JP4415624B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition containing a silane condensate and a maleimide compound.

  The curable resin obtained by the reaction of bismaleimide and aromatic diamine is known to be a heat-resistant resin having a high glass transition temperature (Tg), and there is little change in elastic modulus and tan δ accompanying the glass transition. It has been reported as a material excellent in heat resistance (see, for example, Non-Patent Document 1).

"Polymer Papers," October 1984, Vol. 41, No. 10, p. 629-633

  However, the known curable resin obtained by the reaction of bismaleimide and aromatic diamine described in Non-Patent Document 1 and the like described above further improves the heat resistance of the obtained cured product under the current required characteristics. It became clear that there was a need.

  Then, this invention aims at provision of the curable composition containing the silane condensate and the maleimide compound which can obtain the hardened | cured material which has high heat resistance.

The present inventor has found that a curable composition containing a specific silane condensate and a maleimide compound can provide a cured product having high heat resistance, and has completed the present invention. That is, this invention provides the curable composition as described in following (i)- (xi) .

(I) a silane condensate containing at least one of the aminosilane compounds represented by the following general formulas (1) to (4) as a constituent component;
A maleimide compound having two or more maleimide groups represented by the following general formula (5) in one molecule ;
The maleimide compound is used in an amount of 0.1 to 5.0 equivalents of the maleimide group relative to 1.0 equivalent of the amino group (—NH ₂ ) and / or imino group (—NH—) of the silane condensate. Is contained at a ratio of
A curable composition in which the silane condensate and the maleimide compound cause a curing reaction (first embodiment).

In the formula, R ¹ is an alkylene group having 1 to 12 carbon atoms, R ² and R ³ are each independently an optionally branched alkyl group having 1 to 8 carbon atoms, and R ⁴ is 1 to 1 carbon atom. 12 is an alkylene group, R ⁵ is an optionally branched alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and R ⁶ is a carbon number. 1 to 12 alkylene groups, R ⁷ and R ⁸ are each independently an alkylene group having 1 to 12 carbon atoms, and n is an integer of 0 to 2. A plurality of R ¹ , R ² and R ³ may be the same or different. R ⁹ and R ¹⁰ are each independently a hydrogen atom or an optionally branched alkyl group having 1 to 8 carbon atoms.

  (Ii) The curable composition according to the above (i), wherein the aminosilane compound is an aromatic aminosilane compound.

  (Iii) The curable composition according to the above (i) or (ii), further comprising a curing agent having an amino group and / or a thiol group.

  (Iv) The curable composition according to any one of (i) to (iii), further comprising a compound having an epoxy group.

(V) on the Symbol curing agent, relative to the maleimide group 1.0 equivalent of the maleimide compound, the amino groups and / or thiol groups of the curing agent in a proportion equal to or less than 0.9 eq (iii) The curable composition according to 1.

(Vi) a compound having an upper Symbol epoxy group, an amino group of the silane condensates (-NH ₂₎ and / or imino group (-NH-) 1.0 per equivalent of the compound having the epoxy group Epoxy The curable composition as described in (iv) above, which is contained in a ratio such that the group is 0.9 equivalent or less.

(Vii) A silane condensate containing a mercaptosilane compound represented by the following general formula (6) as a constituent component, and a maleimide compound having two or more maleimide groups represented by the following general formula (5) in one molecule containing the door,
The maleimide compound is contained in a proportion such that the maleimide group of the maleimide compound is 0.1 to 5.0 equivalents with respect to 1.0 equivalent of the thiol group of the silane condensate,
A curable composition in which the silane condensate and the maleimide compound cause a curing reaction (second embodiment).

In the formula, R ¹ is an alkylene group having 1 to 12 carbon atoms, R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms, and n is an integer of 0 to 2. It is. A plurality of R ² or R ³ may be the same or different. R ⁹ and R ¹⁰ are each independently a hydrogen atom or an optionally branched alkyl group having 1 to 8 carbon atoms.

(Viii) The curable composition according to (vii) , further comprising a curing agent having an amino group and / or a thiol group.

(Ix) The curable composition according to the above (vii) or (viii) , further comprising a compound having an epoxy group.

(X) is the upper Symbol curing agent, relative to the maleimide group 1.0 equivalent of the maleimide compound, an amino group and / or thiol groups of the curing agent in a proportion equal to or less than 0.9 equivalents above (viii) The curable composition according to 1.

(Xi) The compound having an upper Symbol epoxy group, to a thiol group 1.0 equivalent of the silane condensates, the epoxy group of the compound having the epoxy group is contained in a ratio equal to or less than 0.9 equivalent ( The curable composition as described in ix) .

  As described below, according to the present invention, it becomes possible to obtain a cured product having high heat resistance, and if the silane condensate is liquid at room temperature, the curable resin composition can be used without using a solvent. This is useful because the mixing and curing reaction of the product proceeds.

The present invention is described in detail below.
The curable composition according to the first aspect of the present invention includes a silane condensate containing at least one of the aminosilane compounds represented by the above general formulas (1) to (4) as a constituent component, and the above general formula. And a maleimide compound having two or more maleimide groups represented by (5) in one molecule.
Moreover, the curable composition which concerns on the 2nd aspect of this invention is represented by the silane condensate which contains the mercaptosilane compound represented by the said General formula (6) as a structural component, and the said General formula (5). And a maleimide compound having two or more maleimide groups in one molecule.
Below, each component used for the curable composition which concerns on the 1st aspect of this invention and a 2nd aspect (henceforth "the curable composition of this invention" only) is demonstrated.

