses due to the characteristics resulting from the siloxane bond. For example, insulating materials for power modules, adhesives for assembly, and adhesives for aerospace industry can be mentioned. In such applications, trial and error are currently being repeated in order to improve or improve various properties such as the resin used, and siloxane compounds that can exhibit properties resulting from siloxane bonds are also used. The use for is being considered.

With respect to conventional siloxane compounds, novel compounds characterized by having a maleimide group and an alkoxysilyl group via a urethane bond (for example, see Patent Document 1), silanes containing an imide group (for example, Patent Document 2) And triethoxysilylpropyl-1,8-naphthalimide (see, for example, Patent Document 3), a polynadicimide siloxane precursor (see, for example, Patent Document 4), and an ammonium cation on the surface. A rod-shaped polysiloxane having a thickness (for example, see Patent Document 5), a layered polyaminoalkylsiloxane complex (for example, see Patent Document 6), and the like have been developed. However, it is excellent in various performances, and it can exhibit further sufficient performance in heat resistance etc. so that it can be suitably used in fields where development is strongly demanded such as mounting applications. There was room for ingenuity.

In insulating materials for power modules, adhesives for assembly, and adhesives for aerospace industry, in addition to improving the performance of products, materials that can withstand use under harsh conditions are required. For this reason, a plastic material having excellent mechanical properties and improved heat resistance and solvent resistance for application to the above-mentioned applications is desired.

Conventionally, epoxy-based materials are generally used in such fields. However, when left for a long time at a high temperature of, for example, 200 ° C. or more, a significant decrease in weight and a decrease in mechanical strength are observed, improving heat resistance. Is required. Engineering plastic materials such as polyimide can also be cited as examples of high heat resistant materials, but handling properties are low and it is difficult to obtain workability similar to that of epoxy, and its usage is limited to flexible substrates. Therefore, it is desired to suppress weight reduction, improve heat resistance and solvent resistance, achieve excellent workability, and be usable in various applications.
Examples of organic / inorganic hybrid materials include various polysiloxanes / polysilsesquioxanes or nanocomposite materials. In general, however, the heat resistance cannot be improved sufficiently, or even when excellent heat resistance is exhibited, Since the addition of a noble metal catalyst is necessary, it is expensive and unsuitable for mass consumption applications and the like (for example, see Patent Document 7).
JP 2002-69084 A (2nd and 7th pages) Japanese Patent Laid-Open No. 63-146891 (pages 1 and 9) Special table 2003-502449 gazette (2nd page) JP-A-9-279034 (page 5) JP 2006-45392 A (2nd and 7th pages) JP 2005-120333 A (pages 2, 3, 12) JP 2006-73950 A (pages 2-4 and 7)

The present invention has been made in view of the above-mentioned present situation, and has properties such as heat resistance and solvent resistance that have been remarkably improved while sufficiently improving mechanical properties. As a curable composition capable of forming a cured product with low physical property degradation, in particular, a siloxane compound that can be suitably used for an insulating material for power modules, an adhesive for assembly, an adhesive for aerospace industry, and the like, and The object is to provide a curable composition containing such a siloxane compound.

As a result of various studies on the siloxane compound (I) capable of exhibiting the above-described properties, the present inventors have found that the basic performance such as mechanical strength is sufficient when the siloxane compound (I) has an imide bond. It was found that it was possible to demonstrate excellent heat resistance. Further, when the siloxane compound (I) has an imide bond in the molecular skeleton and at the molecular end, the basic performance is sufficient, and the characteristics such as heat resistance and solvent resistance are further remarkable. The curable composition containing the siloxane compound (I) can be found to form a cured product having a low decrease in various physical properties even under a high temperature environment, and the above-mentioned problems can be solved brilliantly. Thus, the present invention has been achieved. Such curable compositions are used in various applications that require the above-described properties, in particular, insulating materials for power modules such as converters, inverters, hybrid ICs, membrane switches, component potting agents, encap agents, sealants, The present invention can be suitably applied to adhesives for assembly such as substrate coating agents and shock absorbers, adhesives for aerospace industries such as wire sealants and engine gasket agents.

That is, the present invention provides a siloxane compound (I) having an imide bond and a siloxane bond, wherein the siloxane compound (I) has an imide bond in a molecular skeleton and at a molecular end. It is.
This invention is also a curable composition containing the siloxane compound (I) mentioned above, Comprising: The said curable composition is also a curable composition containing a crosslinking agent.
The present invention is described in detail below.

The siloxane compound (I) of the present invention has an imide bond in the molecular skeleton and at the molecular end.
By setting the siloxane compound (I) of the present invention to have such a specific imide bond, the curable composition containing the siloxane compound (I) of the present invention has sufficient basic performance such as mechanical strength. Therefore, the properties such as heat resistance and solvent resistance are remarkably improved, and a cured product in which various physical properties are hardly deteriorated even in a high temperature environment can be formed. This is an essential feature of the present invention in that the siloxane compound (I) has not only one of the imide bond in the molecular skeleton and the imide bond at the molecular end but both of them. Thus, it is considered that the above two types of imide bonds act synergistically to exert a remarkably excellent effect.

The siloxane compound (I) is represented by the following formula (1);

(In the formula, R ¹ is the same or different and represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ² is the same or different and represents a divalent hydrocarbon group having 1 to 20 carbon atoms. R ³ is the same or different and represents a skeleton having at least one structure selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and R ⁴ is the same or different and represents a polymerizable unsaturated bond. Or represents a structure of a heterocyclic ring and / or an alicyclic ring having a polymerizable unsaturated bond, and may have a substituent, and m and n are the same or different and are integers of 1 to 200). It is preferably represented.
Thereby, it is possible to further improve characteristics such as heat resistance and solvent resistance while making basic performance such as mechanical strength sufficient.

R ¹ is preferably a methyl group, an ethyl group, a propyl group, or a phenyl group.
R ² is preferably a divalent hydrocarbon group having 2 to 6 carbon atoms. More preferably, they are a methylene group or a phenyl group.

R ³ is more preferably a skeleton having an aromatic ring. The skeleton may contain a silicon atom or an oxygen atom.
Specifically, a skeleton derived from an acid anhydride in a reaction for introducing an amic acid structure described later is preferable. More preferably, it is a skeleton derived from an acid anhydride having a skeleton having an aromatic ring described later.
R ⁴ is more preferably a polymerizable unsaturated bond. More preferably, it has a carbon-carbon double bond.
Specifically, a bond derived from maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, tetrahydrophthalic anhydride, and phenylethynyl phthalic anhydride is preferable. In other words, it is preferably a bond derived from at least one selected from the group consisting of maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, tetrahydrophthalic anhydride and phenylethynyl phthalic anhydride. Particularly preferred is a bond derived from maleic anhydride.

The above “skeleton derived from acid anhydride” and “bond derived from maleic anhydride” are formed when a skeleton formed using acid anhydride as a raw material or maleic anhydride is used. However, any structure may be used as long as it is recognized as a structure derived from a skeleton derived from an acid anhydride or a bond derived from a maleic anhydride in the technical field of the present invention. The same applies to compounds other than maleic anhydride.
The siloxane compound (I) is reactive due to the unsaturated bond in R ⁴ .
The n is preferably 1-30. More preferably, it is 1-20, More preferably, it is 1-12. When n exceeds 12, the chemical resistance and the adhesion with the bonded portion may be lowered.

