JP2006056933A - Thermosetting composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition which is useful in use for raw materials for paints, coatings, sheet-like materials, sealants, adhesives, molding materials, casting materials and the like and gives a cured product curable even in thick film, heat resistant, containing least ionic impurities and excellent in heat resistance without using an organic solvent. <P>SOLUTION: The thermosetting composition contains (A) a silane-modified oligomer obtained by dealcoholization-condensating (A-1) a compound having a hydroxy group and a cationic ring-opening polymerizable group in the molecule and (A-2) an alkoxy silane, (B) a compound expressed by formula (1) and (C) an organic aluminum compound capable of generating a protonic acid. In formula (1), R represents a hydrogen atom or a 1-6C alkyl group which may or may not be branched. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermosetting composition containing a compound having a specific cationic ring-opening polymerizable group. The composition of the present invention has a thick film curability, is excellent in heat resistance, chemical resistance, electrical characteristics and the like, and gives a cured product with few ionic impurities. It is useful as a material such as a stopper, an adhesive, a molding material, and a casting material.

  Conventionally, an epoxy resin is generally used as an epoxy resin composition in combination with a curing agent, and the composition has been used in the field of electrical / electronic materials. However, with the recent development of the electric / electronic materials field, the epoxy resin cured product is required to have high performance, and in particular, improvement in heat resistance is desired. As a method for improving the heat resistance of the cured epoxy resin, a method using a composite of an epoxy resin and a metal oxide has been proposed (for example, see Patent Document 1). The composite is obtained by adding a metal alkoxide to a solution obtained by partially curing an epoxy resin to obtain a homogeneous sol solution, and then polycondensing the metal alkoxide. However, the cured product obtained from such a composite has a certain degree of improvement in heat resistance as compared to a cured product of a simple epoxy resin, but the cured product is caused by water in the composite, water generated during curing, or alcohol. Voids (bubbles) are generated inside. If the amount of metal alkoxide is increased for the purpose of further improving the heat resistance, the transparency of the cured product obtained by agglomeration of silica produced by sol-gel curing is lost and whitening occurs, and a large amount of metal alkoxide is dissolved in sol. Therefore, a large amount of water is required to convert the resin, and as a result, warpage of the cured product, cracks and the like are caused. In order to improve such defects, a thermosetting composition in which a hydroxyl group of a bisphenol type epoxy resin is modified with a hydrolyzable alkoxysilane and a specific silane-modified epoxy resin is blended with an epoxy resin curing agent has been proposed. (For example, refer to Patent Document 2). Even in the composition proposed by this invention, in order to complete the formation of the inorganic component, it is necessary to remove the lower alcohol bonded to the silane residue, and it is difficult to cure with a thick film. If the ratio of the bisphenol type epoxy resin is increased in order to avoid such an adverse effect of lower alcohol, the viscosity of the composition becomes high, and dilution with an organic solvent is necessary when using the composition, and a complicated drying operation is required. there were.

In general, it is known that an epoxy resin using an acid anhydride or a phenol has a relatively low thermosetting rate. As a thermosetting composition capable of improving the curing rate, one using an epoxy compound using an onium salt having thermal potential is known. Various materials for various epoxy compounds and various cationic curing initiators are widely studied. Has been. However, in the thermal cation curing using the above-described onium salt, there is a concern that the strong acid remaining after the curing has an adverse effect, and therefore the applicable range is limited to limited applications.
In electrical applications, in recent years, electrical circuits have become more multilayered and denser due to miniaturization of electrical equipment. Along with this, heat resistance, low dielectric constant, arc resistance, and tracking resistance are required for the epoxy resin used therein. Ionic residues are known to cause significant deterioration of electrical properties such as decreased electrical insulation, increased dielectric constant, and loss tangent value. To improve these electrical properties, ionic residues Reduction is necessary.

  An epoxy compound polymerization catalyst comprising a specific organosilicon compound and an organic aluminum compound is known (see, for example, Patent Document 3) as an agent that can improve such an adverse effect caused by the remaining of acid. And the epoxy resin composition (for example, refer patent document 4) formed by mix | blending this catalyst and the epoxy resin composition (for example refer patent document 5) which mix | blended alumina instead of the organic aluminum compound are disclosed. . In the curing systems disclosed by these inventions, it has been proposed to use alkoxysilanes as a method of imparting thermal potential to the composition. However, in some cases, the lower alcohol released during the thermosetting process may form voids or remain in the cured product to reduce various properties of the cured product.