<Silane condensate>
The silane condensate used in the curable composition of the present invention is a condensate containing at least one of the aminosilane compounds represented by the general formulas (1) to (4) as a constituent component or the general formula (6). It is not particularly limited as long as it is a condensate containing a mercaptosilane compound represented by the formula, and further contains silicate, alkoxysilane, halogenoalkoxysilane, polysiloxane, polydimethylsiloxane, and a silane coupling agent, which will be described later. You may do it.

  The silyl group in the aminosilane compound represented by the general formulas (1) to (4) or the mercaptosilane compound represented by the general formula (6) has at least one hydrolyzable substituent. More preferably two or more, and particularly preferably three or more. When it has two or more, the silane condensate containing the aminosilane compound or the mercaptosilane compound as a constituent component contributes to the improvement of heat resistance in the curing reaction with the maleimide compound described later.

Specific examples of the hydrolyzable substituent include a hydrogen atom, an alkoxy group, an acyloxy group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Of these, mild hydrolyzable alkoxy groups are preferred.
In addition, by selecting a hydrolyzable substituent, the hydrolysis rate and the adhesive expression time can be adjusted according to the application.

The aminosilane compound will be described in detail.
The aminosilane compound is an aminosilane compound having an amino group and / or an imino group and the silyl group described above, and is represented by the following general formulas (1), (2), (3) and (4) A compound.

In the general formula (1), R ¹ is an alkylene group having 1 to 12 carbon atoms, R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms, and n is It is an integer of 0-2. A plurality of R ¹ , R ² and R ³ may be the same or different.

Specific examples of the alkylene group having 1 to 12 carbon atoms of R ¹ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and an octamethylene group. A trimethylene group is more preferable from the viewpoint of easy availability and excellent adhesiveness.
Specific examples of the optionally branched alkyl group having 1 to 8 carbon atoms of R ² and R ³ include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, and the like. The group may contain a double bond or a triple bond. Of these, a methyl group and an ethyl group are preferable.

  Here, specific examples of the aminosilane compound represented by the general formula (1) include N, N-bis [(3-trimethoxysilyl) propyl] amine, N, N-bis [(3 -Triethoxysilyl) propyl] amine, N, N-bis [(3-tripropoxysilyl) propyl] amine, N, N-bis [(3-methoxydimethoxysilyl) propyl] amine, N, N-bis [( 3-ethoxydiethoxysilyl) propyl] amine and the like.

In the general formula (2), R ² and R ³ are each independently an optionally branched alkyl group having 1 to 8 carbon atoms, R ⁴ is an alkylene group having 1 to 12 carbon atoms, and R ⁵ Is an alkyl group having 1 to 8 carbon atoms which may be branched, an aralkyl group having 7 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and n is an integer of 0 to 2. The plurality of R ² or R ³ may be the same or different.

Here, R ² and R ³ are basically the same as those described in the general formula (1).
Specific examples of the alkylene group having 1 to 12 carbon atoms of R ⁴ include, for example, an alkylene group exemplified by R ¹ in the general formula (1). Preferably there is.

Specific examples of the optionally branched alkyl group having 1 to 8 carbon atoms of R ⁵ include the alkyl groups exemplified as R ² and R ³ in the general formula (1).
Here, as an aminosilane compound represented by the above general formula (2), in which R ⁵ is an optionally branched alkyl group having 1 to 8 carbon atoms, specifically, for example, N-butylaminopropyl Examples include trimethoxysilane (Dynasilane 1189 (Degussa Huls)), N-ethylaminoisobutyltrimethoxysilane (Nihon Unicar).

Specific examples of the optionally branched aralkyl group having 7 to 18 carbon atoms of R ⁵ include a benzyl group and a phenethyl group.

Specific examples of the aryl group having 6 to 18 carbon atoms of R ⁵ include a phenyl group, a methylphenyl group (toluyl group), a dimethylphenyl group, and an ethylphenyl group. In addition to the alkyl group described above, examples of the substituent for the aryl group include an alkoxy group such as a methoxy group and an ethoxy group, and a group composed of a halogen atom such as a fluorine atom and a chlorine atom. These substituents may have 1 or 2 or more, and their substitution positions are not limited.
Here, specific examples of the aminosilane compound represented by the above general formula (2) in which R ⁵ is an aryl group having 6 to 18 carbon atoms include, for example, N-phenyl-γ-aminopropyltrimethoxysilane. (Nihon Unicar Co., Ltd.).

In the general formula (3), R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms, R ⁶ is an alkylene group having 1 to 12 carbon atoms, and n is It is an integer of 0-2. The plurality of R ² or R ³ may be the same or different.

Here, R ² and R ³ are basically the same as those described in the general formula (1).
Specific examples of the alkylene group having 1 to 12 carbon atoms of R ⁶ include, for example, an alkylene group exemplified by R ¹ in the above general formula (1). Preferably there is.

  Here, specific examples of the compound represented by the general formula (3) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- Examples include aminopropylmethyldiethoxysilane and γ-aminopropylethyldiethoxysilane.

In the general formula (4), R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms, and R ⁷ and R ⁸ are each independently an alkylene having 1 to 12 carbon atoms. N is an integer of 0-2. The plurality of R ² or R ³ may be the same or different.