The siloxane compound (I) preferably has a weight average molecular weight of 1000 to 40000. More preferably, it is 2000-4000.
The weight average molecular weight can be measured by gel permeation chromatography (GPC).
For example, the following measurement conditions are preferable.
Column used: Shodex GF-7MHQ (trade name, manufactured by Showa Denko) 2 eluents: DMF (dimethylformamide)
Flow rate: 0.6 ml / min.
Column temperature: 40 ° C
Standard material: polystyrene detector: RI (differential refractive index) detector implantation amount: 10 μL with 0.5 wt% solution

The siloxane compound (I) of the present invention can be produced, for example, by a reaction for introducing an amic acid structure into a siloxane compound containing an amino group and a reaction for forming an organic skeleton having an imide bond.
The reaction for introducing the amic acid structure is, for example, a ring-opening addition reaction of an acid anhydride to a siloxane compound containing an amino group. The reaction for forming an organic skeleton having an imide bond is a reaction for forming an imide bond from the introduced amic acid structure by a dehydration reaction.
The reaction for introducing the amic acid structure and the reaction for forming an organic skeleton having an imide bond may be carried out, for example, as separate steps, or in a form carried out successively in the same system. It is also possible (substantially including two reactions proceeding in time series under a predetermined condition).
In the reaction for introducing the amic acid structure, since the yield of the target compound is reduced due to the hydration of the acid anhydride, the solvent and the reaction apparatus are well dried, and dry nitrogen gas is used during the reaction. The method of circulating is preferable. The solvent may be dried using a publicly known dehydrating agent such as molecular sieve, anhydrous magnesium sulfate, or anhydrous calcium chloride, or may be subjected to distillation before the reaction.
As the siloxane compound containing an amino group, a siloxane compound containing an amino group at both ends is preferable, and examples thereof include an aminoalkyl group both-end dialkylsiloxane oligomer. Specifically, for example, ω, ω′-bis (2-aminoethyl) polydimethylsiloxane, ω, ω′-bis (3-aminopropyl) polydimethylsiloxane, ω, ω′-bis (4-aminophenyl). Examples include polydimethylsiloxane, ω, ω′-bis (3-aminopropyl) polydiphenylsiloxane, and ω, ω′-bis (3-aminopropyl) polymethylphenylsiloxane. These may be used alone or in combination of two or more.

A publicly known aromatic diamine may be used in combination with the siloxane compound containing the amino group.
Examples of the aromatic diamine include 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, and 2,4-diamino. Mesitylene, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylene-2,6-diethylaniline, 2,4-toluenediamine, m-phenylene -Diamine, p-phenylene-diamine, 4,4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, 4,4'-diamino-diphenylethane, 3,3'-diamino-diphenylethane, 4, , 4'-diamino-diphenylmethane, 3,3'-diamino-diphenylmethane, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 4,4'-diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, 4,4'-diamino -Diphenyl ether, 3,3'-diamino-diphenyl ether, benzidine, 3,3'-diamino-biphenyl, 3,3'-dimethyl-4,4'-diamino-biphenyl, 3,3'-dimethoxy-benzidine, 4, 4′-diamino-p-terphenyl, 3,3′-diamino-p-terphenyl, bis (p-amino-cyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p -Β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-amino-pentyl) benzene, p-bi (1,1-dimethyl-5-amino-pentyl) benzene, 1,5-diamino-naphthalene, 2,6-diamino-naphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4 -Diamino-toluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylene-diamine, p-xylylene-diamine, 2,6-diamino-pyridine, 2,5-diamino -Pyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, 1,3-bis (3-aminophenoxy) benzene and the like are exemplified, but not limited thereto.

The acid anhydride is preferably an acid anhydride having a skeleton having an aromatic ring, a skeleton having a heterocyclic ring, or a skeleton having an alicyclic ring. In other words, an acid anhydride having a skeleton having an aromatic ring, an acid anhydride having a skeleton having a heterocyclic ring, or an acid anhydride having a skeleton having an alicyclic ring is preferable.

Examples of the acid anhydride having a skeleton having an aromatic ring include 3,3′-4,4′-diphenylsulfonetetracarboxylic dianhydride and 3,4-3 ′, 4′-biphenyltetracarboxylic dianhydride. , Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1 , 2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4, 8-Dimethyl-1,2 3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene -2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5 , 8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2 , 3,6,7-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyltetracarboxylic dianhydride, 3,3 ′ , 4,4 ″ -p-terphenyltetracarboxylic dianhydride, 2,2 ″, 3,3 ″ -p-terphenyltetracarboxylic dianhydride, 2,3,3 ″, 4 ″ ″ -P-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane Dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis ( 2,3-dicarboxyl Enyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9 , 10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2, 7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, 4,4'- Examples thereof include oxydiphthalic dianhydride.

Examples of the acid anhydride having a skeleton having a heterocyclic ring include pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, and thiophene. Examples include -2,3,4,5-tetracarboxylic dianhydride.
Examples of the acid anhydride having a skeleton having an alicyclic ring include cyclopentane-1,2,3,4-tetracarboxylic dianhydride.
Among these, an acid anhydride having a skeleton having an aromatic ring is preferable.
These acid anhydrides may be used alone or in combination of two or more.

The reaction temperature for introducing the amic acid structure is preferably room temperature to 100 ° C. More preferably, it is 40-90 degreeC. Although the reaction proceeds sufficiently even near room temperature, depending on the reaction product, it may be precipitated during the reaction and stirring of the reaction system may be impossible, so it is preferable to react at a temperature higher than room temperature. The pressure in the above process may be normal temperature, under pressure, or under reduced pressure. The reaction time varies depending on the reaction temperature and reaction composition, but is preferably about 2 to 48 hours.

The reaction for forming the organic skeleton having an imide bond preferably has a reaction temperature of 80 to 300 ° C. More preferably, it is 100-200 degreeC, More preferably, it is 100-150 degreeC, and since water produces | generates as a by-product, it is holding above the azeotropic temperature of water and a solvent. The reaction pressure may be room temperature, under pressure, or under reduced pressure.
As the reaction catalyst, known ring-opening catalysts such as pyridine, triethylamine, imidazole, diazabicycloundecene, tetramethylammonium hydroxide, sulfuric acid, paratoluenesulfonic acid, phosphoric acid, polyphosphoric acid, phosphotungstic acid, etc. It is desirable to add a protic acid or a solvent azeotropically with water such as toluene or xylene.
The reaction time varies depending on the reaction temperature and reaction composition, but is preferably about 2 to 48 hours.

This invention is also a curable composition containing the siloxane compound (I) mentioned above, Comprising: The said curable composition is also a curable composition containing a crosslinking agent.
The crosslinking agent may be any one that is recognized as a crosslinking agent in the technical field of the present invention.
The curable composition of the present invention contains the above-described siloxane compound (I) and further contains a crosslinking agent, so that the basic performance of the curable composition is sufficient and the heat resistance is remarkably excellent. It will be a thing.
In addition, the preferable form of siloxane compound (I) in the curable composition of this invention is the same as the preferable form of siloxane compound (I) of this invention mentioned above.

The crosslinking agent in the curable composition of the present invention is preferably a silane compound having a group capable of reacting with a polymerizable unsaturated bond in the siloxane compound (I). Furthermore, a preferable silane compound is a silane compound having an imide bond and a group capable of reacting with a polymerizable unsaturated bond.
In each of the above embodiments, the silane compound preferably has a main chain skeleton (polysiloxane skeleton) composed of a siloxane bond.
In the silane compound, an organic skeleton having an imide bond or an imide bond and a group capable of undergoing a polymerizable unsaturated bond or a group capable of undergoing a polymerizable unsaturated bond react with at least one silicon atom constituting the main chain skeleton. It is more preferable that the organic skeleton possessed is bonded. The silicon atom to which the organic skeleton having an imide bond or an imide bond is bonded is the same as the silicon atom to which the organic skeleton having a group capable of undergoing a polymerizable unsaturated bond reaction or a group capable of undergoing a polymerizable unsaturated bond is bonded. Or different.
Moreover, the form in which the imide bond and the group capable of reacting with the polymerizable unsaturated bond are included in one organic skeleton (organic skeleton (X)) is preferable.
Accordingly, one particularly preferable form of the silane compound is a silane compound having an organic skeleton (X) having an imide bond and a group capable of reacting with a polymerizable unsaturated bond, and the silane compound is formed from a siloxane bond. The organic skeleton (X) is bonded to at least one silicon atom constituting the main chain skeleton.
As long as the silane compound preferable as a crosslinking agent is a silane compound having an imide bond and a group capable of reacting with a polymerizable unsaturated bond, the type of other bonding groups and the composition of the silane compound are not limited. As the crosslinking agent in the curable composition of the present invention, the following average composition formula (2);
XaYbZcSiOd (2)
(Wherein X is the same or different and represents an organic skeleton having a group capable of reacting with an imide bond and a polymerizable unsaturated bond; Y is the same or different and represents a hydrogen atom, a hydroxyl group, a halogen atom and OR; R represents at least one selected from the group consisting of groups, and R is the same or different and represents at least one group selected from the group consisting of alkyl groups, acyl groups, aryl groups and unsaturated aliphatic residues, Z may be the same or different and represents an organic group that does not have an imide bond, a is a non-zero number of 3 or less, and b is a number of 0 or less than 3. , C is a number less than 0 or 3 and d is a number less than 2 which is not 0 and a + b + c + 2d = 4, and X and Z have a molar ratio of 5/95 to 50/50.) A silane compound (A) represented by It is preferred.
Here, the coefficient a of X is a number satisfying 0 <a ≦ 3. The coefficient b of Y is a number such that 0 ≦ b <3. The coefficient c of Z is a number such that 0 ≦ c <3. The coefficient d of O is 0 <d <2.

