JP2008115299A - Curable resin composition and adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide, in a curable resin composition containing an epoxy compound, a cured product which maintains high rigidity in a high temperature region and which has a high glass transition temperature. <P>SOLUTION: Provided is a one-pack or two-pack curable resin composition comprising a layered polymer 1, an epoxy resin and the like. The layered polymer 1 has a tetrahedron sheet 11 which is arranged with a plurality of tetrahedral structures having silicon atoms as the center atoms and an octahedron sheet 12 which is arranged with a plurality of octahedral structures having metallic atoms as the center atoms and has the silicon atoms of the tetrahedron sheet 11 and the metallic atoms of the octahedron sheet 12 linked through oxygen atoms. The layered polymer 1 has epoxy-containing organic groups bonded to the silicon atoms in the tetrahedron sheet 11 and organic groups selected from aryl groups, etc., that are bonded to the silicon atoms in the tetrahedron sheet 11. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable resin composition and an adhesive using the same.

  In order to improve physical properties such as heat resistance of a curable resin composition containing an epoxy compound, studies on so-called hybrid materials in which an inorganic material is combined with an epoxy compound have been made conventionally (for example, Non-Patent Document 1). -3)).

The present inventors have already synthesized a layered polymer containing a layered silicate structure similar to smectite and having an epoxy group introduced therein, and has already reported an organic / inorganic hybrid material in combination with an epoxy compound (non-patent document). Reference 4).
Polymer Papers, 2000, 57 (4), p. 220 Polymer Preprints Japan, 2002, Vol. 51, p. 2253-2254 Polymer, 2001, Vol. 42, p. 4493 Polymer Journal, 2002, Vol. 59, No. 10, p. 631-636

However, in the case of a curable resin composition using a conventional layered polymer into which an epoxy group has been introduced, there is room for further improvement particularly in terms of the rigidity of the cured product at a high temperature. In order to increase the rigidity of the cured product, a method of adding other inorganic fillers such as SiO ₂ particles to the curable resin composition can be considered. However, in the case of a conventional layered polymer, the curable resin is used to increase the viscosity. It was difficult to add a large amount of inorganic filler to the composition.

  This invention is made | formed in view of the said situation, In the curable resin composition containing an epoxy compound, high rigidity is maintained in a high temperature range, and formation of hardened | cured material with a high glass transition temperature is enabled. With the goal.

  The curable resin composition according to the present invention includes a tetrahedral sheet in which a plurality of tetrahedral structures having silicon atoms as central atoms are arranged, and an octahedral sheet in which a plurality of octahedral structures having metal atoms as central atoms are arranged. A layered polymer in which silicon atoms in a tetrahedral sheet and metal atoms in an octahedral sheet are bonded via an oxygen atom, an epoxy compound having an epoxy group, and a curing agent. A one-component or two-component curable resin composition. The layered polymer in the curable resin composition has an epoxy-containing organic group containing an epoxy group bonded to a silicon atom in the tetrahedral sheet and a substituent bonded to the silicon atom in the tetrahedral sheet. And at least one organic group selected from an aryl group which may have a substituent and a cycloalkyl group which may have a substituent.

  In the curable resin composition according to the present invention, in addition to the epoxy-containing organic group, the specific organic group is introduced into the layered polymer. Thereby, the curable resin composition according to the present invention enables the formation of a cured product having a high glass transition temperature while maintaining high rigidity in a high temperature range. The presence of the organic group such as an aryl group as an organic side chain of the layered polymer stabilizes the structure in terms of stereochemistry compared to the case of an epoxy-containing organic group having an epoxy group alone. Crystallinity is increased. The present inventors presume that the above-described effects are obtained.

  The adhesive according to the present invention comprises the curable resin composition according to the present invention. Since the rigidity at high temperature is high and the heat resistance is excellent, the curable resin composition according to the present invention is particularly useful when used as an adhesive.