Here, R ² and R ³ are basically the same as those described in the general formula (1).
Specific examples of the alkylene group having 1 to 12 carbon atoms of R ⁷ and R ⁸ include, for example, an alkylene group exemplified by R ¹ in the general formula (1). An alkylene group is preferred.

  Here, specific examples of the compound represented by the general formula (4) include N-β (aminoethyl) γ-aminopropyltrimethoxysilane and N-β (aminoethyl) γ-aminopropyl. Examples include aminosilanes such as methyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, and N-β (aminoethyl) γ-aminopropylethyldiethoxysilane.

If the aminosilane compound mentioned above is an aromatic aminosilane compound, it is preferable because the storage stability of the resulting curable composition according to the first aspect of the present invention is excellent. That is, R ⁵ in the general formula (2) is preferably an aryl group having 6 to 18 carbon atoms, specifically, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino. Propyltriethoxysilane and derivatives thereof (for example, N- (2-methylphenyl) -γ-aminopropyltrimethoxysilane, N- (3-methylphenyl) -γ-aminopropyltriethoxysilane, etc.) are used. More preferred.
Moreover, if the aminosilane compound mentioned above is an aliphatic aminosilane compound, the curing reaction of the silane condensate containing the aminosilane compound as a constituent component and the maleimide compound described later proceeds at a low temperature (for example, 20 to 50 ° C.). It is preferable for the reason. That is, R ⁵ in the general formula (2) is preferably an alkyl group having 1 to 8 carbon atoms which may be branched. Specifically, N-butylaminopropyltrimethoxysilane, N-ethylamino More preferably, isobutyltrimethoxysilane is used.
Furthermore, if the aminosilane compound described above is a compound that becomes liquid at room temperature (for example, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, etc.), the aminosilane compound is The silane condensate contained as a constituent component can be made liquid at room temperature, which is preferable because a solvent is unnecessary during mixing and curing reaction with the maleimide compound described below.

Next, the mercaptosilane compound will be described in detail.
The mercaptosilane compound is a mercaptosilane compound having a thiol group and the above-described silyl group, and is a mercaptosilane compound represented by the following general formula (6).

In the general formula (6), R ¹ is an alkylene group having 1 to 12 carbon atoms, R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms which may be branched, and n is It is an integer of 0-2. The plurality of R ² or R ³ may be the same or different.

Here, R ¹ , R ² and R ³ are basically the same as those described in the general formula (1).
Specific examples of the compound represented by the general formula (6) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyl. Examples thereof include diethoxysilane and γ-mercaptopropylethyldiethoxysilane.

  Similarly to the aminosilane compound described above, if the mercaptosilane compound is a compound that becomes liquid at room temperature (for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, etc.), the mercaptosilane compound is constituted. The silane condensate contained as a component can be made liquid at room temperature, which is preferable because a solvent is not required at the time of mixing and curing reaction with a maleimide compound described later.

The silane condensate used in the curable composition of the present invention is represented by the aminosilane compound represented by the general formulas (1), (2), (3) and (4) or the general formula (6). The mercaptosilane compound may be contained alone as a constituent component, or two or more may be used in combination.
The silane condensate contains the aminosilane compound or mercaptosilane compound contained as a constituent component in an amount of 0.1 to 1.5 with respect to 1.0 equivalent of the condensable group in the aminosilane compound or mercaptosilane compound. Equivalent, preferably 0.1 to 5 parts by weight, preferably 1 to 2 parts by weight with respect to 100 parts by weight of water and aminosilane compound or mercaptosilane compound added at a ratio of 0.8 to 1.2 equivalents It can be obtained by reacting (condensation reaction) in the presence of an acid catalyst or a base catalyst to be added at 30 to 60 ° C., preferably at room temperature, for 5 to 30 hours, preferably for 10 to 20 hours. Not.
Further, when the aminosilane compound or the mercaptosilane compound contained as a constituent component is a liquid at room temperature, the silane condensate is based on 1.0 equivalent of a condensable group in the aminosilane compound or the mercaptosilane compound. 0.1 to 1.2 equivalents, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of water and the aminosilane compound or mercaptosilane compound added at a ratio of 0.8 to 1.0 equivalents, By reacting (condensation reaction) for 5 to 30 hours, preferably for 10 to 20 hours, preferably at 30 to 60 ° C., preferably at room temperature, in the presence of an acid catalyst or a base catalyst added preferably by 1 to 2 parts by mass. It becomes a liquid condensate at room temperature.
Specific examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, n-butylphosphoric acid; tin-based acid catalysts such as dibutyltin dilaurate and dioctyltin; tetraisopropoxytitanium and titanium acetylacetonate. Specific examples of the base catalyst include amine catalysts such as triethylamine, pyridine, and 2,4,6-tris (dimethylaminomethyl) phenol. . Of these, triethylamine and pyridine are preferably used because the base catalyst can be easily removed by desolvation after the condensation reaction.

Further, as described above, the silane condensate used in the curable composition of the present invention may further contain silicate, alkoxysilane, halogenoalkoxysilane, polysiloxane, polydimethylsiloxane, silane coupling agent, and the like. .
Here, the silicate is a compound represented by the following general formula (7). Specific examples thereof include tetrahydroxysilane, tetramethoxysilane, tetraethoxysilane (TEOS), and tetrapropoxysilane. Can be mentioned.