  Protonic acid is generated by the interaction between the silane-modified oligomer (A) obtained by reacting the compound (A-1) having a hydroxyl group and a cationic ring-opening polymerizable group with the alkoxysilane (A-2), and a silanol group. Thermosetting composition in which a compound (C) having a cationic ring-opening polymerizable group other than the silane-modified oligomer (A) is added to a thermosetting composition containing an aluminum compound (B) The thing is reported (for example, refer patent document 6). Examples of the compound (C) having a cationic ring-opening polymerizable group include an aliphatic oxetane compound having two oxetanyl groups in one molecule, and a specific compound is bis (3-ethyl-3-oxetanyl). Methyl) ether).

  The thing which the following formula (4) couple | bonded with the cyclohexane is illustrated (for example, refer patent document 7).

As R < ₂ > of Formula (4), the alkyl group etc. which may have a hydrogen atom or a C1-C6 branch etc. are illustrated. However, this report does not synthesize by way of example only.

  Synthesis of 3-ethyl-3-cyclohexyloxymethyloxetane has been reported (see, for example, Patent Document 8). This report is only a manufacturing method and there is no description of a curing example.

Japanese Patent Laid-Open No. 08-100107 JP 2001-59013 A Japanese Examined Patent Publication No. 57-57488 Japanese Patent Publication No.57-57487 Japanese Patent Publication No.57-57490 JP 2003-12879 A Japanese Patent Laid-Open No. 10-158581 JP 2003-012661 A

  The present invention solves the above problems and is useful as a material such as a paint / coating agent, a sheet-like material, a sealing material, an adhesive, a molding material, a casting material, and the like, without using an organic solvent. It is an object of the present invention to provide a curable composition that can be cured and provides a cured product with less ionic impurities and excellent heat resistance.

  In order to solve the above-mentioned problem, it is obtained by subjecting a compound (A-1) having a hydroxyl group and a cationic ring-opening polymerizable group in the molecule to an alkoxysilane (A-2) to a dealcoholization condensation reaction. A thermosetting composition containing a silane-modified oligomer (A), a compound (B) represented by the following general formula (1), and an organoaluminum compound (C) capable of generating a protonic acid.

  R in the formula (1) represents a hydrogen atom or an alkyl group which may have 1 to 6 carbon atoms.

  The silane-modified oligomer (A) is represented by the following general formula (2).

  X in the formula (2) is represented by the following general formula (3), Y is a methoxy group and / or ethoxy group, n is a number from 1 to 10, and a is between 0 and 2. m is 0 to 3 and the value in (5-am) / (a + m + 1) is 0 to 1. Note that n in the formula (2) is an average value.

R _{1 in the} formula (3) represents an alkyl group which may have a branch having 1 to 6 carbon atoms.

The thermosetting composition described above can be further blended with a compound (D) having at least one cationic ring-opening polymerizable group in the molecule.
And it is a hardened material formed by heating the above-mentioned thermosetting composition.
Hereinafter, the present invention will be described in more detail.

  The silane-modified oligomer (A) of the present invention comprises a compound having a hydroxyl group and a cationic ring-opening polymerizable group (A-1, hereinafter A-1 component) and alkoxysilanes (A-2, hereinafter A-2 component) in the molecule. ) And a dealcoholization reaction.

  The A-1 component is not particularly limited as long as it is a compound having a hydroxyl group and a cationic ring-opening polymerizable group in the molecule, but is a compound and an epoxy group in which the cationic ring-opening polymerizable group is an oxetanyl group. A compound (hereinafter also referred to as a hydroxyl group-containing epoxy resin) can be exemplified.

  Examples of the compound in which the component A-1 is an oxetanyl group include those represented by the following general formula (5), and examples of the hydroxyl group-containing epoxy resin include an epoxy compound having a bisphenol skeleton (also referred to as a bisphenol type epoxy resin). It can be illustrated.

R _{1 in the} formula (5) represents an alkyl group which may have a branch having 1 to 6 carbon atoms.

  Examples of the compound represented by the formula (5) that can be used as the A-1 component include 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane.