  ADVANTAGE OF THE INVENTION According to this invention, in the curable resin composition containing an epoxy compound, high rigidity is maintained in a high temperature range, and formation of hardened | cured material with a high glass transition temperature is possible. According to the present invention, the cured product can exhibit a high elastic modulus of about 10 GPa up to near the glass transition temperature. The resulting cured product has a high resistance to creep deformation.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  FIG. 1 is a schematic diagram showing the structure of a layered polymer according to an embodiment. The layered polymer 1 shown in FIG. 1 includes a tetrahedral sheet 11 in which a plurality of tetrahedral structures having silicon atoms as central atoms are arranged, and an octahedral sheet 12 in which a plurality of octahedral structures having Mg atoms as central atoms are arranged. And have. And the silicon atom in the tetrahedral sheet | seat 11 and the Mg atom in the octahedral sheet | seat 12 are couple | bonded through the oxygen atom. The silicon atom in the tetrahedral structure is an epoxy-containing organic group, or at least one organic group selected from an aryl group which may have a substituent and a cycloalkyl group which may have a substituent ( In some cases, it is hereinafter referred to as “aryl group etc.”) and is directly bonded by a covalent bond. These organic groups constitute the organic side chain portion of the layered polymer. In the case of the structure shown in FIG. 1, a 3-glycidoxypropyl group as an epoxy-containing organic group and a phenyl group as an aryl group or the like are bonded to a silicon atom.

  The layered polymer according to the present embodiment is not composed of only the structure shown in FIG. 1, and includes, for example, a portion where a silicon atom is substituted with a hydroxyl group, a portion where Mg is substituted with a hydroxyl group, and the like. May be. Further, in the structure shown in FIG. 1, 3-glycidoxypropyl groups and phenyl groups are regularly arranged alternately, but the portions where 3-glycidoxypropyl groups or phenyl groups are continuous are layered. It may be present in the polymer, or there may be a portion where an organic group other than an epoxy-containing organic group and an aryl group is bonded to a silicon atom.

In the layered polymer according to the present embodiment, the inorganic part constituting the part other than the organic side chain part has a structure similar to the layered silicate composed of the Si—O tetrahedral sheet and the metal oxide octahedral sheet. have. As minerals (layered silicate) having such a structure, pyrophyllite (Al ₂ Si ₄ O ₁₀ (OH) ₂ ), talc (Mg ₃ Si ₄ O ₁₀ (OH) ₂ ) and the like are known. Yes. For example, when the composition of talc is divided into a tetrahedral sheet, an octahedral sheet, and a hydroxyl group, it can be expressed as (SiO ₂ ) _4/3 (MgO) (H ₂ O) _1/3 . According to this notation, the composition of the layered polymer is, for example, the following formula:
^{_{(R 1 Am R 2 (1}} -A) n SiO (4-Am + An-n) / 2) x M 2 / Z O (H 2 O) w ··· (1)
Can be expressed as In the layered polymer, the formula (1) is a tetrahedral sheet portion (R ¹ _Am R ² _{(1-A) n} SiO _{(4-Am + An− ) with} respect to 1 mol of the octahedral sheet portion (M _{2 / Z 2} O). _{It means that} the ratio of _{n) / 2} ) is x mol and the ratio of structural water (H ₂ O) is w mol.

In formula (1), R ¹ represents an epoxy-containing organic group, and R ² represents at least one selected from an aryl group which may have a substituent and an cycloalkyl group which may have a substituent. A represents an organic group, A represents a numerical value greater than 0 and less than 1, m and n represent an integer of 1 to 3, x represents a numerical value of 0.5 to 2, M represents a metal atom or an ion thereof. Z represents 2 or 3, and w represents a numerical value of 0-2. A plurality of R ¹ , R ² and M in the layered polymer may be the same or different.

Examples of the epoxy-containing organic group represented by R ¹ include a glycidoxyalkyl group such as a 3-glycidoxypropyl group and a 3,4-epoxycyclohexylalkyl group such as a 2- (3,4-epoxycyclohexyl) ethyl group. There is. The number of carbon atoms of the alkyl group in the glycidoxyalkyl group is preferably 1-6.

The aryl group of R ² or the like generally has higher lipophilicity than the above-described epoxy-containing organic group, thereby increasing the affinity of the layered polymer for other organic components in the curable resin composition. As a result, it is considered that the dispersibility of the layered polymer in the curable resin composition is improved. Since the dispersibility is good, there is also an advantage that a curable resin composition containing a layered polymer can be easily prepared.

  The aryl group which may have a substituent is typically a phenyl group which may have a substituent. Specific examples include a phenyl group, an o-tolyl group, a 4- (chloromethyl) phenyl group, a pentafluorophenyl group, and a 4-perfluorotolyl group. Specific examples of the cycloalkyl group which may have a substituent include a cyclohexyl group.