In the general formula (7), each R ^a is an independently branched alkyl group having 1 to 8 carbon atoms. Specific examples thereof include R ² and R ³ in the general formula (1). The alkyl group illustrated can be mentioned.

  The alkoxysilane is a compound represented by the following general formula (8), and specific examples thereof include compounds represented by the following formulas (9), (10) and (11). Can be mentioned.

In the general formula (8), R ^b is each independently an alkyl group having 1 to 8 carbon atoms, and specific examples thereof include R ² and R ³ in the general formula (1). The alkyl group illustrated can be mentioned, m is an integer of 2-10.

  The halogenoalkoxysilane is a compound represented by the following general formula (12).

In the general formula (12), R ^c and R ^d are each independently an alkyl group having 1 to 3 carbon atoms, R ^e is a divalent hydrocarbon group having 1 to 9 carbon atoms, and X is a halogen atom And k is an integer of 1 to 3. Moreover, several ^Rc or ^Rd may be same or different, respectively.
Specific examples of the alkyl group having 1 to 3 carbon atoms of R ^c and R ^d include, for example, a methyl group, an ethyl group, and a propyl group, and R ^e is a divalent hydrocarbon having 1 to 9 carbon atoms. Examples of the group include a divalent aliphatic hydrocarbon group such as an alkylene group and a vinylene group; a divalent alicyclic hydrocarbon group such as a 1,4-cyclohexylene group; a 1,4-phenylene group, and a 1,3 group. -A divalent aromatic hydrocarbon group such as a phenylenebis (methylene) group; and a combination thereof. More specifically, preferred examples of the alkylene group include an ethylene group, a 1,3-propylene group, a 1,4-butylene group, and a 1,8-octylene group.
Specific examples of the halogen atom for X include F (fluorine), Cl (chlorine), Br (bromine), and the like.

  Specific examples of the polysiloxane include compounds represented by the following formulas (13) and (14).

  Specific examples of the polydimethylsiloxane include a compound having a mercapto group represented by the following general formula (15), a compound having a sulfide bond represented by the following general formula (16), and the following general formula The compound which has a silanol group represented by Formula (17) is mentioned, More specifically, the compound represented by following formula (18) and (19) is illustrated suitably.

In the general formula (15), R ^f is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ^g is independently a methyl group or an ethyl group, and R ^h is 1 having 1 to 10 carbon atoms. It is a valent hydrocarbon group and may contain at least one heteroatom selected from the group consisting of O, N and S. R is a number from 10 to 1000.
Specific examples of the divalent hydrocarbon group having 1 to 10 carbon atoms of R ^f include the divalent hydrocarbon groups exemplified by R ^e in the general formula (12).
Specific examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms of R ^h include, for example, monovalent aliphatic hydrocarbon groups such as alkyl groups and vinyl groups; monovalent hydrocarbon groups such as cyclohexyl groups. Examples include alicyclic hydrocarbon groups; monovalent aromatic hydrocarbon groups such as phenyl groups; and groups combining these. More specifically, preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-octyl group.

Moreover, in said general formula (16), ^Rf is a C1-C10 bivalent hydrocarbon group, ^Rg is a methyl group or an ethyl group each independently, x is an integer of 2-6. is there. A plurality of R ^f and R ^g may be the same or different.
Here, R ^f and R ^g are basically the same as those described in the general formula (15).
Moreover, in the said General formula (17), s is a number of 5-1000.

  Further, as the silane coupling agent, specifically, for example, methyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Su- [3- (triethoxysilyl) -propyl] -disulfide, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, trimethoxysilylpropyl-N, N represented by the following formula (20) -Dimethylthiocarbamoyl-tetrasulfide, trimethoxysilylpropyl-mercaptobenzothiazole-tetrasulfide represented by the following formula (21), triethoxysilylpropyl-methacrylate-monosulfide represented by the following formula (22), Examples thereof include methyldimethoxysilylpropyl-N, N-dimethylthiocarbamoyl-tetrasulfide represented by (23), a compound represented by the following formula (24), and the like.

  The total content in the case of containing such silicate, alkoxysilane, halogenoalkoxysilane, polysiloxane, polydimethylsiloxane, silane coupling agent and the like is 50 mass with respect to the total mass of the silane condensate after inclusion. % Or less, and more preferably 20% by mass or less.

In the curable composition of the present invention containing such a silane condensate, the silane condensate contributes to the improvement of the heat resistance, elastic modulus, strength, heat resistance, corrosion resistance and optical properties of the obtained cured product. Useful. This is considered to be because the silane condensate has a three-dimensional cross-linked structure by condensation, and the silane condensate is further cross-linked by the maleimide compound in the curing reaction with the maleimide compound described later. It is done.
Further, as described above, if the silane condensate is liquid at room temperature, the curable composition of the present invention containing the silane condensate may undergo mixing and curing reaction without using a solvent. It is particularly useful because it can.

<Maleimide compound>
The maleimide compound used for the curable composition of this invention will not be specifically limited if it is a compound which has two or more maleimide groups represented by following General formula (5) in 1 molecule.

In the general formula (5), R ⁹ and R ¹⁰ are each independently a hydrogen atom or an optionally branched alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.
Specific examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and isopentyl group. , Neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group and the like.

Among these, as R ⁹ and R ¹⁰ , both are a hydrogen atom, one is a hydrogen atom and the other is an alkyl group, and both are an alkyl group, a maleimide group represented by the general formula (5), It is preferable because the addition reaction with the amino group, imino group or thiol group in the silane condensate easily proceeds.