As described above, in order to impart heat resistance and the like, it is preferable to use the siloxane compound (I) of the present invention in combination with a crosslinking agent, but it is particularly preferable to use the silane compound (A) as a crosslinking agent. . That is, by using the silane compound (A) as the crosslinking agent in the curable composition, the resulting cured product has an imide structure introduced into the silicone resin skeleton, and the silane compound (A) has a T-type siloxane structure. Since it is introduced, the heat resistance is further improved. In addition, compared with conventional silicone, it can be used in a wider range and in a severe temperature environment.
The T-type siloxane structure means a branched structure in which three are Si—O bonds and one is Si—C.

In addition, since the said silane compound (A) is a crosslinking agent which a crosslinking reaction advances by radical polymerization, a radical polymerization initiator is required. That is, the curable composition of the present invention preferably contains a radical polymerization initiator when the crosslinking agent is the silane compound (A).
As the radical polymerization initiator, organic peroxides and organic azo compounds are preferably used.
Specific examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide, cycloxanone peroxide, and methyl isobutyl ketone peroxide; hydrous such as cumene hydroperoxide and tertiary butyl hydroperoxide. Peroxyesters such as tertiary butyl peroxyoctate and tertiary butyl peroxybenzoate; 1,3-bis (t-butylperoxyisopropyl) benzene, dicumyl peroxide, tris- (tertiary butyl) Dialkyl peroxides such as peroxy) triazine; diacyl peroxides such as isobutyryl peroxide, lauroyl peroxide, benzoyl peroxide; Peroxyketals such as tertiary butyl peroxycyclohexane, 2,2-di- (tertiary butyl peroxy) -butane: tertiary butyl peroxyisopropyl carbonate, bis (4-tertiary butyl cyclohexyl And percarbonates such as peroxydicarbonate and di-3-methoxybutylperoxydicarbonate. Specific examples of the organic azo compound include azobisalkanonitriles such as azobisisobutyronitrile and azobiscarbonamide. These radical polymerization initiators may be used alone or in combination of two or more.

The amount of these radical polymerization initiators used is 0.05 to 15% by mass, preferably 0.1 to 10% by mass, and particularly preferably 0.2 to 5% by mass with respect to 100% by mass of the silane compound (A). % Amount.
Examples of the radical polymerization initiator include organic acid salts of polyvalent metals such as octylate or naphthenate of cobalt, manganese, iron, copper, and other heavy metals, and a third such as dimethylaniline and dimethylparatoluidine if necessary. Addition of small amounts of polymerization accelerators such as secondary amines and polymerization inhibitors such as hydroquinone, naphthoquinone, tertiary butylcatechol, p-benzoquinone, butylated hydroxytoluene, nitroxide radicals, etc. also controls reaction rate and improves pot life Therefore, it can be preferably implemented.

The silane compound (A) is a structural unit in which at least one organic skeleton (X) having a group capable of reacting with an imide bond and a polymerizable unsaturated bond is bonded to a silicon atom (hereinafter referred to as a structural unit (i)). And a siloxane bond. For example, a structure such as a siloxane skeleton, an imide bond, and an organic skeleton (X) having a group capable of reacting with a polymerizable unsaturated bond, the structural unit (i), and the like are appropriately selected to exhibit high compatibility with various polymers. By setting it as a thing, heat resistance etc. can be easily provided to this polymer. A polymer imparted with heat resistance or the like can form a cured product with low deterioration of various physical properties even under a high temperature environment.

In the silane compound (A), “an organic skeleton (X) having a group capable of reacting with an imide bond and a polymerizable unsaturated bond” means an imide bond and a group capable of reacting with a polymerizable unsaturated bond. Any structure may be used as long as it is essential, for example, a structure including an imide structure and an alkylene group having 1 to 6 carbon atoms, a structure including an imide structure and a secondary amino group, and a structure including an imide structure and a tertiary amino group. Etc. are preferred. Among these, a structure containing an imide structure and an alkylene group having 1 to 6 carbon atoms is more preferable in terms of excellent heat resistance and solvent resistance.
The group capable of reacting with the polymerizable unsaturated bond is a reactive group that is essential for reacting with the polymerizable unsaturated bond of the siloxane compound (I) in order for the silane compound (A) to act as a crosslinking agent. is there. The group capable of reacting with the polymerizable unsaturated bond is preferably a polymerizable unsaturated bond.
In the silane compound (A), the proportion of the organic skeleton (X) having a group capable of reacting with the imide bond and the polymerizable unsaturated bond is 100 mol of silicon atoms contained in the silane compound (A). And it is preferable that it is 100-5 mol.
More preferably, it is 10 mol or more, More preferably, it is 15 mol or more, Most preferably, it is 20 mol or more.

The silicon skeleton bonded to the organic skeleton (X) having a group capable of reacting with the imide bond and the polymerizable unsaturated bond is bonded to the organic skeleton (X) and at least one oxygen atom, Siloxane bonds are formed through oxygen atoms. That is, the silicon atom to which the organic skeleton (X) is bonded is bonded to the organic skeleton (X), the oxygen atom, and optionally other skeleton, and the organic skeleton (X), the oxygen atom, and the other skeleton. The total number of bonds is 4.

The silane compound (A) preferably has a siloxane skeleton (also referred to as main chain skeleton). As such a siloxane skeleton, any siloxane bond may be used, and the structure of the siloxane skeleton may be linear or branched. In the silane compound (A), the proportion of the siloxane skeleton is preferably 80 to 10% by mass in 100% by mass of the silane compound (A). More preferably, it is 70-15 mass%, More preferably, it is 50-20 mass%.

Although the said silane compound (A) will not be specifically limited if it is the above-mentioned structure, As suitable embodiment, (1) Silane which has a group which can react with a siloxane bond, an imide bond, and a polymerizable unsaturated bond The silane compound has a main chain skeleton in which a siloxane bond (polysiloxane bond) is essential, and a structure in which a group capable of reacting with an imide bond and a polymerizable unsaturated bond is essential. (2) A silicon atom is bonded to at least one organic skeleton containing a group capable of reacting with an imide bond and a polymerizable unsaturated bond, and an oxygen atom is bonded to the silicon atom. A form in which at least one unit is bonded, a structural unit is essential, and the silicon atom of the structural unit forms a siloxane skeleton through an oxygen atom, (3) a main chain skeleton formed of a siloxane bond; A silane compound comprising an organic skeleton containing a group capable of reacting with an imide bond and a polymerizable unsaturated bond, wherein a structural unit in which at least a part of silicon atoms of the main chain skeleton is bonded to the organic skeleton is an essential unit. (4) A silane compound comprising an organic skeleton containing a group capable of reacting with a siloxane bond and an imide bond and a polymerizable unsaturated bond, and the silane compound mainly comprises a polysiloxane bond. Examples include a form in which an organic skeleton having a chain skeleton and containing an imide bond and a group capable of reacting with a polymerizable unsaturated bond is bonded to at least one silicon atom in the main chain skeleton.

In the preferred embodiment (1), “a structure in which a structure that can react with an imide bond and a polymerizable unsaturated bond is bonded to a main chain skeleton” means the imide bond and the polymerizable unsaturated bond. At least one of the structures (an organic skeleton including a group capable of reacting with an imide bond and a polymerizable unsaturated bond) that requires a group that can react with the bond is bonded to the main chain skeleton (siloxane skeleton) of the silane compound (A). Any structure can be used. In other words, any structure other than the main chain skeleton may be used as long as it has a structure capable of reacting with the imide bond and a polymerizable unsaturated bond. Specifically, the silane compound (A) preferably has a structure having a side chain having an imide bond and a group capable of reacting with a polymerizable unsaturated bond. In this case, the structure having an imide bond and a group capable of reacting with the polymerizable unsaturated bond as essential is not limited to having a repeating unit in the form of a “chain”, and it is sufficient that at least one side chain is included. .