A in Formula (1) represents the ratio (molar ratio) of R ^{1 to} the total amount of R ¹ and R ^{2 in} the layered polymer. In order to make the effect of the present invention remarkable, A is preferably 0.25 to 0.75. In this case, R ¹ : R ² (molar ratio) = 1: 3 to 3: 1.

M and n in the formula (1) are each the number of R ¹ or R ² bonded to one silicon atom, and are typically 1.

  M in the formula (1) represents a metal atom as the central atom of the octahedral sheet of the layered polymer. M is not particularly limited as long as it is a metal that forms a 2: 1 type layered silicate structure in addition to Mg. Specifically, M is at least one selected from the group consisting of Al, Mg, Fe, Li, Mn, Cu, Co, Ni, Zn, Cd, and Pb. These metal atoms may be ionized. Z in Formula (1) is a numerical value corresponding to the valence of M. w is a numerical value corresponding to the ratio of water contained as structured water, and is usually about 1 to 3 in the case of this embodiment.

The layered polymer is, for example, a method of reacting an organosilane compound having R ¹ bonded to a silicon atom and an organosilane compound having R ² bonded to a silicon atom with a metal compound containing a metal atom forming an octahedral structure. Can be obtained. The ratio of R ¹ and R ² in the obtained layered polymer can be controlled by the ratio of these two types of organosilane compounds. The organosilane compound only needs to have R ¹ or R ² and a hydrolyzable group such as an alkoxy group or an acetoxy group bonded to a silicon atom. Such organic silane compounds are generally available as silane coupling agents.

Specific examples of the organic silane compound having R ¹ include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) bis (trimethoxysiloxy) methylsilane, 2- (3,4-epoxycyclohexyl) ) Ethylmethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These organosilane compounds are used alone or in combination of two or more.

Specific examples of the organic silane compound having an R ^2, when R ² is an aryl group which may have a substituent, phenyl trimethoxy silane, dimethoxy methyl phenyl silane, dimethyl-methoxyphenyl silane, phenyl trimethoxy silane , Diethoxymethylphenylsilane, phenyltriacetoxysilane, p-tolyltrimethoxysilane, 4- (chloromethyl) phenyltrimethoxysilane, pentafluorophenyltriethoxysilane, pentafluorophenyltrimethoxysilane, pentafluorophenylethoxydimethylsilane And (4-perfluorotolyl) triethoxysilane. When R ² is a cycloalkyl group which may have a substituent, cyclohexyltrimethoxysilane and cyclohexylmethyldimethoxysilane are exemplified. These organosilane compounds are used alone or in combination of two or more.

  As the metal compound to be reacted with the organosilane compound, metal salts such as chlorides and nitrates and metal alkoxides are preferably used. For example, when an octahedral sheet having Mg as a central atom is formed, a magnesium salt such as magnesium chloride hexahydrate is used.

  The reaction between the organosilane compound and the metal compound can proceed in an alkaline aqueous solution at room temperature or with heating, as will be understood by those skilled in the art.

  The curable resin composition includes the layered polymer described above, an epoxy compound having an epoxy group, and a curing agent. In the case of a one-component curable resin composition, the curable resin composition before curing is stored in a state in which a curing agent is premixed in a main agent composition containing a layered polymer and an epoxy compound. In the case of a two-component curable resin composition, the main agent composition and the curing agent are stored separately and mixed during curing.

  The epoxy compound preferably has 2 or more epoxy groups, and more preferably 3 or more. Epoxy compounds are available as epoxy resins. Epoxy resins are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, glycidylamine type epoxy resin, tris (glycidylphenyl) methane, resorcinol diglycidyl ether, bisresorcinol tetraglycidyl ether, tetraglycidyl benzophenone, Glycidyl ester epoxy resin, glycidyl ether of aliphatic alcohol, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl novolac type epoxy resin, DPP novolac type epoxy resin, biphenyl type epoxy resin, cyclopentadienyl type epoxy resin, Trishydroxyphenylmethane type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopenta Including ene phenol epoxy resin and naphthalene type epoxy resin.

  Examples of glycidylamine type epoxy resins include tetraglycidyldiaminodiphenylmethane, triglycidyldiaminodiphenylmethane, tetraglycidylmetaxylylenediamine, triglycidylparaaminophenol, triglycidylmetaaminophenol, tetraglycidylbisaminomethylcyclohexane and N, N-glycidylaniline. Is mentioned.