  The maleimide compound having two or more maleimide groups represented by the general formula (5) in one molecule is a compound represented by the following general formula (25), and in the following general formula (25), A bismaleimide compound which is a compound represented by t = 2 is preferable.

In the above general formula (25), t is an integer of 2 or more, preferably 2 or 3, and R ⁹ and R ¹⁰ are each independently a hydrogen atom or a branch having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. And a plurality of R ⁹ and R ¹⁰ may be the same or different from each other.
R ¹¹ is not particularly limited as long as it is an organic group, and may be a non-cyclic aliphatic group having 1 to 24 carbon atoms which may be branched, a cyclic aliphatic group having 5 to 18 carbon atoms which may be branched, or carbon. It is preferably an optionally branched aromatic group having 6 to 18 carbon atoms or an optionally substituted alkyl aromatic group having 7 to 24 carbon atoms, and at least selected from the group consisting of O, N and S One kind of hetero atom may be contained.

Here, R ⁹ and R ¹⁰ are basically the same as those described in the general formula (5).
Specific examples of the optionally substituted non-cyclic aliphatic group having 1 to 24 carbon atoms, which is preferably exemplified as the organic group for R ¹¹ , include, for example, a methylene group, an ethylene group, and 1,3- Propylene group, 1,4-butylene group, 1,8-octylene group, 1,10-decylene, 1,12-dodecylene group; propane-1,2,3-triyl group, butane-1,2,4-triyl Groups, etc.
Specific examples of the cyclic aliphatic group having 5 to 18 carbon atoms which may be branched include, for example, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group; and cyclopentane-1, 3,4-triyl group, cyclohexane-1,3,5-triyl group, etc.
Specific examples of the aromatic group optionally having 6 to 18 carbon atoms include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2-methyl- 1, 4-phenylene group, biphenyl-4,4′-diyl group, diphenylmethane-4,4′-diyl group, diphenylsulfone-3,3′-diyl group, a substituent represented by the following formula (26); A phenyl-1,3,5-triyl group etc. are mentioned.

  Specific examples of the alkyl aromatic group having 7 to 24 carbon atoms which may be branched include, for example, 3,3′-dimethylbiphenyl-4,4′-diyl group, 3,3 ′, 5,5. Examples include a '-tetramethyldiphenylmethane-4,4'-diyl group.

Of these, R ¹¹ in the general formula (25) is 1,2-phenylene group, 1,3-phenylene group, diphenylmethane-4,4′-diyl group, diphenylsulfone-3,3′-diyl. The group is preferable because the molecular skeleton of the obtained cured product becomes rigid and heat resistance is improved.
In addition to these, R ¹¹ in the general formula (25) may be a residue obtained by removing the maleimide group represented by the general formula (5) from a specific example of the maleimide compound described later.

Here, specific examples of the maleimide compound represented by the general formula (25) include 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, N, N′-1,2, and the like. -Phenylene dimaleimide, N, N'-1,3-phenylene dimaleimide, N, N'-1,4-phenylene dimaleimide, N, N'-1,4-phenylene-2-methyl dimaleimide, N, N ′-(1,1′-biphenyl-4,4′-diyl) bismaleimide, N, N ′-(3,3′-dimethyl-1,1′biphenyl-4,4′-diyl) bismaleimide, 4,4'-diphenylmethane bismaleimide, N, N '-(methylenebis (2-chloro-4,1-phenylene)) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (trade name) : MI-70 (manufactured by KAI Kasei Co., Ltd.)), 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (trade name: BMI-80 (manufactured by KAI Kasei Co., Ltd.)), N, N ′-(sulfonyl) T = 2 such as bis (1,3-phenylene)) dimaleimide, N, N ′-(4,4′-trimethylene glycol dibenzoate) bismaleimide, compounds represented by the following formulas (27) to (34) A compound represented by t = 3 such as a compound represented by the following formulas (35) and (36), etc., and these may be used alone or in combination of two or more. You may use together. Further, it may be a maleimide-modified polymer compound (resin, rubber, etc.).
Of these, it is economical to use 1,6-bismaleimide hexane, 1,2-bismaleimide ethane, N, N′-1,3-phenylene dimaleimide, or 4,4′-diphenylmethane bismaleimide. To preferred.

The curable composition of the present invention containing such a maleimide compound is useful because the maleimide compound contributes to improving the heat resistance of the resulting cured product. This is presumably because the molecular skeleton is rigid.
In the curable composition of the present invention, the maleimide compound has an amino group (—NH ₂ ) and / or imino group (—NH—) of 1.0 equivalent of the silane condensate, or a thiol group of 1.0. The reason that the maleimide group of the maleimide compound is contained in a proportion of 0.1 to 5.0 equivalents, preferably 1.0 equivalent, with respect to the equivalent is to improve the crosslinking density of the resulting cured product. preferable.
Here, in the above “amino group (—NH ₂ ) and / or imino group (—NH—) 1.0 equivalent”, “amino group (—NH ₂ ) and imino group (—NH—) 1.0 equivalent” Means “1.0 equivalent in total of amino group (—NH ₂ ) and imino group (—NH—)”.

<Curing agent>
The curable composition of the present invention may further contain a curing agent having an amino group and / or a thiol group as a curing agent other than the aminosilane compound or the mercaptosilane compound, if desired.