  The bisphenol type epoxy resin that can be used as the component A-1 is obtained by a reaction between bisphenols and a haloepoxide such as epichlorohydrin or β-methylepichlorohydrin. Examples of bisphenols used include bisphenol F, bisphenol A, and compounds in which two methyl groups of bisphenol A are substituted with trifluoromethyl. Among these bisphenol-type epoxy resins, in particular, bisphenol A-type epoxy resins using bisphenol A as bisphenols are the most widely used and are inexpensive and preferable. The bisphenol type epoxy resin has a hydroxyl group that can react with the A-2 component. The bisphenol type epoxy resin may be a mixture of one having only one bisphenol unit and two or more having the bisphenol unit. The former has no hydroxyl group in the molecule, and the latter has one or more hydroxyl groups in the molecule. Have. Such a mixture may be sufficient as the bisphenol type epoxy resin used by this invention. The epoxy equivalent of the bisphenol-type epoxy resin varies depending on the structure of the bisphenol-type epoxy resin, and an epoxy equivalent according to the application can be appropriately selected and used. If the epoxy equivalent is too small, there are few alcoholic hydroxyl groups in the epoxy resin, so the reaction with the component A-2 is not carried out smoothly, and the resulting silane-modified oligomer (A) tends to have poor uniformity and is further obtained. The cured product may become cloudy. Therefore, the epoxy equivalent of the bisphenol type epoxy resin is preferably 180 (g / eq) or more. On the other hand, if the epoxy equivalent is too large, the number of hydroxyl groups in one molecule of the epoxy resin increases, and gelation is likely to occur during the dealcoholization condensation reaction with the A-2 component. Therefore, the epoxy equivalent of the bisphenol-type epoxy resin is 1000 (g / Eq) or less is preferred.

  A compound represented by the formula (5) and a hydroxyl group-containing epoxy resin can be used in combination, whereby the fluidity of the composition and the physical properties of the cured product can be controlled. When these are used in combination, the mixing ratio can be arbitrary.

  In order to make the thermosetting composition of the present invention have a relatively low viscosity and good workability, the blending ratio of the A-1 component when producing the silane-modified oligomer (A) is 50% by mass or more. This is preferably 60% by mass or more, and more preferably 70% by mass or more.

  When the bisphenol type epoxy resin is used as the A-1 component, it is preferable because the resulting cured product has excellent heat resistance, but the one using the compound represented by the formula (5) is particularly thick film cured. It is preferable because the cured product obtained is excellent in heat resistance and has particularly excellent heat resistance. As the compound represented by the formula (5) used as the component A-1, 3-hydroxymethyl-3-methyloxetane or 3-hydroxymethyl-3-ethyloxetane is preferable.

As alkoxysilane (A-2), what is generally used for the sol-gel method can be used. For example, the general formula:
(R ₄ ) _p Si (OR ₅ ) _4-p (6)
(In formula (6), p represents an integer of 0 or 1. R ₄ represents a lower alkyl group, an aryl group or an unsaturated aliphatic residue which may have a functional group directly connected to a carbon atom. R ₅ represents a hydrogen atom or a lower alkyl group, and R ⁵ may be the same or different.
Or a partial condensate thereof. As said functional group, a vinyl group, a mercapto group, an epoxy group, a glycidoxy group etc. can be mentioned, for example. The lower alkyl group means a linear or branched alkyl group having 6 or less carbon atoms. Specific examples of such alkoxysilanes (A-2) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane; methyltrimethoxysilane, methyl Triethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane , Trialkoxysilanes such as 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, or the like And a partial condensate thereof. As the A-2 component, those exemplified above can be used without particular limitation.

  Among these A-2 components, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane or partial condensates thereof are preferable. Particularly preferred is one represented by the following general formula (7).

R _{3 in the} formula (7) represents a methoxy group and / or an ethoxy group, and n represents a number of 1 to 10.

  The number average molecular weight of the formula (7) is preferably about 260 to 1200, and if the value of n exceeds 11, the solubility is deteriorated. From this, the number of n in the formula (7) is preferably 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 5. Note that n in the equation (7) is an average value.