  Examples of glycidyl ester epoxy resins include orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, tetrahydrolophthalic acid diglycidyl ester, and hexahydrophthalic acid diglycidyl ester. Succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, diglycidyl paraoxybenzoic acid, dimer acid glycidyl ester and trimellitic acid triglycidyl ester.

  Examples of glycidyl ethers of aliphatic alcohols include glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, and glycerol alkylene oxide adduct.

  The curable resin composition contains one or more selected from the above epoxy compounds and the like. The epoxy compound in the curable resin composition is preferably liquid at room temperature.

  The curing agent is not particularly limited as long as it functions as a curing agent for an epoxy compound or an epoxy resin. In this specification, a hardening | curing agent contains what acts as a hardening accelerator or a hardening catalyst other than what has functional groups, such as an amino group which reacts directly with an epoxy group.

  Examples of the curing agent include aromatic amines, chain aliphatic polyamines, cycloaliphatic polyamines, acid anhydrides, polyamide resins, imidazoles and derivatives thereof, polymercaptan, dicyandiamide, and organic acid hydrazides. Among these, aromatic amines are particularly preferable because the effect of improving heat resistance by the layered polymer is remarkable. Dicyandiamide and organic acid hydrazide are suitably used as a latent curing agent for a one-component curable resin composition.

  Specific examples of the aromatic amine include metaxylenediamine, metaphenylenediamine, orthophenylenediamine, paraphenylenediamine, 2,4-diaminoanizole, 2,4-toluenediamine, 2,4-diaminodiphenylamine, 4,4. Examples include '-methylenedianiline, diaminodiphenylmethane, diaminodiphenylsulfone, and diaminodixylylsulfone. Specific examples of the chain aliphatic polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine and diethylaminopropylamine. Specific examples of the cycloaliphatic polyamine include N-aminoethylpiperazine, mensendiamine, isofuronediamine and 1,3-diaminocyclohexane.

  Specific examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Examples include dodecenyl succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride and methylenecyclohexenedicarboxylic anhydride.

  Examples of imidazole derivatives include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole and 1-cyanoethyl-2-undecylimidazolium trimellitate.

  Tertiary and secondary amines (piperidine, N, N-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethylphenol) and the like) are used together with the above curing agent or alone.

  The curing agents listed above are used in the curable resin composition by one kind or in combination of two or more kinds.

It is preferable that the curable resin composition further contains an inorganic filler. Thereby, the rigidity of the cured product is further increased. In the case of this embodiment, since a performance improvement effect such as heat resistance improvement is obtained by a relatively small amount of the layered polymer, the amount of the inorganic filler is relatively large without excessively increasing the viscosity of the curable resin composition. It is possible to add. Therefore, higher rigidity can be obtained more easily than in the case of using a conventional layered polymer. For example, SiO ₂ particles are used as the inorganic filler.

  The ratio of the layered polymer in the curable resin composition is preferably 5 to 20% by mass based on the amount of the epoxy compound. If this ratio is less than 5% by mass, the effect of the present invention tends to be difficult to obtain. On the other hand, when it exceeds 20% by mass, the effect of improving heat resistance and rigidity tends to decrease. This is considered to be because when the amount of the layered polymer is excessively large, the movement of the curing agent in the curable resin composition is hindered and the curing does not proceed sufficiently.

  The ratio of the curing agent can be determined by a person skilled in the art by optimizing the equivalent ratio so that curing proceeds appropriately in consideration of the amount of epoxy groups in the epoxy compound and the epoxy groups in the layered polymer. It can be determined as appropriate.

  The ratio of the inorganic filler may be 50 to 90% by mass based on the mass of the main component composition containing the layered polymer and the epoxy compound (that is, the portion excluding the curing agent from the entire curable resin composition). preferable. If the ratio of the inorganic filler is less than 50% by mass, the reinforcing effect tends to be small, and if it exceeds 90% by mass, it becomes difficult to uniformly mix before curing due to high viscosity, resulting in poor curing. It tends to be easier.

