TW201141949A - Benzoxazine-ring-containing theremosetting resin composition, process for production thereof, and molded products and cured products thereof - Google Patents

Abstract

Provided is a benzoxazine-ring-containing thermosetting resin composition which exhibits a reduced linear thermal expansion coefficient in a temperature region (a2 region) not lower than the glass transition temperature (Tg). A thermosetting resin composition which comprises: a benzoxazine-ring-containing thermosetting resin that contains both a structure (A) represented by general formula (1) and a structure (B) represented by general formula (2); and an at least bifunctional epoxy resin.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition of a benzophenone well ring, a method for producing the same, a molded article thereof, and a cured body. • [Prior Art] • The thermosetting resin with a benzopyrene ring in the molecular structure is excellent in heat resistance, flame retardancy, electrical insulation, and low water absorption, and has excellent properties not seen by other thermosetting resins. A combination of an electronic material such as a laminate or a semiconductor sealing material, a friction material, or a grindstone has attracted attention. The thermosetting resin having a benzofluorene ring is a thermosetting resin having a structure in which the α-cultivating ring is adjacent to the benzene ring, and for example, by using a phenol compound or an amine compound,

Lipid (left of formula (i)).

Borrow). [Chemical 1]

The thermosetting resin having a benzopyrene ring, such as the thermosetting resin of Patent Document 1, 154535.doc 201141949, discloses a thermosetting property of a benzofluorene ring obtained by reacting difunctional phenols, amines, and aldehydes. Resin. [Prior Art Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-64180 (Draft of the Invention) [Problems to be Solved by the Invention] However, the above-mentioned members such as electronic materials are required to have a high temperature environment. Excellent dimensional stability, but the above thermosetting resin has a problem that the reduction in the coefficient of thermal linear expansion (CTE) is insufficient. Generally, the temperature region below the glass transition temperature (Tg) is referred to as the α 1 region, and the temperature region above the glass transition temperature (Tg) is referred to as the α 2 region, and the coefficient of thermal linear expansion greatly changes around the glass transition temperature ' α 2 region The coefficient of thermal linear expansion tends to be a maximum value. In order to suppress such thermal behavior, it is also attempted to be composited with glass fibers, etc., but there are still many areas for improvement. The present invention is based on the above-mentioned circumstances. The object of the present invention is to provide a thermosetting resin composition having a reduced thermal expansion coefficient, particularly a temperature region (α2 region) of a glass transition temperature (Tg) or higher. Things. [Means for Solving the Problem] The present inventors have intensively studied to solve the above problems, and as a result, found that a difunctional or higher thermosetting resin having a benzofluorene ring having at least two specific structures in a molecule is prepared. The resin composition obtained from the epoxy resin can greatly reduce the coefficient of thermal linear expansion of the temperature region (?2) above the glass transition temperature (Tg), thereby completing the present invention. 154535.doc 201141949 That is, the present invention is as follows. [1] A thermosetting resin composition comprising a thermosetting resin having a benzofluorene ring and a difunctional or higher epoxy resin, wherein the thermosetting resin having a stupid and ploughing ring comprises a structure represented by the following formula (1) Α and the structure shown by the following formula (2) • B : [Chemical 2]

[Chemical 3]

Wherein R 1 to R 4 each independently represent hydrogen or an organic group having a carbon number of i 2 to 2 Å, and X represents an aliphatic group having a linear, branched or cyclic structure having a carbon number of 1 to 20 or containing a hetero element; The aromatic organic group, Y and γ2, respectively, represent an organic group having a linear, branched or cyclic structure of an aliphatic or aromatic diamine residue having 1 to 20 carbon atoms. , n&m independently represents an integer of 1-500; further, * represents the bonding site. [2] 154535.doc 201141949 [The thermosetting resin composition, wherein the above has benzo. In the thermosetting resin of the No. ρ well ring, R and R2 of the above structure are hydrogen. [3] The thermosetting resin composition according to [1] or [2], wherein in the above thermosetting resin having a benzofluorene ring, the above structures 8 and 2 and the structures B and R3 and R4 are hydrogen. [4] The thermosetting resin composition according to any one of [3], wherein the ratio of the content of the above structure A to the content of the above structure B in the thermosetting resin having a benzofluorenyl ring (A/B) ; Moerby) is 1/99 to 99n. [5] The thermosetting resin composition according to any one of [1] to [4] wherein at least one of the above γΐ or the above γ2 in the thermosetting resin having a benzene p-cultivating ring is a following formula (3) The structure shown: [Chemical 4]