  The silane-modified oligomer (A) of the present invention can be obtained by subjecting the A-1 component and the A-2 component to a dealcohol condensation reaction. The use ratio of the A-1 component and the A-2 component is not particularly limited. However, when the silane-modified oligomer (A) has many lower alkoxy groups such as a methoxy group or an ethoxy group derived from the A-2 component not having a reactive group, the composition is cured. In addition to forming silanol groups, volatile compounds such as methanol or ethanol are likely to be generated, which may cause foaming. Therefore, the silane-modified oligomer (A) is one in which 50% or more of the alkoxy group of the component A-2 is substituted with a residue excluding the hydrogen atom derived from the hydroxyl group of the component A-1 (formula (3) ), More preferably 60% or more is substituted, and particularly preferably 70% or more is substituted.

In addition, a part of the residue except the hydrogen atom derived from the hydroxyl group of the A-1 component introduced into the silane-modified oligomer (A) by the substitution reaction is converted into the A-1 component when the composition is cured. Although it is converted to produce a silanol group at the same time, the A-1 component is used for the curing reaction and thus does not cause foaming.
The composition mainly composed of the silane-modified oligomer (A) in which the concentration of the lower alkoxy group having no reactive group is controlled to be small can be suitably used even when the composition is cured with a thick film.

  The production of the silane-modified oligomer (A) is performed, for example, by charging the A-1 component and the A-2 component and subjecting to a dealcoholization condensation reaction while distilling off the alcohol produced by heating. This reaction temperature is about 50 to 250 ° C, preferably 80 to 200 ° C, and more preferably 90 to 180 ° C. The reaction time at this time is about 1 to 15 hours. This reaction is preferably carried out under substantially anhydrous conditions in order to prevent the polycondensation reaction of the alkoxysilanes (A-2) and to prevent the product from being colored.

  The above dealcoholization condensation reaction is preferably carried out without a catalyst, but a catalyst that does not promote the ring-opening reaction of a cationic ring-opening polymerizable group such as an oxetane ring or an epoxy ring among the conventionally known catalysts for promoting the reaction. Can be used. Specific examples include dibutyltin dilaurate and tin octylate. The above reaction can be performed in a solvent or without a solvent. The solvent is not particularly limited as long as it dissolves the A-1 component and the A-2 component and does not react with these components.

  As R of the compound (B) represented by the above formula (1) blended in the thermosetting composition of the present invention, an alkyl group which may have 1 to 6 carbon atoms is preferable. Further, an alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable. Specific examples of the compound (B) include 3-ethyl-3-cyclohexyloxymethyl oxetane (CHOX) and 3-methyl-3-cyclohexyloxymethyl oxetane.

  The blending ratio of the silane-modified oligomer (A) and the compound (B) represented by the formula (1) in the thermosetting composition of the present invention is expressed by the formula (A) with respect to 100 parts by mass of the silane-modified oligomer (A). The compound (B) represented by 1) is preferably 30 to 150 parts by mass, more preferably 50 to 120 parts by mass, and particularly preferably 60 to 100 parts by mass. The ratio of the silane-modified oligomer (A) and the compound (B) represented by the formula (1) is preferably higher in the silane-modified oligomer (A), and this difference may be 5 parts by mass or more. Preferably, those having a difference of 10 parts by mass or more are preferred. Other than this blending ratio, foaming may occur during curing, or the cured product may not be flexible.

As an aluminum compound (C) mix | blended with the thermosetting composition of this invention, a protonic acid can be generated by interaction with a silanol group. In the present invention, when the silane-modified oligomer (A) is heated, a silanol group is generated, and a protonic acid can be generated by the interaction between the silanol group and the aluminum compound (C).
Examples of the aluminum compound (C) include organoaluminum compounds described in JP-B-57-57488 and JP-B-57489, aluminum complexes and aluminas described in JP-B-57-57491 and JP-B-57492. And inorganic aluminum compounds.

  Examples of the aluminum compound (C) include alkoxides such as aluminum trimethoxide, aluminum tripropoxide and aluminum tributoxide, halides such as aluminum chloride and aluminum fluoride, tris (ethylacetoacetate) aluminum, tris ( Propyl acetate) aluminum, tris (butylacetoacetate) aluminum, propoxybis (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, tris (propionylacetonato) aluminum, chelate compounds such as tris (acetoacetonato) aluminum, alumina, etc. Is mentioned. These can be used alone or in combination of two or more.