  The curable resin composition is prepared by a method in which the above components and other components as necessary are mixed and kneaded while heating. The kneading can be performed using, for example, a kneader.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Synthesis Example (1) Synthesis of layered polymer having 3-glycidoxypropyl group and phenyl group 50.8 g of magnesium chloride hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 500 mL of methanol, and 3-glycided therein. 59.0 g of xylpropyltrimethoxysilane (Syra Ace S510, manufactured by Chisso) and 60.1 g of phenyltriethoxysilane (manufactured by Shin-Etsu Chemical) were added. Thereafter, an aqueous sodium hydroxide solution (concentration: 1 M) in which 20 g of sodium hydroxide was dissolved in 500 mL of ion-exchanged water was further added and stirred for 30 minutes. After standing overnight, the solution was filtered to remove the solids and washed with water. This was dispersed in 2 L of ion exchange water using a mixer for 1 minute. The suspension after dispersion was dried by freeze vacuum drying to obtain a fine powdery layered polymer (hereinafter referred to as “Ph-E-Mg layered polymer”).

(2) Synthesis of layered polymer having 3-glycidoxypropyl group and not having phenyl group Magnesium chloride hexahydrate 1018 g (5 mol) was added to 10 L of ion-exchanged water and dissolved therein. -2360 g (10 mol) of glycidoxypropyltrimethoxysilane was added and stirred well. Thereafter, when a sodium hydroxide aqueous solution (concentration: 1 mol / L) obtained by dissolving 400 g (10 mol) of sodium hydroxide pellets in 10 L of ion-exchanged water was added, a white precipitate was formed. After leaving as it is for 2 days, it was filtered using a filter press (manufactured by Nippon Filtration Equipment), and the precipitate was taken out. 20 L of ion-exchanged water was added to the taken out precipitate and the mixture was stirred for 1 hour for washing with water, and further filtered to collect the precipitate. The collected precipitate was dried by freeze vacuum drying to obtain a layered polymer (hereinafter referred to as “E-Mg layered polymer”).

X-ray diffraction measurement of layered polymer The crystallinity of the synthesized Ph-E-Mg layered polymer was measured by X-ray diffraction measurement (XRD). The X-ray diffraction measurement was performed using a Rigaku LINT2000 X-ray diffraction apparatus and using a Cu source.

  FIG. 2 is a graph showing an XRD pattern of the Ph-E-Mg layered polymer. From the XRD pattern, it is recognized that the Ph-E-Mg layered polymer forms a smectite-like layered structure, and the interlayer distance is approximately 15 nm. Since only one peak indicating the interlayer period is observed, it is considered that the 3-glycidoxypropyl group and the phenyl group are uniformly dispersed in the Ph-E-Mg layered polymer.

Measurement of Solid State Nuclear Magnetic Resonance (MAS NMR) Spectrum of Layered Polymer The ¹³ C and ²⁹ Si MAS NMR spectra of the layered polymer were measured using AVANS400 (Bruker BioSpin).

FIG. 3 is a graph showing a ¹³ C MAS NMR spectrum of the Ph-E-Mg layered polymer, and FIG. 4 is a graph showing the ¹³ C MAS NMR spectrum of the E-Mg layered polymer. In addition, FIG. 5 shows a ¹³ C MAS NMR spectrum of 3-glycidoxypropyltrimethoxysilane used as a synthetic raw material. As shown in FIG. 3, in the case of Ph-E-Mg layered polymer, it is derived from the phenyl group indicated by “+” together with the signal derived from the epoxy group found in 3-glycidoxypropyltrimethoxysilane. A signal was observed. On the other hand, as shown in FIG. 4, in the case of an E-Mg layered polymer, carbon atoms of -C-OH produced by hydrolysis of a part of the ether bond of 3-glycidoxypropyltrimethoxysilane during synthesis are obtained. An originating signal (indicated by “*”) was observed. This signal was not observed for the Ph-E-Mg layered polymer. Therefore, the Ph-E-Mg layered polymer into which the phenyl group is introduced is an ether located between the epoxy group and the silicon atom as compared with the E-Mg layered polymer into which the phenyl group is not introduced. It can be seen that the bond is hardly hydrolyzed.

6 is a graph showing a ²⁹ Si MAS NMR spectrum of the Ph-E-Mg layered polymer, and FIG. 7 is a graph showing a ²⁹ Si MAS NMR spectrum of the E-Mg layered polymer. As shown in FIG. 6, in the case of the Ph-E-Mg layered polymer, the signal “T ₃ (Ph)” derived from Si—Ph is observed together with the signal “T ₃ ” derived from Si—CH ₂ —. These had almost the same strength. From this, it was confirmed that the phenyl group was introduced to the extent assumed from the charging ratio. Although signals “T ₁ ” and “T ₂ ” derived from silanol (Si—OH) generated by hydrolysis of the siloxane bond were also observed, the strength was higher than that of the E-Mg layered polymer (FIG. 7). It was low. From this fact, the P-E-Mg layered polymer is more silicate layer than the E-Mg layered polymer in spite of using phenyltriethoxysilane having a low reactivity ethoxysilyl group as a synthesis raw material. It was found that the degree of polymerization of the tetrahedral sheet) portion was high.