In the preferred embodiment (2), “a silicon atom is bonded to at least one organic skeleton containing a group capable of reacting with an imide bond and a polymerizable unsaturated bond, and the silicon atom is an oxygen atom. Is a structural unit formed by bonding at least one of the following general formula (3):

(In the formula, X represents an organic skeleton having a group capable of reacting with an imide bond and a polymerizable unsaturated bond. S is an integer of 1 to 3, and 2t is an integer of 1 to 3. s + 2t = 4).

In the average composition formula (2), Y is preferably a hydroxyl group or an OR group. More preferred is an OR group, and even more preferred is an OR group in which R is an alkyl group having 1 to 8 carbon atoms. Z is preferably at least one selected from the group consisting of aromatic residues such as alkyl groups, aryl groups and aralkyl groups, and unsaturated aliphatic residues. These may have a substituent. More preferably, it is an aromatic residue such as an alkyl group or aryl group having 1 to 8 carbon atoms or an aralkyl group, which may have a substituent.

The organic group (Z) having no imide bond is preferably at least one selected from the group consisting of alkyl groups; aromatic residues such as aryl groups and aralkyl groups; and unsaturated aliphatic residues. These may have a substituent. Among these, a long-chain organic group is more preferable. Specifically, an organic group having 4 or more carbon atoms is more preferable, and an alkyl group having 4 or more carbon atoms is particularly preferable. As a result, the cured molded body is less likely to become brittle and has excellent mechanical strength. Specific examples include butyl, pentyl, hexyl, decyl and the like. Particularly preferred is hexyl.
In order to make the cured molded body difficult to become brittle and excellent in mechanical strength, the proportion of the organic group (Z) in the silane compound (A) is 100 mol of silicon atoms contained in the silane compound (A). The amount is preferably 5 to 95 mol. More preferably, it is 10 mol or more, More preferably, it is 20 mol or more, Most preferably, it is 50 mol or more.
Since the cured molded body is difficult to become brittle and excellent in mechanical strength and excellent in both crosslinking effects as a crosslinking agent, the total moles of the organic skeleton (X) and the organic group (Z) in the silane compound (A). The content of the organic skeleton (X) with respect to the amount is preferably 5 mol% to 95 mol%. More preferably, it is 10 mol%-90 mol%. More preferably, it is 15 mol% or more, and particularly preferably 20 mol% or more.

The silane compound (A) is, for example,

(Wherein X, Y and Z are the same or different and are the same as described above. N ₁ and n ₂ represent the degree of polymerization, n ₁ is a non-zero positive integer, and n ₂ is 0 or a positive integer). Y / Z- represents that Y or Z is bonded, X _1-2- represents that one or two Xs are bonded, and (Z / Y) _1-2- Represents that one Z or Y is bonded, two Z or Y are bonded, or one Z and one Y are bonded in total. Si- (X / Y / Z) ₃ indicates that any three kinds selected from X, Y and Z are bonded to a silicon atom. In the above formula, Si-Om ₁ and Si-Om ₂ is not intended to define the binding order of Si-Om ₁ and Si-Om _2, for example, Si-Om ₁ and Si-Om ₂ is alternately or randomly A co-condensed form, a form in which a polysiloxane composed of Si—Om ₁ and a polysiloxane of Si—Om ₂ are bonded are suitable, and the condensed structure is arbitrary.

The silane compound (A) can be represented by the above average composition formula (2), and the siloxane skeleton of the silane compound (A) (the main chain skeleton that requires a siloxane bond) is (SiO _m ) _n. Can also be expressed. The structure other than (SiO _m ) _n is an organic skeleton having a group capable of reacting with an imide bond and a polymerizable unsaturated bond (a structure requiring an imide bond and a group capable of reacting with a polymerizable unsaturated bond) X , A hydrogen atom, a hydroxyl group and other Y, and an organic group Z that does not contain an imide bond, and these bond to the silicon atom of the main chain skeleton. X, Y and Z may or may not be included in the repeating unit in the form of a “chain”. For example, one or more Xs may be contained in one molecule as a side chain. In the above (SiO _m ) _n , n represents the degree of polymerization. The degree of polymerization represents the degree of polymerization of the main chain skeleton, and an organic skeleton having a group capable of reacting with an imide bond and a polymerizable unsaturated bond ( X) does not necessarily have to be n. In other words, the organic skeleton (X) having one imide bond and a group capable of reacting with the polymerizable unsaturated bond may not necessarily exist in one unit of (SiO _m ) _n . In addition, one or more organic skeletons (X) having a group capable of reacting with an imide bond and a polymerizable unsaturated bond may be contained in one molecule. An organic skeleton having a group capable of reacting with a polymerizable unsaturated bond may be bonded to one silicon atom.

In the main chain skeleton (SiO _m ) _n , m is preferably a number of 1.0 or more and less than 2.0. More preferably, m = 1.5 to 1.8. Particularly preferably, m = 1.5. In the main chain skeleton (SiO _m1 ) _n1 and (SiO _m2 ) _n2 , the range of (n ₁ +1) / (n ₁ + n ₂ +1) is the same as the preferable range of a in the average composition formula (2). It is preferable that Further, the number of Si atoms bonded to (X / Y / Z) ₃ in the above formula and the number of X bonded to Si atoms in (SiO _m1 ) is preferably one.
The above n represents the degree of polymerization and is preferably 1 to 5000. More preferably, it is 1-2000, More preferably, it is 1-1000, Most preferably, it is 1-200.
The silane compound (A) when n is 2 is a structural unit in which at least one organic skeleton (X) having a group capable of reacting with an imide bond and a polymerizable unsaturated bond is bonded to a silicon atom. Examples include a form in which two (constituent units (i)) are included and a form in which only one constituent unit (i) is included. In particular,

(Wherein A is Y or Z, and X, Y and Z are the same as described above) and the like, and the form of a homopolymer containing two identical structural units (i), There are a homopolymer form containing two different structural units (i) and a copolymer form (cocondensed structure form) containing only one structural unit (i).

The organic skeleton (X) having a group capable of reacting with the imide bond and the polymerizable unsaturated bond has the following formula (4):

(In the formula, R ⁵ has at least one structure selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and has a group capable of reacting with a polymerizable unsaturated bond. X and z are the same. Or it is an integer of 0 or more and 5 or less, and y is preferably a group represented by 0 or 1. In the above R ⁵ , at least one structure selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring is a group in which R ⁵ has a ring structure (aromatic ring) of an aromatic compound, a ring of a heterocyclic compound This represents at least one group selected from the group consisting of a group having a structure (heterocycle) and a group having a ring structure (alicyclic ring) of an alicyclic compound. R ⁵ is preferably a phenylene group, naphthylidene group, norbornene divalent group, (alkyl) cyclohexylene group, cyclohexenyl group or the like. More preferably, it is a norbornene and / or cyclohexenyl group, and more preferably norbornene.
R ⁵ preferably further has a polymerizable unsaturated bond.
Specific examples of R ⁵ having a polymerizable unsaturated bond include a cyclohexenyl group and norbornene.

In the above formula (4), x and z are the same or different and are integers of 0 or more and 5 or less.
X + y may be an integer from 0 to 10, but is preferably from 3 to 7. More preferably, it is 3-5, Most preferably, it is 3.
The y is 0 or 1, and is preferably 0.

When X in the average composition formula (2) is a group represented by the formula (4), the silane compound (A) of the present invention is also referred to as a silane compound (4) in the present specification.
Since the said silane compound (4) has very high heat resistance, and shows high compatibility with respect to various polymers, it can provide heat resistance easily.
The silane compound (A) represented by the average composition formula XaYbZcSiOd can be obtained by any method. For example, a group capable of reacting with an imide bond and a polymerizable unsaturated bond in the silane compound (A). The manufacturing method including the process of imidating the intermediate body (consisting of a silane compound) represented by the average composition formula X′aYbZcSiOd having an organic skeleton X ′ having an amide bond corresponding to the organic skeleton X containing siloxane and a siloxane bond Is preferred.