  Specific examples of the curing agent having an amino group include primary amines such as butylamine, hexylamine, octylamine, dodecylamine, oleylamine, cyclohexylamine, benzylamine, methanediphenyldiamine (MDA); Secondary amines such as butylamine; polyamines such as diethylenetriamine, triethylenetetramine, guanidine, diphenylguanidine, xylylenediamine; triethylenediamine, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8- Cyclic amines such as diazabicyclo [5.4.0] -7-undecene; aminoalcohol compounds such as monoethanolamine, diethanolamine, and triethanolamine; 2,4,6-tris (dimethylaminometh) And amine compounds such as aminophenol compounds such as phenol, carboxylates of these amine compounds; quaternary ammonium salts such as benzyltriethylammonium acetate; low polyamines obtained from excess polyamines and polybasic acids. A molecular weight amide resin or the like can also be used.

  Specific examples of the curing agent having a thiol group include 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, and 1,3-benzene. Dithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol 1,2-propanedithiol, 1,3-propadithiol, toluene-3,4-dithiol, 3,6-dichloro-1,2-benzenedithiol, 1,3,5-triazine-2,4,6- Trithiol (trimercapto-triazine), 1,5-naphthalenedithiol, 1,2-benzenedimethanethiol, 1,3- Zendimethanethiol, 1,4-benzenedimethanethiol, 4,4′-thiobisbenzenethiol, 2-di-n-butylamino-4,6-dimercapto-s-triazine, trimethylolpropane tris (β- Dithiols such as thiopropionate), 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6-dioxaoctane, 1,5-dimercapto-3-thiapentane; Name: Thiol compounds such as polythiol such as Thiocol LP70 (manufactured by Toraythiol Co.).

In addition, the curing agent to be added as the case requires, in the curable composition of the present invention, the amino group and / or thiol group of the curing agent is 0.9 equivalent to 1.0 equivalent of the maleimide group of the maleimide compound. It is preferable from the viewpoint of control of physical properties (for example, bending, tension, and compression characteristics) that it is contained at a ratio that is equal to or less than the equivalent.
Here, in the above “amino group and / or thiol group is 0.9 equivalent or less”, “amino group and thiol group is 0.9 equivalent or less” means “the total of amino group and thiol group is 0.9 equivalent or less” ".

<Compound having an epoxy group>
If desired, the curable composition of the present invention may further contain a compound having an epoxy group in addition to the maleimide compound.
Specific examples of the compound having an epoxy group include bisphenyl A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type and the like. A bifunctional glycidyl ether type epoxy resin such as an epoxy compound having a group, a polyalkylene glycol type, an alkylene glycol type epoxy compound, an epoxy compound having a naphthalene ring, an epoxy compound having a fluorene group;
Polyfunctional glycidyl ether type epoxy resins such as phenol novolac type, orthocresol novolak type, DPP novolak type, tris-hydroxyphenylmethane type, trifunctional type, tetraphenylolethane type, etc .;
Glycidyl ester type epoxy resin of synthetic fatty acid such as dimer acid;
N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM), tetraglycidyl-m-xylylenediamine, triglycidyl-p-aminophenol, N, N-diglycidyl represented by the following formula (37) An aromatic epoxy resin having a glycidylamino group in aniline mould;

Formula (38) epoxy compound having a tricyclo [5,2,1,0 ^2,6] decane ring represented by, specifically, for example, the cresols or phenols such as dicyclopentadiene and cresol An epoxy compound which can be obtained by a known production method of reacting epichlorohydrin after polymerization;

式中、ｍは、０〜１５の整数を表す。

In formula, m represents the integer of 0-15.

  Cycloaliphatic epoxy resin; epoxy resin represented by Toraythiol Co., Ltd. Frep 10 epoxy resin main chain having sulfur atom; urethane modified epoxy resin having urethane bond; polybutadiene, liquid polyacrylonitrile-butadiene rubber or acrylonitrile butadiene rubber Examples thereof include a rubber-modified epoxy resin containing (NBR).

In addition, the compound having an epoxy group, which is optionally added, is 1.0 equivalent of the amino group (—NH ₂ ) and / or imino group (—NH—) of the silane condensate in the curable composition of the present invention. Alternatively, the ratio of the epoxy group of the compound having an epoxy group to 0.9 equivalent or less with respect to 1.0 equivalent of the thiol group is a control of physical properties (for example, bending, tensile, and compression characteristics). It is preferable from the viewpoint.

In addition to the above components, the curable composition of the present invention can contain an organic solvent as desired in order to improve ease of preparation and workability of the coating process.
The organic solvent is not particularly limited as long as it is inert to the above components and has an appropriate volatility.
Specific examples of the organic solvent include m-cresol, methyl ethyl ketone, dimethylacetamide, acetone, ethyl acetate, butyl acetate, cellosolve acetate, mineral spirit, toluene, xylene, n-hexane, isohexane, methylene chloride, tetrahydrofuran, Examples thereof include ethyl ether and dioxane, which may be used alone or in combination of two or more.
Among these, the use of m-cresol, which is a protic solvent, in a polymer of a maleimide compound in which a proton in the solvent is generated by addition of a nucleophile (for example, a curing agent having an amino group or a thiol group) This is preferable because the possibility that the polymerization reaction of the maleimide compound continuously occurs by adding the anion to the maleimide group is reduced.
These organic solvents are preferably used after sufficiently dried.