Where * represents the bonding site. [6] The thermosetting resin composition according to any one of [1] to [5] wherein at least one of the above γ1 or the above Υ2 in the thermosetting resin having a benzo-11 ρ well ring is the following formula (4) ) The structure shown: [Chemical 5] 154535.doc 201141949

Where * represents the bonding site. [7] The thermosetting resin composition of any one of [1] to [6], wherein the enthalpy of the above-mentioned constitutive group Φ resin is at least selected from the group consisting of the group GU described below. One: [Chemical 6] G1a:

wood

In the filial group Gla, * indicates the bonding portion. [8] The thermosetting resin composition according to any one of [1] to [7] wherein the thermosetting resin having the benzophenone P well ring is formed by the following formula (5) XL·^ ~Γ*, a thermosetting resin obtained by reacting a compound represented by the above formula (6), a diamine compound, and an aldehyde compound: [Chem. 7]

154535.doc 201141949 where 'R and R2 each independently represent the organic group of hydrogen or carbon number. [Chem. 8]

Wherein R 3 and R 4 each independently represent an organic group of hydrogen or carbon number, and X represents an aliphatic or aromatic group having a linear, branched or cyclic structure which may contain a hetero atom. The organic base of the family. [9] The thermosetting resin composition according to [8], wherein the above reaction is carried out in a lactone. [10] The thermosetting resin composition according to any one of [1] to [9] wherein the epoxy resin is a trifunctional or higher epoxy resin. [11] The thermosetting resin composition according to any one of [10], wherein the above-mentioned cycloester comprises two or more kinds of difunctional or higher epoxy resins. [12] The thermosetting resin composition according to any one of [1] to [11] which further comprises an inorganic filler. [13] The thermosetting resin composition according to any one of [1] to [12] which further comprises a phenol hardener and a hardening accelerator. [14] 154535.doc 201141949 Electricity::3. a thermosetting resin composition wherein the above-mentioned phenolic hardener has a thermosetting resin composition of the same or a crucible, wherein the thermosetting resin having the above-mentioned % of the well ring, the above-mentioned clothing oxygen, and The total amount of the phenolic curing agent is 100 parts by weight, and the inorganic filler of the above-mentioned 3 is 200 to 400 parts by weight. [16] A thermosetting resin composition wherein the above-mentioned epoxy resin and the phenolic hard metal 3 are set to 20 to 4% by weight. For example, in the total of the thermosetting resinizing agent of the above-mentioned epoxy resin [17] in the total of the thermosetting resinifying agent of the ring of any one of [13] to [15], the thermosetting tree coating method is suitable for the method. Visiting the thermosetting resin of the cultivating ring and the second official ρ 八有牌^ 鳏, -, the step of mixing the above epoxy resin The above-mentioned thermosetting resin having the combined value of the total length and the total length includes the following formula (1) The structure of the structure and the structure shown in the following formula (2).

[Chemistry 9]

154535.doc - (2) 201141949 where R1 to R4 each independently represent an organic group of hydrogen or carbon number (10), and X represents a linear, branched, or cyclic group having a carbon number of 1 to 20 which may contain a hetero element. The aliphatic or aromatic organic group of the structure, γι and γ2 each independently represent an aliphatic or aromatic diamine having a direct bond, a bond bond, or a cyclic structure, which may have a carbon number of 1 to 20. The organic group of the residue, n&m, respectively, represents an integer from 1 to 500; further, * represents a bonding site. [18] A molded article obtained by the thermosetting resin composition according to any one of [1] to [16] or the thermosetting resin composition obtained by the production method of [17]. [19] A hardened body obtained by hardening a molded body of [18]. [20] An electronic device' comprising a shaped body as in [18] or a hardened body as in [19]. [Effects of the Invention] According to the present invention, it is possible to provide a thermosetting resin composition having a benzofluorene ring having a reduced (lower) coefficient of thermal linear expansion in a temperature region (cx2) of a glass transition temperature (Tg) or more. [Embodiment] Hereinafter, a mode for carrying out the invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The following examples are intended to illustrate the invention and are not intended to limit the invention to the following. The present invention can be suitably modified and implemented within the scope of the gist of the invention. 154535.doc •10· 201141949 The thermosetting resin composition of the present embodiment comprises a thermosetting resin having a benzofluorene ring and a difunctional or higher epoxy resin, and the thermosetting resin having a benzofluorene ring comprises the following formula (1); Structure A and structure B shown by the following formula (7) are shown. [化11]