The silicon atom to which X in the above average composition formula is bonded preferably has 3 bonds with an oxygen atom. According to this, since the silicon atom to which X is bonded is not bonded to another functional group, a silane compound having excellent heat resistance, moisture resistance, and hydrolysis resistance can be obtained. For example, when a silicon atom to which X is bonded is bonded to one oxygen and has another functional group, heat resistance, moisture resistance, and hydrolysis resistance may be lowered depending on the type of the functional group. The silicon atom constituting the siloxane bond preferably has 3 bonds with oxygen atoms. According to this, since the silicon atom which comprises a siloxane bond is not couple | bonded with functional groups other than the organic group represented by X, it can be set as the silane compound which was more excellent in heat resistance and hydrolyzability.

The compounding ratio (mass ratio) of the siloxane compound (I) and the silane compound (A) represented by the average composition formula (2) in the curable composition of the present invention is 10/90 to 95/5. It is preferable. More preferably, it is 40 / 60-90 / 10, More preferably, it is 60 / 40-85 / 15.

When the curable composition of this invention is 100 mass%, it is preferable that the silane compound (A) represented by the said average compositional formula (2) is 10-60 mass%. If it is less than 10% by mass, properties such as heat resistance may not be sufficiently exhibited, and if it exceeds 60% by mass, moldability may be deteriorated.
The lower limit is more preferably 12% by mass. More preferably, it is 15 mass%. The upper limit is more preferably 40% by mass. More preferably, it is 30 mass%.

Specifically, the method for producing the silane compound (A) preferably includes any of the following steps. By including such a process, it is possible to use industrially available raw materials, which can be manufactured to be suitable for an industrial production process, and can be manufactured efficiently by selecting a manufacturing route and an intermediate. There is an advantage that can be done.

As said manufacturing method, it is the method of manufacturing the said silane compound (The said silane compound (A) or the silane compound (4) represented by the said Formula (4)), Comprising: This manufacturing method is the following average composition formula:
X'aYbZcSiOd
(In the formula, X 'is the same or different and represents an organic skeleton containing a group capable of reacting with an amide bond and a polymerizable unsaturated bond. Y is the same or different and represents a hydrogen atom, a hydroxyl group, a halogen atom and OR. R represents at least one selected from the group consisting of groups, and R is the same or different and represents at least one group selected from the group consisting of alkyl groups, acyl groups, aryl groups and unsaturated aliphatic residues, Z may be the same or different and represents an organic group having no amide bond, a is a number not greater than 0 and 3 or less, and b is 0 or a number less than 3. , C is a number less than 0 or 3 and d is a number less than 2 which is not 0 and a + b + c + 2d = 4 X ′ and Z have a molar ratio of 5/95 to 50/50. X ′ in the following formula (5):

(Wherein R ⁶ represents an organic skeleton having at least one structure selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and having a group capable of reacting with a polymerizable unsaturated bond. X and z is the same or different, and is an integer of 0 or more and 5 or less, and y is 0 or 1. The silane compound (silane compound ( It is also preferable that it is a manufacturing method of 4) or a silane compound (A)). The term “intermediate comprising a silane compound represented by the formula (5)” above refers to a silane compound in which X ′ is represented by the formula (5) as an intermediate. The Y, Z, a, b, c, and d are preferably the same as those described in the above average composition formula, and the R ⁶ , x, y, and z are the silane compound (4). It is preferable that R ⁵ , x, y and z described in the above are the same.

In the said manufacturing method (it is also mentioned manufacturing method (I)), especially if it includes the process of imidating the intermediate body (henceforth intermediate body (5)) represented by the said Formula (5). It is not limited. An imidation process is a process of imidating by dehydration ring closure of an amic acid, and reaction conditions are shown below.

The reaction temperature in the imidization step is preferably 80 to 300 ° C. More preferably, it is 100-200 degreeC, More preferably, since water arises as a by-product, it is hold | maintaining above the azeotropic temperature of water and a solvent. The reaction pressure may be room temperature, under pressure, or under reduced pressure, but the reaction is likely to proceed by efficiently distilling by-product water out of the reaction system. The following is preferable. Specifically, 0.01 to 0.5 MPa or the like is preferable.
In addition, as a reaction catalyst, a known and publicly used amine such as pyridine, triethylamine, imidazole, diazabicycloundecene, tetramethylammonium hydroxide, or a solvent azeotropic with water such as toluene or xylene should be added as a ring-closing catalyst. Is desirable.
The reaction time varies depending on the reaction temperature and reaction composition, but is preferably about 2 to 48 hours.

The above production method (production method (I)) is represented by the following formula (6):

(Wherein R ⁷ represents an organic skeleton having at least one structure selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and having a group capable of reacting with a polymerizable unsaturated bond. R ⁸ Are the same or different and each represents an organic group, and R ⁹ is the same or different and represents at least one group selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR ⁹ ′ group, wherein R ^9. ′ May be the same or different and represents at least one group selected from the group consisting of an alkyl group, an acyl group, an aryl group, and an unsaturated aliphatic residue, and may have a substituent. The same or different, an integer of 0 or more and 5 or less, y is 0 or 1, and p is an integer of 0 or more and 2 or less. Preferably including a step of polycondensation Arbitrariness.
That is, such a production method (also referred to as production method (II)) includes an intermediate represented by the above formula (6) (also referred to as intermediate (6)) in addition to the imidization step (I). This includes a step of obtaining intermediate (5) (also referred to as step (II)). In addition, it is preferable that said R < ⁷ >, x, y, and z are the same as that of R < ⁵ >, x, y, and z demonstrated in the said silane compound (4), respectively. R ⁸ and R ⁹ correspond to Y and Z in the formula (2). p is preferably 0 or 1.

The step (II) is a step of obtaining the intermediate (5) by forming a polysiloxane skeleton by hydrolysis / polycondensation reaction of the alkoxysilyl group of the intermediate (6).
If the step (II) is included, the intermediate (5) is passed through a highly hydrophilic intermediate (6) (intermediate represented by the above formula (6)), so the hydrolysis of the alkoxysilyl group -There are advantages that the reaction efficiency of the polycondensation reaction is increased and the degree of polymerization of the polysiloxane skeleton is easily increased.

In the step (II), the intermediate (6) is mixed with water or an organic solvent containing water to hydrolyze and condense the intermediate (6).
By such a hydrolysis / condensation reaction, a polysiloxane skeleton that is a hydrolysis / condensation product can be formed. The hydrolyzed / condensed product refers to a compound obtained by further condensing a product obtained by the hydrolysis reaction.
The hydrolysis reaction and condensation reaction of intermediate (6) are shown below.
^{_{SiR 8 p (OR 9 ')}} 3-p + (3-p) H 2 O ( ^{_{hydrolysis) → SiR 8 p (OH)}} 3-p + (3-p) R 9'OH
^{_{SiR 8 p (OH) 3-}} p → SiR 8 p (OH) e O u → SiR 8 p O 2 / u ( condensate)
(In the formula, R ⁸ , R ⁹ ′ and p are as described above. E and u are arbitrary numerical values.)
Thus, the intermediate (5) having a high degree of polymerization of the polysiloxane skeleton can be obtained by hydrolyzing and condensing the intermediate (6).

In the hydrolysis / condensation reaction, water is used, and it is preferable to add 10 to 50% by mass of water to 100% by mass of the intermediate (6). Preferably, it is 20-40 mass%.
As the water used for the above reaction, any of ion-exchanged water, pH-adjusted water and the like may be used, but water having a pH of around 7 is preferably used. By using such water, the amount of ionic impurities in the composition can be reduced, and a resin composition having low hygroscopicity or high insulation can be obtained. The purity of water is preferably pH 7, but hydrogen chloride, oxalic acid, pyridine, triethylamine, etc. are volatilized out of the reaction system at a high temperature. You may adjust.
As a usage form of the water, a form in which it is dropped onto the intermediate (6) may be used, or a form in which it is charged in a lump may be used.