  In addition, the curable composition of the present invention is a dehydrating agent, a plasticizer, a filler, a reinforcing agent, an anti-sagging agent, a colorant (pigment), an anti-aging agent, as necessary, within the range where the effects of the present invention are exhibited. Various additives such as a contact accelerator may be blended.

  Specific examples of the dehydrating agent include, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthoisopropionate, triethyl orthoisopropionate, Hydrolysable ester compounds such as trimethyl orthobutyrate, triethyl orthobutyrate, trimethyl orthoisobutyrate, triethyl orthoisobutyrate; or dimethoxymethane, 1,1-dimethoxyethane, 1,1-dimethoxypropane, 1,1-dimethoxybutane; or Ethyl silicate (tetramethoxysilane), methyl silicate (tetramethoxysilane), methyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, and other vinylsilanes . Of these, vinylsilane is preferably used from the viewpoint of dehydration effect. These may be used alone or in combination of two or more.

Plasticizers are used to adjust viscosity and physical properties, and generally include derivatives such as benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, and citric acid. Examples thereof include polyester, polyether, and epoxy.
Various fillers can be blended in order to adjust the mechanical properties. Generally, calcium carbonate, talc, silica, carbon black, etc. are used. Depending on the activity of the filler, particle shape, pH, presence / absence of surface treatment, etc., the effect on storage stability, curing speed, physical properties, and foaming is large, and it is necessary to be careful in determining the type and amount. Particularly, calcium carbonate treated with a fatty acid ester or a higher alcohol urethane compound is preferably used.

Specific examples of the colorant (pigment) include, for example, inorganic pigments such as titanium oxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, azo pigments, Phthalocyanine pigment, quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, anthrapyrimidine pigment, ansanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, perinone pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment, anthraquinone pigment, thioindigo pigment And organic pigments such as benzimidazolone pigments, isoindoline pigments, and carbon black.
As specific examples of the antioxidant, commonly used antioxidants, ultraviolet absorbers, light stabilizers, and the like are appropriately used. Examples include hindered amine, benzotriazole, benzophenone, benzoate, cyanoacrylate, acrylate, hindered phenol, phosphorus, and sulfur compounds.

  As described above, when the silane condensate is a liquid at room temperature, the curable composition of the present invention having such a structure has a solvent when mixing and curing the silane condensate and the maleimide compound. It is not necessary to use, and as shown in the examples described later, since the glass transition temperature of the obtained cured product is 300 ° C. or higher, it is useful because it has an effect of having high heat resistance.

The method for producing the curable composition of the present invention is not particularly limited. For example, the silane condensate, the maleimide compound, and the curing agent to be contained as required, a compound having an epoxy group, an organic solvent, and various additives are mixed. The mixture is sufficiently mixed using a roll, a kneader, an extruder, a universal stirrer or the like at room temperature or under heating (40 to 60 ° C., for example, 40 ° C.) and dispersed uniformly.
In the curable composition of the present invention, if the aminosilane compound forming the silane condensate is an aliphatic aminosilane compound, the curing reaction proceeds at room temperature for 2 hours or more, preferably about 5 to 10 hours. If the aminosilane compound that forms the silane condensate is an aromatic aminosilane compound, the curing reaction proceeds at 180 ° C. or higher for 2 hours or longer, preferably 180 to 200 ° C. for 2 to 10 hours, and the silane condensate is mercapto. If it is formed of a silane compound, the curing reaction proceeds at 180 ° C. or higher for 2 hours or longer, preferably 180 to 200 ° C. for 2 to 10 hours.
Furthermore, when the silane condensate is liquid at room temperature, the curing reaction proceeds without using a solvent.

  Although the use of the hardened fat composition of the present invention is not particularly limited, for example, it can be used for a semiconductor sealing agent, a binder resin for a conductive adhesive, a prepreg, a sealing material, and the like.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this.
(Synthesis of silane condensate 1)
By stirring 500 g of N-phenyl-γ-aminopropyltrimethoxysilane in the presence of 35.3 g of water and 7 g of triethylamine (N (Et) ₃ ) at room temperature for 15 hours, it is represented by the following formula (39). Silane condensate 1 was obtained as a white-yellow transparent liquid.

(Synthesis of silane condensate 2)
Silane condensate 2 represented by the following formula (40) was obtained as a white transparent liquid by stirring 35.9 g of γ-aminopropyltrimethoxysilane in the presence of 3.6 g of water at room temperature for 1 hour. .

(Synthesis of silane condensate 3)
Silane condensate 3 represented by the following formula (41) is obtained as a white transparent liquid by stirring 100.0 g of γ-mercaptopropyltrimethoxysilane in the presence of 18.3 g of water at 50 ° C. for 5 hours. It was.

Example 1
A composition containing the obtained silane condensate 1 and 4,4'-diphenylmethane bismaleimide (BMI) in the composition components (functional group ratio) shown in Table 1 below using a universal stirrer at room temperature without solvent. After mixing, the cured product of Example 1 represented by the following formula (42) was obtained by heating at 180 ° C. for 4 hours (180 ° C. × 4 hours).

(Example 2)
The composition containing the obtained silane condensate 2 and 4,4'-diphenylmethane bismaleimide (BMI) as composition components (functional group ratios) shown in Table 1 below using a universal stirrer at room temperature without solvent. After mixing, the cured product of Example 2 represented by the following formula (43) was obtained by heating at 180 ° C. for 4 hours (180 ° C. × 4 hours).