  The compounding quantity of an aluminum compound (C) component is 0.001-10 mass parts with respect to 100 mass parts silane modified oligomer (A), Preferably it is 0.01-3 mass parts, Especially 0.01. A range of ˜1 part by mass is preferred. If the blending ratio is less than 0.001 part by mass, the curability may be lowered, and if it exceeds 10 parts by mass, storage stability, yellowing resistance, etc. may be lowered.

The thermosetting composition of the present invention may further contain a compound (D) having one or more cationic ring-opening polymerizable groups in one molecule. In addition, this compound (D) does not contain the compound (B) represented by Formula (1). As this compound (D), a bisphenol type epoxy resin; a novolak type epoxy resin such as an orthocresol novolak type epoxy resin and a phenol novolak type epoxy resin; polybasic acids such as phthalic acid and dimer acid, and epichlorohydrin are reacted. A glycidyl ester type epoxy resin obtained by oxidation; a linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; and an alicyclic epoxy resin can be used. A compound having an oxetane ring in the molecule other than the compound (B) represented by the formula (1) can also be used. Of course, these can also be used together.
In the case of compounding, the amount of the compound (D) used is not particularly limited, but is preferably 0.1 to 1000 parts by mass based on 100 parts by mass of the silane-modified oligomer (A), and further 5 to 100 parts by mass. 10 to 80 parts by mass are particularly preferable.

Specific examples of the compound (D) include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, and 3-ethyl-3-hydroxymethyloxetane as oxetane compounds having one oxetanyl group in one molecule. 1,4-{[(3-Ethyloxetane-3-yl) methoxy] methyl} which is an oxetane compound having two oxetanyl groups in one molecule such as ethyl-3- (2-ethylhexyloxymethyl) oxetane 3,4-bis, which is a bifunctional alicyclic epoxide compound such as benzene, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, bis (3-ethyl-3-oxetanylmethyl) ether) And epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.
Preferred examples of the compound (D) include 3-ethyl-3-hydroxymethyloxetane and 3-ethyl-3- (2-ethylhexyloxymethyl) which are aliphatic oxetane compounds having one oxetanyl group in one molecule. 3,4-epoxycyclohexyl which is a bifunctional alicyclic epoxide compound such as bis (3-ethyl-3-oxetanylmethyl) ether) which is an aliphatic oxetane compound having two oxetanyl groups in one molecule such as oxetane And methyl-3 ′, 4′-epoxycyclohexanecarboxylate.

The thermosetting composition of the present invention may further contain other components as necessary. What is mix | blended below is illustrated.
Powdery reinforcing agents and fillers, eg metal oxides such as magnesium oxide, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, basic magnesium silicate, calcined clay, fine powder silica, fused silica, crystals Silicon compounds such as silica, metal hydroxides, others, kaolin, mica, quartz powder, graphite, molybdenum disulfide, and other fibrous reinforcing agents and fillers such as glass fibers, ceramic fibers, carbon fibers, silicon carbide fibers Boron fibers, polyester fibers and polyamide fibers. These can be blended in an amount of 10 to 900 parts by mass with respect to 100 parts by mass of the composition of the present invention.
Colorants, pigments, flame retardants such as titanium dioxide, iron black, molybdenum red, bitumen, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, bromine compounds and triphenyl phosphate. These can be blended in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the composition of the present invention.
Various synthetic resins can be blended for the purpose of improving the properties of the resin in the adhesive layer, molded product, and the like. For example, 1 type, or 2 or more types of combinations, such as a phenol resin, an alkyd resin, a melamine resin, a fluororesin, a vinyl chloride resin, an acrylic resin, a silicone resin, a polyester resin, can be mentioned. The blending ratio of these resins is preferably 50 parts by mass or less with respect to an amount within a range not impairing the original properties of the resin composition of the present invention, that is, 100 parts by mass of the composition of the present invention.

Examples of the blending means of the composition and optional components of the present invention include heat-melt mixing, roll, melt-kneading using a kneader, wet mixing using an appropriate organic solvent, and dry mixing. The composition of the present invention can be cured by heat. The curing temperature is preferably 50 to 300 ° C, more preferably 60 to 250 ° C, and particularly preferably 80 to 210 ° C.
The heating time may be determined while observing the cured state of the thermosetting composition of the present invention. Specifically, it is preferably 1 to 300 minutes, and more preferably 5 to 250 minutes.
When the polymerization is carried out by heat, it can be heated by a generally known method, and the conditions are not particularly limited.