The reaction temperature in the hydrolysis / polycondensation reaction of the alkoxysilyl group is preferably room temperature to 200 ° C. More preferably, the temperature is from room temperature to 100 ° C., and most preferably, it is maintained under azeotropic reflux of alcohol, water and solvent since alcohol is produced as a by-product. The pressure in the above reaction may be room temperature, under pressure, or under reduced pressure, but the reaction tends to proceed by efficiently distilling by-product alcohol out of the reaction system. The pressure is preferably less than the pressure. The reaction time varies depending on the reaction temperature and reaction composition, but is preferably 2 to 48 hours.

Although it does not specifically limit as a manufacturing method of the said intermediate body (6), It is preferable to obtain from the compound (it is called a compound (7)) represented by following formula (7). That is, the above production method (production method (II)) is represented by the following formula (7):

(Wherein R ¹⁰ is the same or different and represents an organic group, and R ¹¹ is the same or different and represents at least one group selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR ¹¹ ′ group. Wherein R ¹¹ ′ is the same or different and represents at least one group selected from the group consisting of an alkyl group, an acyl group, an aryl group, and an unsaturated aliphatic residue, and may have a substituent. And x and z are the same or different and are an integer of 0 or more and 5 or less, y is 0 or 1, and v is an integer of 0 or more and 2 or less. It is preferable to include a step (also referred to as step (III)) in which an acid anhydride having a group capable of reacting with an unsaturated bond is subjected to ring-opening addition to obtain an intermediate composed of a silane compound represented by formula (6). .
That is, such a production method (also referred to as production method (III)) includes a hydrolysis / polycondensation step (II) in addition to the imidization step (I), and further includes an intermediate from the compound (7). The step of obtaining (6) (step (III)) will be included. By including such a process, there exists an advantage that an inexpensive manufacturing raw material can be used. The x, y and z are preferably the same as x, y and z described in the silane compound (4). R ¹⁰ , R ¹¹ and v are preferably the same as R ⁸ , R ⁹ and p described in the above formula (6).

The step (III) is an acid anhydride ring-opening addition step for obtaining the intermediate (6) from the compound (7). The reaction conditions are shown below.
As the water concentration in the above step (III), the yield of the target compound is reduced due to the hydration of the acid anhydride, so the solvent and the reactor are well dried, and dry nitrogen gas is circulated during the reaction. Is preferred. The solvent may be dried by using a publicly known dehydrating agent such as molecular sieve, anhydrous magnesium sulfate, anhydrous calcium chloride, or by distillation before the reaction.
The reaction temperature in the above step is preferably room temperature to 100 ° C. More preferably, it is 40-90 degreeC. Although the reaction proceeds sufficiently even near room temperature, depending on the reaction product, it may be precipitated during the reaction and stirring of the reaction system may be impossible, so it is preferable to react at a temperature higher than room temperature. The pressure in the above process may be normal temperature, under pressure, or under reduced pressure. The reaction time varies depending on the reaction temperature and reaction composition, but is preferably about 2 to 48 hours.

As a suitable form of the said manufacturing method (III), the form (form (A)) containing process (III), process (II), and process (I) is suitable.
In the above form (A), intermediate (6) is obtained from compound (7) by ring-opening addition reaction of acid anhydride (step (III)), and intermediate (6) is hydrolyzed and polycondensed. In this embodiment, the intermediate (5) is obtained (step (II)), and the intermediate (5) is further imidized to obtain the silane compound (A) or the silane compound (4).

As said crosslinking agent, things other than the silane compound (A) mentioned above can be used, for example, 1 type (s) or 2 or more types, such as a polyvalent amine, a polyvalent thiol, and a polyvalent acrylate, can be used. is there. Here, the polyvalent amine and polyvalent thiol are cross-linking agents that undergo a cross-linking reaction by an addition reaction, and the polyvalent acrylate is a cross-linking agent that undergoes a cross-linking reaction by radical polymerization.
When using a crosslinking agent that undergoes a crosslinking reaction in radical polymerization, the above-described radical polymerization initiator is required.

The curable composition of the present invention may further contain a thermosetting resin. As said thermosetting resin, what is recognized as a thermosetting resin in the technical field of this invention can be used suitably, and an epoxy resin, epoxy acrylate resin, unsaturated polyester resin, cyanate ester resin, urethane resin, bis Maleimide-triazine resin and phenol resin are preferred. In addition to the above, for example, melamine resin, guanamine resin, urea resin, xylene resin, polyurethane resin, alkyd resin, vinyl ether resin, polyaniline resin and the like can be used.
These compounds may be used alone or in combination of two or more.
For example, when the above epoxy resin, epoxy acrylate resin, unsaturated polyester resin, or cyanate ester resin is used, a curing catalyst / curing agent is usually required. The urethane resin and bismaleimide-triazine resin can usually be cured only by heat. The phenolic resin can be cured only by heat, or can be cured using a curing catalyst / curing agent.

The said curable composition may contain the hardening component as needed. Examples of the curing component include a curing catalyst and a curing agent. In addition, a curing catalyst means what does not become a resin structure, and a hardening | curing agent means what is integrated in resin.

The curing components (specifically, curing catalyst and curing agent) that may be contained in the curable composition of the present invention will be described below.
Examples of the curing catalyst include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; 2,4,6-tris (dimethylaminomethyl) phenol, benzylmethylamine, DBU (1,8- Amines such as diazabicyclo [5.4.0] -7-undecene) and DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea); for example, triphenylphosphine, tributylhexadecylphosphonium One or more of organic phosphorus compounds such as bromide, tributylphosphine, and tris (dimethoxyphenyl) phosphine are suitable.

Examples of the curing agent include acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, and methylnadic acid; phenol novolac resin, cresol novolac resin, bisphenol A Novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, terpene phenol resin and other various phenol resins; obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde and glyoxal 1 type, or 2 or more types, such as various phenol resins, such as a polyhydric phenol resin, can be used.

The said curable composition may contain the solvent as needed. As the solvent, those having at least one structure composed of the above-described ether bond, ester bond and nitrogen atom are preferable, and either alone or 2 depending on the drying process conditions so as to have the optimum viscosity for impregnation or coating process. Can be used with more than one kind of mixture.

The curable composition of the present invention further includes other additives such as a stabilizer, a release agent, a coupling agent, a colorant, a plasticizer, a diluent, a photosensitizer, a flame retardant, a stress relaxation agent, and a filler. Various rubber-like materials, anion exchangers and the like can be blended as necessary.

As described above, the curable composition of the present invention can form a cured product having improved properties such as heat resistance and solvent resistance while ensuring sufficient basic performance such as mechanical strength. In particular, the cured products include insulating materials for power modules such as converters, inverters, hybrid ICs, membrane switches, component potting agents, encap agents, sealants, substrate coating agents, adhesives for assemblies such as shock absorbers, It can be suitably used for an aerospace adhesive such as a wire sealant and an engine gasket agent.

The curable composition of the present invention has the above-described configuration, and has properties such as heat resistance and solvent resistance that are remarkably improved while sufficient basic performance such as mechanical strength is obtained. Is a curable composition capable of forming a cured product with low deterioration of various physical properties.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
N in the chemical formula described below indicates that the siloxane bond in parentheses is repeated, and the chemical formula of the compound obtained in each synthesis example indicates the main composition of the synthesized compound.
The GPC measurement conditions and the NMR measurement conditions are as follows.
(GPC measurement conditions)
Column used: Shodex GF-7MHQ (manufactured by Showa Denko) 2 eluents: DMF (dimethylformamide)
Flow rate: 0.6 ml / min.
Column temperature: 40 ° C
Standard material: polystyrene detector: RI (differential refractive index) detector implantation amount: 10 μL with 0.5 wt% solution
(NMR measurement conditions)
Solvent: CDCl ₃
Concentration: 5 wt%