[化 12]

Wherein R 1 to R 4 each independently represent hydrogen or an organic group having a carbon number of i 2 to 2 Å, and X represents an aliphatic group having a linear, branched or cyclic structure having a carbon number of 1 to 20 or containing a hetero element; The aromatic organic group, γι and γ2 each independently represent an organic group having a linear, branched or cyclic structure of an aliphatic or aromatic diamine residue having 1 to 20 carbon atoms. η and m each independently represent an integer of 1 to 500. Furthermore, * indicates the bonding portion. <Hot Curable Resin and Thermophilic Resin> In the present embodiment, the ratio of the content of the structure A to the content of the structure b in the thermosetting resin having a benzene and a cultivating ring (A/B; It is not particularly limited to preferably 1/99 to 99/1, and it is more preferably 10/90 to improve the heat resistance of the resin composition from the viewpoint of lowering the coefficient of thermal linear expansion of 154535.doc -11-201141949. 90/10 ' Especially good is 70/30~9〇/1〇, especially good for 5〇/5〇~9〇/1〇, the best is 70/30~90/10. Further, in addition to improving the balance between the heat resistance of the resin composition and the coefficient of thermal linear expansion, the ratio of the content of the structure A to the content of the structure B is further improved from the viewpoint of compatibility with other types of resins or inorganic substances ( A/B; Moerby) is better for 5〇/5〇~7〇/3〇. The resin obtained by setting the lower limit of the ratio of the content of the structure A to the content of the structure b (A/B; molar ratio) to 1/99 or more is formed when a molded body such as a cured film is formed. The tendency of the coefficient of thermal expansion of the hot wire to decrease further. The resin obtained by setting the upper limit to 99/1 or less has a tendency to be further improved in compatibility with other materials or solubility in a solvent to be formulated, and forms a cured film or the like. The tendency to further increase the flexibility of the body. Further, the content ratio of the structure A to the structure B herein can be determined by > H-NMR. R1 and R2 of the structure A of the formula (1) and the ruler 3 and R4 of the structure 3 of the formula (2) each independently represent hydrogen or an organic group having 1 to 20 carbon atoms, and X represents a carbon number 加 and may contain a hetero element. An aliphatic, or aromatic, organic group having a linear, branched, or cyclic structure. W and R2, and R3 and R4 may be the same or different. In particular, from the viewpoint of lowering the coefficient of thermal linear expansion, it is preferred that both R and R2 are hydrogen, more preferably R1 and R2, and R3 and R4 are hydrogen. In the above thermosetting resin having a benzofluorene ring, Y1 and γ2 each independently represent an aliphatic or aromatic diamine having a linear, branched or cyclic structure which may contain a hetero atom. The organic group, particularly in terms of the reduction of the coefficient of thermal linear expansion, is preferably at least one of γ ΐ and γ 2 154535. doc • 12 - 201141949 is a structure represented by the following formula (3). Or preferably, at least one of Y1 and γ2 is a structure represented by the following formula (4). γ] and Υ2 may be the same or different. [Chem. 13]

Wherein * represents the bonding site. [Chem. 14]

Wherein * represents the bonding site. In the above thermosetting resin having a benzophenone ring, m and η respectively represent an integer of 500, more preferably an integer of 2 to, particularly preferably an integer of 2 to integer, particularly preferably an integer of 2 to 300. The best is an integer of 2 to 25 inches. X represents an aliphatic or aromatic organic group having a linear, branched or cyclic structure which may contain a hetero element. Specific examples of the oxime include at least one selected from the group consisting of the following group (1). From the viewpoints of compatibility with other materials, solubility in a solvent used for formulation, and flexibility in forming a molded body, it is preferably selected from the group consisting of the following group Gla. At least one of them. , [Chem. 15] G1:

154535.doc -13- 201141949

In group G1, * indicates the bonding portion. [Chem. 16] G1a:

*

* In the group Gla, * indicates the bonding point. The thermosetting resin having a benzo-11 p-well ring of the present embodiment can be reacted by a compound represented by the following formula (5), a compound represented by the following formula (6), a diamine compound, and an aldehyde compound. Got it. In the present embodiment, as the difunctional phenol compound, at least a compound represented by the formula (5) and a compound represented by the formula (6) can be used. By reacting the difunctional phenol compound, the diamine compound, and the aldehyde compound, a benzoxene ring comprising the structure A represented by the formula (1) and the structure B represented by the formula (2) can be obtained. Thermosetting resin. [Chem. 17]

154535.doc ... (5) 201141949 In the formula (5), R 1 » D2 Λ base. The knives independently represent hydrogen or an organic group having a carbon number of 1 to 2 Å. When the organic group is an organic group, the structure thereof is not particularly limited. In the case of the example 3, the hetero amide or the functional group has a linear chain, a bond, or a ring; Work: aliphatic 'or aromatic organic base. Rl and R2 may be the same or not, and may be, for example, a succinyl group, an anthracene group, a syllabic group, a succinyl group, a decyl group or a carboxyl group. R丨 and R2 are preferably hydrogen. 9 In the formula (5), the carbonyl group is bonded to any of the adjacent 4-position and the para-position with respect to the bonding position of the left and right hydroxyl groups, and the bonding position of the several groups may be the same in the left and right benzene rings. The position can also be different as the adjacent position and the opposite position. The difunctional phenol compound represented by the formula (5) is not particularly limited, and examples thereof include 2,2,-dihydroxybenzophenone, 4, dihydroxydibenzopyrene (DHBP), and the like. Of these, 4,4,-dihydroxydiphenylhydrazine_(DHBP) is preferred. The coefficient of thermal expansion can be further reduced by using a difunctional compound. In particular, by using DHBP as a difunctional phenolated product, the coefficient of thermal linear expansion can be more significantly lowered. The difunctional compound represented by the formula (5) may be used alone or in combination of two or more. [Chem. 18]

(6) In the formula (6), R3 and R4 each independently represent hydrogen or a carbon number (~(10) of an organic group 'X represents a carbon number of 1 to 2 〇 which may contain a hetero bond having a straight bond, a branch, and 154535. Doc -15- 201141949 Or an aliphatic or aromatic organic group of a cyclic structure. The difunctional compound represented by the formula (6) is not particularly limited. For example, J. 4, 4'-mono-diphenyl-2,2-propane (double), 4, 4 '_ [, Benzyl bis(1-methyl-ethylidene)] biguanide, 4,4,-[1,4-phenylphenylbisindenyl]ethylene)]bisphenol, 4,4 · Bisphenols such as methylene diphenol (bisphenol F). Among these, 3, 4, 4, and 2 are preferable from the viewpoints of compatibility with other materials, cold solution property in a solvent used for formulation, and flexibility in forming a molded body such as a cured film. Hydroxydiphenyl-2,2-propane (bisphenol A). The difunctional phenol compound which is not a compound may be used singly or in combination of two kinds, and the above formula (5) and formula (6) iRi, r2, r3, r4, and fork may be used as long as Unless otherwise specified, it is the same as the above formula (1) and formula (7). The diamine compound is not particularly (IV), and an aliphatic diamine compound having a linear bond, a branched chain or a cyclic structure, an aromatic diamine compound or the like can be used. These may be substituted or unsubstituted, and may also contain a hetero element or an official base. Here, examples of the functional group include a county, a methoxy group, a decyl group, an ester group, a decylamino group, and a carboxyl group. As the alicyclic diamine compound, there is no tetrazide, and for example, a compound represented by the formula (9) and a compound represented by the formula (?) are preferable. [Chem. 19]