Preparation of curable resin composition and its curing Preparation Example 1
Ph-E-Mg layered polymer, tetraglycidyldiaminodiphenylmethane (Epicoat 604, manufactured by Japan Epoxy Resin, hereinafter referred to as “604”), which is a tetrafunctional epoxy resin, and optionally SiO ₂ particles (TSS-4, Ryu (Mori Co., Ltd.) was mixed at the blending amount (g) shown in Table 1, and kneaded while heating to 80 ° C. to obtain a main agent composition. However, for Example 4 and Example 5, first, an epoxy resin and an equivalent amount of a layered polymer were kneaded at 80 ° C., and then an epoxy resin and an inorganic filler were added so as to have the ratio shown in Table 1. Further, the curable resin compositions of Example 4-2 and Example 5-2 were separately prepared by kneading at 80 ° C. In addition, when the thermogravimetry (TG) measurement of the layered polymer was measured, the ratio of the inorganic content contained in the layered polymer was 40.6% by weight. Based on this ratio, the value of the inorganic component / main agent composition shown in the table is calculated using the formula:
Inorganic content / main agent mixture = [layered polymer weight × 40.6 / 100 + inorganic filler weight] / total weight of main agent composition.

  4,4′-Diaminodiphenylmethane (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as “DDM”) as a curing agent is added to the main agent composition at a blending amount (g) shown in Table 1, and the temperature is increased to 110 ° C. Kneading while heating. Thereafter, a curable resin composition comprising a mixture of the main composition and the curing agent was cured by heating at 105 ° C. for 2 hours, 150 ° C. for 3 hours, and 200 ° C. for 2 hours to form a cured product. .

  Moreover, as a comparative example, a curable resin composition having the composition shown in Table 1 was prepared and cured under the same conditions as in the above examples to obtain a cured product.

Preparation Example 2
3.575 g of Ph-E-Mg layered polymer and the same amount of Epicoat 604 were softened by heating to about 90 ° C. on a hot plate and mixed well with a spatula. 17.88 g of Epicoat 604 and 78.55 g of TSS-4 were added thereto and kneaded while heating to about 80 ° C. using a table kneader (PNV-01 type, manufactured by Irie Shokai). Obtained.

  The main agent composition and the curing agent (dicyandiamide or terephthalic acid dihydrazide) were mixed while being heated to about 90 ° C. on a hot plate to obtain a one-component curable resin composition. 0.064 g of dicyandiamide and 0.1673 g of terephthalic acid dihydrazide were used with respect to 3 g of the main agent composition. The case of dicyandiamide is Example 7, and the case of terephthalic acid dihydrazide is Example 8.

  The obtained curable resin composition was cured by heating at 105 ° C. for 2 hours, 150 ° C. for 3 hours, and 200 ° C. for 2 hours to form a cured product.

Measurement of dynamic viscoelasticity of cured product The dynamic viscoelasticity (DMA) of the test piece cut out from the cured product obtained above was measured. As a dynamic viscoelasticity measuring apparatus, DVA-220 manufactured by IT Measurement Control Co., Ltd. was used. Tensile mode, measurement frequency: 10 Hz, heating rate: 4 ° C./min. , Static / dynamic stress ratio: 1.5, set strain: 0.01%, temperature range: room temperature to 300 ° C. DMA measurement results are shown in FIGS.

FIG. 8 shows a DMA measurement result of a curable resin containing no SiO ₂ particles, and FIG. 9 shows a curable resin composition containing SiO ₂ . As shown in FIGS. 8 and 9, the position of the tan δ peak indicating the glass transition temperature moved to the high temperature side as the amount of the Ph—E—Mg layered polymer was increased. In the case of Example 1 in which the ratio of the Ph—E—Mg layered polymer was 16.7% by mass, the glass transition temperature increased by 16 ° C. relative to Comparative Example 1 in which the layered polymer was not used. Further, in Example 3 using the Ph-E-Mg layered polymer, the storage elastic modulus and the glass transition temperature were greatly increased as compared with Comparative Example 3 using the E-Mg layered polymer (FIG. 9). .