<Example>
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the part in each example means a mass part.

<Production Example 1>
○ Synthesis of silane-modified oligomer (A) 3-ethyl-3- (hydroxymethyl) oxetane (Aron Oxetane OXT manufactured by Toagosei Co., Ltd.) was added to a 300 mL four-necked glass flask equipped with a stirrer, thermometer and distillation apparatus -101) 100 g and 30 g of tetramethoxysilane oligomer (MKC silicate MS51, manufactured by Mitsubishi Chemical Corp.) were charged, heated and stirred in an oil bath at 80 to 150 ° C., and reacted for 5 hours while distilling methanol. Further, the mixture was heated at 150 ° C. for 2 hours while distilling 3-ethyl-3- (hydroxymethyl) oxetane under reduced pressure. The yield of the final product (silane-modified oligomer (A)) was 53 g.
The molar ratio of oxetanyl group to methoxy group in the final product evaluated from ¹ H-NMR was 98: 2.

<Example 1 and Comparative Example 1>
Silane-modified oligomer (A) synthesized according to Production Example 1, 3-ethyl-3-cyclohexyloxymethyloxetane (manufactured by Toagosei Co., Ltd., CHOX), bis (3-ethyl-3-oxetanylmethyl) ether (Toagosei ( OXT-221), 3-ethyl-3- (2-ethylhexyl) oxetane (manufactured by Toagosei Co., Ltd., OXT-212), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexane Carboxylate (Dow Chemical Japan Co., Ltd., UVR-6110) and tris (acetylacetonato) aluminum (Al (acac) ₃ ) were sufficiently stirred and mixed at room temperature so as to be uniform with the composition shown in Table 1. And then degassing under reduced pressure to obtain a curable resin composition.
Next, 3 g of the above composition was added to a 9 cc glass sample bottle and cured in an oven at 150 ° C. for 2 hours.
Further, the above composition was poured into a mold and cured in an oven at 80 ° C. for 1 hour, 100 ° C. for 1 hour, and further at 200 ° C. for 2 hours to obtain a test piece having a thickness of 1 mm.

The results of the following evaluation for each sample are shown in Table 1.
O Thick film curability: 3 g of the composition was added into a 9 cc glass sample bottle and cured in an oven at 150 ° C. for 2 hours to evaluate the uniformity of the cured product.
○: No foam in the cured product ×: Foam in the cured product ○ Crack resistance: 1 mm thick test sample was folded by hand,
○: not destroyed Δ: cracked ×: assumed to be destroyed

  As shown in Table 1, the compositions shown in Examples 1 to 4 were excellent in thick film curability and very excellent in crack resistance. Moreover, coloring was not recognized by hardened | cured material.

  As is clear from the examples, the thermosetting composition provided by the present invention has thick film curability and crack resistance, is excellent in heat resistance, chemical resistance, electrical properties, etc., and is ionic. It can give a cured product with few impurities and can be applied to a wide range of applications. In particular, it can be advantageously used in applications such as the electric / electronic field as materials such as paints / coating agents, sheet-like materials, sealing materials, adhesives, molding materials, and casting materials.

Claims (4)

A silane-modified oligomer (A) obtained by dealcoholization condensation reaction of a compound (A-1) having a hydroxyl group and a cationic ring-opening polymerizable group in the molecule and an alkoxysilane (A-2), represented by the following general formula ( A thermosetting composition containing the compound (B) represented by 1) and an organoaluminum compound (C) capable of generating a protonic acid.

(R in Formula (1) represents a hydrogen atom or an alkyl group that may have 1 to 6 carbon atoms branched.) The thermosetting composition according to claim 1, wherein the silane-modified oligomer (A) is represented by the following general formula (2).

(X in the formula (2) is represented by the following general formula (3), Y is a methoxy group and / or ethoxy group, n is a number from 1 to 10, and a is between 0 and 2. And m is 0 to 3 and the value in (5-am) / (a + m + 1) is 0 to 1.)

(R _{1 in} Formula (3) represents an alkyl group that may have 1 to 6 carbon atoms branched.)   The thermosetting composition according to claim 1 or 2, further comprising a compound (D) having one or more cationic ring-opening polymerizable groups in the molecule.   Hardened | cured material formed by heating the thermosetting composition of each of Claims 1-3.