Synthesis Example 1 Synthesis of Polysiloxane A To a 200 mL four-necked flask equipped with a 7% O ₂ gas introduction tube, a stirrer, a temperature sensor, and a Dean-Stark trap, 95 g of toluene and a 3-aminopropyl group both-end dimethylsiloxane oligomer ( 73.93 g of trade name “Silaplane FM-3311” (manufactured by Chisso Corporation) was added and stirred and homogenized at room temperature. Then, 3.40 ′ 3,4′-diphenylsulfonetetracarboxylic dianhydride 14.40 g And 8.20 g of maleic anhydride were added and stirring was continued overnight at 40 ° C. After confirming that the reaction solution became cloudy and highly viscous, 9.84 g of 80% phosphoric acid was added while circulating 7% O ₂ gas, and the temperature was raised. When the temperature exceeded 100 ° C., the produced water began to be collected in the Dean-Stark trap, and when the temperature was raised to 120 ° C. over 8 hours, 4.5 g of water could be collected. After cooling, the reaction solution had a lower viscosity than before the temperature increase but became yellow and transparent. After this reaction solution was washed with water, polysiloxane A was obtained by removing volatiles with a rotary evaporator. When molecular weight analysis was performed by GPC, it was Mw3830 and Mn2630. Further, in ¹ H-NMR measurement, δ = 0.08 ppm (derived from dimethylsiloxane skeleton), 0.48 ppm, 1.41 ppm, 3.23 ppm (all derived from propyl bond), 7.10 ppm (derived from maleimide group), 7.16 ppm , 7.92 ppm (both derived from diphenylsulfone skeleton), in ¹³ C-NMR measurement, δ = −0.13 ppm (derived from dimethylsiloxane skeleton), 9.7 ppm, 21.5 ppm, 40.6 ppm (both propyl From the bond), 118.9 ppm, 130.7 ppm, 133.9 ppm, 161.6 ppm (all from the diphenylsulfone skeleton), 135.4 ppm, 170.2 ppm (all from the maleimide group), respectively. Therefore, polysiloxane A is a polysiloxane of formula (8) It was determined to have a mer structure.

Synthesis Example 2 Synthesis of Polysiloxane B Into a 200 mL four-necked flask equipped with a 7% O ₂ gas introduction tube, a stirrer, a temperature sensor, and a Dean-Stark trap, 93 g of toluene and dimethyl 3-aminopropyl group at both ends with a molecular weight of 920 Siloxane oligomer (trade name “Silaplane FM-3315”, manufactured by Chisso Corporation) 39.53 g and 3-aminopropyl group-terminated dimethylsiloxane oligomer having a molecular weight of 9620 (trade name “Silaplane FM-3325”, manufactured by Chisso Corporation) When 45.93 g was added and the mixture was stirred and homogenized at room temperature, 9.55 g of maleic anhydride was added and stirring was continued overnight at 40 ° C. As the unreacted maleic anhydride was consumed, the disappearance of the solid matter could be visually confirmed, and the reaction solution became highly viscous. Subsequently, 11.70 g of 80% phosphoric acid was added while circulating 7% O ₂ gas, and the temperature was started. When the temperature exceeded 100 ° C., the produced water began to be collected in the Dean-Stark trap, and when the temperature was raised to 120 ° C. over 8 hours, 4.1 g of water could be collected. After cooling, the reaction solution had a lower viscosity than before the temperature increase but became yellow and transparent. After this reaction solution was washed with water, polysiloxane A was obtained by removing volatiles with a rotary evaporator. Molecular weight analysis by GPC revealed Mw3910 and Mn1820. Further, in ¹ H-NMR measurement, δ = 0.08 ppm (derived from dimethylsiloxane skeleton), 0.48 ppm, 1.41 ppm, 3.23 ppm (all derived from propyl bond), 7.10 ppm (derived from maleimide group), ¹³ C In NMR measurement, δ = −0.13 ppm (derived from dimethylsiloxane skeleton), 9.7 ppm, 21.5 ppm, 40.6 ppm (all derived from propyl bond), 135.4 ppm, 170.2 ppm (all derived from maleimide group) Thus, it was determined that polysiloxane A had a polymer structure of formula (9).

Synthesis Example 3 Synthesis of Polysiloxane C To a 200 mL four-necked flask equipped with a nitrogen gas inlet tube, a stirrer, a temperature sensor, and a Dean-Stark trap, 30 g of toluene, 70 g of N, N′-dimethylacetamide and 3-amino of molecular weight 920 36.13 g of a propyl group-terminated dimethylsiloxane oligomer (trade name “Silaplane FM-3311”, manufactured by Chisso Corporation) and 13.51 g of 3,3′-4,4′-diphenylsulfonetetracarboxylic dianhydride are added. After stirring and homogenizing at room temperature, stirring was continued at 80 ° C. for 6 hours. Unreacted tetracarboxylic dianhydride disappeared to increase the viscosity. Subsequently, 0.096 g of 80% phosphoric acid was added while flowing 7% O ₂ gas, and the temperature was started. The generated water started to be collected in the Dean-Stark trap when the temperature exceeded 100 ° C., and further raised to 160 ° C. over 8 hours, 1.5 g of water and toluene as an azeotropic component could be recovered. After cooling, the reaction solution had a lower viscosity than before the temperature increase but became yellow and transparent. This reaction solution was washed with water to obtain polysiloxane C as a viscous fluid component. Molecular weight analysis by GPC revealed Mw30800 and Mn24200. ^{In 1} H-NMR measurement, δ = 0.08 ppm (derived from dimethylsiloxane skeleton), 0.48 ppm, 1.41 ppm, 3.23 ppm (all derived from propyl bond), 7.16 ppm, 7.92 ppm (all from diphenylsulfone skeleton) Origin) peak in ¹³ C-NMR measurement, δ = −0.13 ppm (derived from dimethylsiloxane skeleton), 9.7 ppm, 21.5 ppm, 40.6 ppm (all derived from propyl bond), 118.9 ppm, 130. Since peaks of 7 ppm, 133.9 ppm, and 161.6 ppm (both derived from diphenylsulfone skeleton) were confirmed, it was determined that polysiloxane C had a polymer structure of formula (10).

Synthesis Example 4 Synthesis of Polysiloxane D 3,4-3 ′, 4′-biphenyltetracarboxylic dianhydride instead of 3,3′-4,4′-diphenylsulfonetetracarboxylic dianhydride of Synthesis Example 1 Polysiloxane D was obtained by using 11.82 g. Molecular weight analysis by GPC revealed Mw3490 and Mn2180. Further, in ¹ H-NMR measurement, δ = 0.08 ppm (derived from dimethylsiloxane skeleton), 0.48 ppm, 1.41 ppm, 3.23 ppm (all derived from propyl bond), 7.10 ppm (derived from maleimide group), 7.91 ppm , 8.19Ppm, peaks of 8.35Ppm (both from biphenyl skeleton) ^is, in 13 C-NMR measurement δ = -0.13ppm (from dimethylsiloxane skeleton), 9.7ppm, 21.5ppm, 40.6ppm ( All are derived from a propyl bond), 126.3 ppm, 127.9 ppm, 130.9 ppm, 131.2 ppm, 140.1 ppm (all derived from a biphenyl skeleton), 135.4 ppm, 170.2 ppm (all derived from a maleimide group) Were confirmed, polysiloxane D was determined to be the polymer structure of formula (11).

Synthesis Example 5 Synthesis of Polysiloxane E 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride instead of 3,3′-4,4′-diphenylsulfonetetracarboxylic dianhydride of Synthesis Example 1 Polysiloxane D was obtained by using 12.95 g.
Molecular weight analysis by GPC revealed Mw3600 and Mn2210. Further, in ¹ H-NMR measurement, δ = 0.08 ppm (derived from dimethylsiloxane skeleton), 0.48 ppm, 1.41 ppm, 3.23 ppm (all derived from propyl bond), 7.10 ppm (derived from maleimide group), 8.13 ppm , 8.23 ppm, 8.57 ppm (both derived from benzophenone skeleton), δ = −0.13 ppm (derived from dimethylsiloxane skeleton), 9.7 ppm, 21.5 ppm, 40.6 ppm in ¹ H-NMR measurement ( All are derived from a propyl bond), 127.0 ppm, 129.1 ppm, 132.2 ppm, 133.6 ppm, 136.0 ppm, 141.3 ppm, 187.2 ppm (all derived from a benzophenone skeleton), 135.4 ppm, 170.2 ppm ( Both are derived from maleimide groups) Since each could be confirmed, it was determined that polysiloxane E had a polymer structure of formula (12).