Furthermore, as shown in FIGS. 10 and 11, there was a tendency for the glass transition point and the storage elastic modulus to increase as the SiO ₂ particles increased. In particular, in the case of Example 5-1 in which the ratio of the inorganic content in the main agent composition is 0.8, the storage elastic modulus is higher than that of Comparative Example 2 in which the layered polymer is not used, and is 10 GPa or more up to 200 ° C. The storage modulus was maintained. Moreover, the glass transition temperature of Example 5-1 was 280 degreeC, and rose 24 degreeC with respect to 256 degreeC of the comparative example 2. FIG.

  In FIG. 12, the DMA measurement result of the curable resin composition using dicyandiamide or terephthalic acid dihydrazide as a curing agent is shown together with the result of Example 5-2 using DDM. The glass transition temperature was 217 ° C. in Example 7 (dicyandiamide) and 241 ° C. in Example 8 (terephthalic acid dihydrazide), both of which showed high heat resistance of 200 ° C. or higher. The storage elastic modulus was almost the same, and showed a value of 10 GPa or more at 120 ° C. Further, the temperature dependence of the storage elastic modulus was smaller in Example 7 (dicyandiamide) and Example 8 (terephthalic acid dihydrazide) than DDM. In any case, since temporary curing conditions are employed in this embodiment, further improvement in performance is expected by optimizing the blending ratio of curing agents and curing conditions.

Evaluation of Elastic Modulus, Linear Expansion Coefficient and Creep Elongation Characteristics of Cured Product Regarding the cured products obtained from the curable resin compositions of Examples 5-1 and 5-2 and Comparative Example 2, the elastic modulus, linear expansion coefficient and creep were obtained. Elongation was measured. The measurement results are shown in Table 2. The elastic modulus was measured at 25 ° C. The linear expansion coefficient was determined in the range of 30 ° C to 200 ° C. The creep elongation was measured using a dynamic viscoelasticity measuring device (Pyris 1, manufactured by PerkinElmer). A tensile load was applied to the test piece at the temperature shown in Table 2, and the amount of the test piece extended from the initial length after 10 hours in that state was determined as the creep elongation. As shown in Table 2, in the case of Examples 5-1 and 5-2 using the Ph-E-Mg layered polymer, creep elongation was compared with Comparative Example 2 using only SiO ₂ particles as the inorganic component. The amount was very low.

It is a schematic diagram which shows the structure of the layered polymer which concerns on one Embodiment. It is a graph which shows the XRD pattern of Ph-E-Mg layered polymer. It is a graph which shows the ¹³ C HD NMR spectrum of Ph-E-Mg layered polymer. It is a graph which shows the ¹³ C HD NMR spectrum of an E-Mg layered polymer. It is a graph which shows the ¹³ C HD NMR spectrum of 3-glycidoxypropyl trimethoxysilane. Is a graph showing the ²⁹ Si HD NMR spectra of Ph-E-Mg layered polymer. Is a graph showing the ²⁹ Si HD NMR spectra of E-Mg layered polymer. It is a graph which shows a DMA measurement result. It is a graph which shows a DMA measurement result. It is a graph which shows a DMA measurement result. It is a graph which shows a DMA measurement result. It is a graph which shows a DMA measurement result.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Layered polymer, 11 ... Tetrahedral sheet, 12 ... Octahedral sheet.

Claims (6)

A tetrahedral sheet in which a plurality of tetrahedral structures having a silicon atom as a central atom are arranged; and an octahedral sheet in which a plurality of octahedral structures having a metal atom as a central atom are arranged. A layered polymer in which silicon atoms and metal atoms in the octahedral sheet are bonded via oxygen atoms;
An epoxy compound having an epoxy group;
A curing agent,
The layered polymer is
An epoxy-containing organic group containing an epoxy group bonded to a silicon atom in the tetrahedral sheet;
Having at least one organic group selected from an aryl group which may have a substituent and a cycloalkyl group which may have a substituent, bonded to a silicon atom in the tetrahedral sheet,
One-component or two-component curable resin composition.   The curable resin composition according to claim 1, wherein the epoxy compound has 3 or more epoxy groups.   The curable resin composition of Claim 1 or 2 containing an inorganic filler.   The curable resin composition according to any one of claims 1 to 3, wherein the curing agent is an aromatic amine.   An adhesive comprising the curable resin composition according to any one of claims 1 to 4. Hardened | cured material formed by hardening | curing the curable resin composition as described in any one of Claims 1-4.

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