(Example 3)
A composition containing the obtained silane condensate 3 and 4,4'-diphenylmethane bismaleimide (BMI) as composition components (functional group ratios) shown in Table 1 below using a universal stirrer without solvent at room temperature. After mixing, the cured product of Example 3 represented by the following formula (44) was obtained by heating at 180 ° C. for 4 hours (180 ° C. × 4 hours).

(Comparative Examples 1 and 2)
A composition containing an amine curing agent (methanediphenyldiaminemaleimide (MDA)) and 4,4′-diphenylmethanebismaleimide (BMI) in the compositional components (functional group ratios) shown in Table 1 below is represented by N-methyl-2. -Using pyrrolidone (NMP), NMP was distilled off after mixing in a flask at 100-130 ° C. Then, the hardened | cured material of the comparative examples 1 and 2 was obtained by heating at 200 degreeC for 1 day (200 degreeC x 1 day).

The temperature dependence of the elastic modulus (G ′, G ″) and tan δ of each obtained cured product was examined (temperature rising condition: 5 ° C./min). Here, G ′ (Gee prime) means storage elastic modulus (Pa), and G ″ (Gee double prime) means loss elastic modulus (Pa).
In the cured products of Comparative Examples 1 and 2, the elastic modulus (G ′) greatly decreased in the high temperature range from the glass transition temperature Tg (around 280 ° C.), whereas the cured products of Examples 1, 2 and 3 It was found that in the temperature range of 300 ° C. or lower, the glass transition point Tg disappeared, the elastic modulus (G ′) was not greatly reduced, and the heat resistance was improved.
The glass transition temperatures (Tg) of Examples 1, 2, and 3 and Comparative Examples 1 and 2 are shown in Table 1 below. The temperature, elastic modulus (G ′, G ″) and tan δ of the cured product of Example 1 The relationship is shown in FIG.

4 is a graph showing the relationship between temperature, elastic modulus (G ′, G ″) and tan δ in the cured product of Example 1.

Claims (11)

A silane condensate containing at least one of the aminosilane compounds represented by the following general formulas (1) to (4) as a constituent component;
A maleimide compound having two or more maleimide groups represented by the following general formula (5) in one molecule ;
The maleimide compound is contained at a ratio of 0.1 to 5.0 equivalents of the maleimide group of the maleimide compound with respect to 1.0 equivalent of the amino group and / or imino group of the silane condensate,
A curable composition in which the silane condensate and the maleimide compound cause a curing reaction .

Wherein R ¹ is an alkylene group having 1 to 12 carbon atoms, R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms, and R ⁴ is 1 carbon atom. Is an alkylene group having ˜12, R ⁵ is an optionally branched alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and R ⁶ is carbon. An alkylene group having 1 to 12 carbon atoms, R ⁷ and R ⁸ are each independently an alkylene group having 1 to 12 carbon atoms, and n is an integer of 0 to 2. A plurality of R ¹ , R ^2, and R ³ May be the same or different, and R ⁹ and R ¹⁰ are each independently a hydrogen atom or an optionally branched alkyl group having 1 to 8 carbon atoms.)   The curable composition according to claim 1, wherein the aminosilane compound is an aromatic aminosilane compound.   Furthermore, the curable composition of Claim 1 or 2 containing the hardening | curing agent which has an amino group and / or a thiol group.   Furthermore, the curable composition in any one of Claims 1-3 containing the compound which has an epoxy group. Curing according a pre Symbol curing agent, to claim 3 with respect to the maleimide group 1.0 equivalent of the maleimide compound, an amino group and / or thiol groups of the curing agent in a proportion equal to or less than 0.9 equivalents Sex composition. The compound having a front Symbol epoxy group, the amino group and / or imino group 1.0 equivalent of the silane condensates, epoxy group of a compound having the epoxy group is contained in a ratio equal to or less than 0.9 equivalents The curable composition according to claim 4. A silane condensate containing a mercaptosilane compound represented by the following general formula (6) as a constituent component;
A maleimide compound having two or more maleimide groups represented by the following general formula (5) in one molecule ;
The maleimide compound is contained in a ratio such that the maleimide group of the maleimide compound is 0.1 to 5.0 equivalents relative to 1.0 equivalent of the thiol group of the silane condensate,
A curable composition in which the silane condensate and the maleimide compound cause a curing reaction .

(In the formula, R ¹ is an alkylene group having 1 to 12 carbon atoms, R ² and R ³ are each independently an alkyl group having 1 to 8 carbon atoms, and n is 0 to 2). R ² or R ³ may be the same or different from each other, and R ⁹ and R ¹⁰ may each independently be a hydrogen atom or branched from 1 to 8 carbon atoms. An alkyl group.) Furthermore, the curable composition of Claim 7 containing the hardening | curing agent which has an amino group and / or a thiol group. Furthermore, the curable composition of Claim 7 or 8 containing the compound which has an epoxy group. Curing according a pre Symbol curing agent, in claim 8 with respect to the maleimide group 1.0 equivalent of the maleimide compound, an amino group and / or thiol groups of the curing agent in a proportion equal to or less than 0.9 equivalents Sex composition. Describes a compound having the previous SL epoxy groups, to claim 9 to a thiol group 1.0 equivalent of the silane condensates, epoxy group of a compound having the epoxy group is contained in a ratio equal to or less than 0.9 equivalents Curable composition.

Images