Synthesis Example 6 Synthesis of Silane Compound a Into a 200 mL four-necked flask equipped with a nitrogen gas introduction tube, a stirrer, a temperature sensor, and a cooling tube, 75 g of diglyme previously dried with molecular sieve, 77.76 g of n-hexyltrimethoxysilane, 3 -After adding 22.52 g of aminopropyltrimethoxysilane to obtain a homogeneous solution, 20.62 g of 5-norbornene-2,3-dicarboxylic anhydride was added all at once at room temperature. The reaction solution rose to 47 ° C. due to the heat of reaction, and it became impossible to confirm the insoluble content of 5-norbornene-2,3-dicarboxylic anhydride as the reaction proceeded. Thereafter, the mixture was stirred for 2 hours while maintaining the reaction solution temperature at 80 ° C. Subsequently, 27.16 g of deionized water and 0.382 g of zinc 2-ethylhexanoate (II) were added to the reaction solution, and then refluxing by by-product methanol started to be maintained for 6 hours in the refluxed state. Subsequently, the cooling pipe was replaced with a partial condenser, and the temperature was raised again. While collecting by-product methanol and condensed water, the reaction liquid temperature reached 160 ° C. over 6 hours, and the internal pressure was reduced to 30 Torr at the same temperature. Volatile components were subsequently recovered and held for 2 hours. As a result, about 160 ml of volatile components were recovered. 83 g of silane compound a as a reaction product was obtained. The reaction product was a pale yellow high-viscosity liquid, and molecular weight analysis by GPC revealed Mw 5420 and Mn 1910.

Synthesis Example 7 Synthesis of Silane Compound b In a 200 mL four-necked flask equipped with a nitrogen gas introduction tube, a stirrer, a temperature sensor, and a cooling tube, 65 g of diglyme previously dried with molecular sieve, 94.81 g of n-hexyltrimethoxysilane, 3 -After 27.46 g of aminopropyltrimethoxysilane was added to obtain a homogeneous solution, 23.30 g of cis-4-cyclohexene dicarboxylic acid anhydride was added all at once at room temperature. The reaction solution rose to 47 ° C. due to the heat of reaction, and it became impossible to confirm the insoluble matter of cis-4-cyclohexene dicarboxylic acid anhydride as the reaction proceeded. Thereafter, the mixture was stirred for 2 hours while maintaining the reaction solution temperature at 80 ° C. Subsequently, 33.12 g of deionized water and 0.116 g of zinc 2-ethylhexanoate (II) were added to the reaction solution, and refluxing by by-product methanol started to be maintained for 6 hours in the refluxed state. Subsequently, the cooling pipe was replaced with a partial condenser, and the temperature was raised again. While collecting by-product methanol and condensed water, the reaction liquid temperature reached 160 ° C. over 6 hours, and the internal pressure was reduced to 30 Torr at the same temperature. Volatile components were subsequently recovered and held for 2 hours. As a result, about 160 ml of volatile components were recovered. 97 g of silane compound b as a reaction product was obtained. The reaction product was a pale yellow high-viscosity liquid, and molecular weight analysis by GPC revealed Mw5520 and Mn2090.

Synthesis Example 8 Synthesis of Silane Compound c In a 200 mL four-necked flask equipped with a nitrogen gas introduction tube, a stirrer, a temperature sensor, and a cooling tube, 65 g of diglyme previously dried with molecular sieve, 55.85 g of n-hexyltrimethoxysilane, 3 -After 48.52 g of aminopropyltrimethoxysilane was added to obtain a homogeneous solution, 41.59 g of cis-4-cyclohexene dicarboxylic acid anhydride was added all at once at room temperature. The reaction solution rose to 58 ° C. due to the heat of reaction, and it became impossible to confirm the insoluble content of cis-4-cyclohexenedicarboxylic anhydride as the reaction proceeded. Thereafter, the mixture was stirred for 2 hours while maintaining the reaction solution temperature at 80 ° C. Subsequently, 29.26 g of deionized water and 0.103 g of zinc 2-ethylhexanoate (II) were added to the reaction solution. As a result, refluxing with by-product methanol started and the mixture was maintained for 6 hours in the refluxed state. Subsequently, the cooling pipe was replaced with a partial condenser, and the temperature was raised again. While collecting by-product methanol and condensed water, the reaction liquid temperature reached 160 ° C. over 6 hours, and the internal pressure was reduced to 30 Torr at the same temperature. Volatile components were subsequently recovered and held for 2 hours. As a result, about 180 ml of volatile components were recovered. 105 g of silane compound c as a reaction product was obtained. The reaction product was a pale yellow high-viscosity liquid, and molecular weight analysis by GPC revealed Mw 4880 and Mn 2020.

Example 1
After 80 parts by weight of the above polysiloxane A and 20 parts by weight of the silane compound a were uniformly mixed at 60 ° C., 1 part by weight of t-butyl peroxybenzoate (trade name “Perbutyl Z”, manufactured by NOF Corporation) was added. After that, it was poured into a 1 mm thick aluminum molding frame and left in an oven at 150 ° C. for 2 hours to obtain a molded product after demolding. For comparison, a two-component addition type silicone resin (trade name “TSE3033”, manufactured by Momentive Performance Materials) was used. The mechanical properties were measured according to JIS K7113: 1995, and the solvent resistance was examined based on the weight increase rate before and after immersion of the test piece in toluene. The toluene immersion condition was 60 ° C. × 24 hours, and a lower weight increase rate was suitable.
For Examples 2 to 9 and Comparative Examples 1 to 3, mechanical properties and solvent resistance were evaluated in the same manner as in Example 1 except that the components were changed as shown in Table 1 below.

In the above-described examples, the siloxane compound (I) represented by the above formula (1) is used, R ¹ is a skeleton having a methyl group, R ² is C ₃ H ₆ , and R ³ is an aromatic ring. As long as R ⁴ is a CH═CH group, as long as the siloxane compound (I) is in a form having an imide bond in the molecular skeleton and at the molecular end, the action mechanism that produces the effect of the present invention is It is the same. That is, if the siloxane compound (I) has the above bond in the molecular skeleton and at the molecular end, the essential feature of the present invention is that if the bond has similar chemical characteristics, The effect as shown in the example will be achieved. Therefore, it can be said that if the siloxane compound (I) has the above bonds in the molecular skeleton and at the molecular terminal in the present invention, the advantageous effects of the present invention are surely exhibited. In the case where at least the siloxane compound (I) is represented by the above formula (1), the advantageous effects of the present invention are sufficiently proved by the examples and comparative examples described above, and the technical significance of the present invention. Is supported.

Claims (4)

A siloxane compound (I) having an imide bond and a siloxane bond,
The siloxane compound (I) has an imide bond in the molecular skeleton and at the molecular terminal. The siloxane compound (I) has the following formula (1);

(In the formula, R ¹ is the same or different and represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ² is the same or different and represents a divalent hydrocarbon group having 1 to 20 carbon atoms. R ³ is the same or different and represents a skeleton having at least one structure selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and R ⁴ is the same or different and represents a polymerizable unsaturated bond. Or represents a structure of a heterocyclic ring and / or an alicyclic ring having a polymerizable unsaturated bond, and may have a substituent, and m and n are the same or different and are integers of 1 to 200). The siloxane compound (I) according to claim 1, which is represented by: A curable composition containing the siloxane compound (I) according to claim 1 or 2,
The curable composition further contains a crosslinking agent. The crosslinking agent has the following average composition formula (2):
XaYbZcSiOd (2)
(Wherein X is the same or different and represents an organic skeleton having a group capable of reacting with an imide bond and a polymerizable unsaturated bond; Y is the same or different and represents a hydrogen atom, a hydroxyl group, a halogen atom and OR; R represents at least one selected from the group consisting of groups, and R is the same or different and represents at least one group selected from the group consisting of alkyl groups, acyl groups, aryl groups and unsaturated aliphatic residues, Z may be the same or different and represents an organic group that does not have an imide bond, a is a non-zero number of 3 or less, and b is a number of 0 or less than 3. , C is a number less than 0 or 3 and d is a number less than 2 which is not 0 and a + b + c + 2d = 4, and X and Z have a molar ratio of 5/95 to 50/50.) A silane compound (A) represented by The curable composition according to claim 3, characterized in.