...(9) »54535.d〇c 16- ...(10)201141949

When a structural isomer is present in the compound represented by the formula (9) and the compound represented by the formula (10), respectively, it may be a cis isomer, a trans isomer, or a cis isomer and a counter Any mixture of isomers. The linear aliphatic diamine compound is not particularly limited, and examples thereof include a linear aliphatic diamine compound selected from the group consisting of the following group G2. [20] G2:

In addition, the aromatic diamine compound is not particularly limited, and is preferably a compound represented by the following formula (11), a compound represented by the following formula (12), and a formula (13): Compounds, etc. [Chem. 21] 154535.doc -17- 201141949

The compound represented by the formula (11) is, for example, more preferably a compound represented by the following formula (7) (p-phenylenediamine). [化22] h2n

- (7) In the formula (丨3), D independently represents a direct bond (there is no atom or atomic group), or a linear, branched, or cyclic structure of a hetero atom or a functional group, or In the aromatic organic group Kl3), D may be the same or different, β is not a direct bond (there is no atom or atomic group), or a fat containing a linear bond, a branched chain, or a cyclic structure of a heteropolysaccharide or a functional group. The organic base of the family, or ^xiang. The organic group of the above aliphatic or organic group may have a substituent. Examples of the substituent include a straight bond of a carbon number, a branch, or a (tetra) (tetra) group of a structure, or a silk or an unsubstituted aromatic hydrocarbon group. Here, examples of the functional group include an ether group, a field oxide, a ketone group, an ester group, a decylamino group, and a few groups. The fragrant ring may have a substituent. The linear group having a carbon number of 1 to 20, and the respective aryl groups of the formula (11), the formula (12), and the formula (13) are not particularly limited, and may be, for example, a branch or a ring. A structural aliphatic hydrocarbon group, an aromatic hydrocarbon group or the like. The substituent may contain a hetero element or a functional group. Here, the functional group may, for example, be an ether group, an alkoxy group, a ketone group, an ester group, a decylamino group or a fluorenyl group. In the formula (13), D is in the ortho position and the 4-position is relative to the bonding position of the left and right amine groups. [The bonding is performed on the vertical position, and the bonding position is in the left and right benzene rings. It can be the same position 'may be different from the adjacent position and the opposite position. Ε Relative to the left and right D's bonding position', and bonding at any position of the ortho, meta and para positions, the bond position of the bond is in the left and right benzene rings, which can be the same position. Such as the adjacent position is different from the opposite position. When the diamine compound is a compound represented by the formula (13), and D of the formula (13) is the above organic group, D may be selected from the group consisting of the following group (7). [Chem. 23] G3:

*

* In group G3, * indicates the bonding point on u 々 'square scent. When the diamine compound is a compound represented by + _ _ U3), and the formula (13) is the above-mentioned 154535.doc 201141949 organic group, E may be at least any one selected from the group consisting of the following group G4. [Chem. 24] G4:

In group G4, * indicates the bonding site on the aromatic ring. In the formula (13), η' and m are each independently an integer of 〇 10, preferably an integer of 0 to 5, and more preferably from the viewpoint of easiness. In the formula (13), when η' and m are oxime, the diamine compound is a compound represented by the following formula. [Chem. 25]

(14) In the formula (14), 'E represents a direct bond (there is no atom or a group of atoms), or an aliphatic or aromatic group which may contain a direct bond, a bond, or a structure of a hetero element or a functional group. The organic ruthenium as a functional group may, for example, be an ether group or an alkoxy group, or a decyl group, an ester group, a decylamino group or a carboxyl group, etc., 154535.doc -20- 201141949. 8. In the case where u is an organic group of an aliphatic group or an aromatic organic group, the stalk has a substituent. The substituent may, for example, be a carbon number of 1 to 1, a (four) group (tetra) of a "structure", or a substituted or unsubstituted perylene aromatic hydrocarbon group. In the formula (14), e is bonded to any position of the ortho position and the para position with respect to the storage bond position of the left and right amine groups, and the bond position of E may be in the left and right loops. The same position 'can also be different as the adjacent position and the opposite position. The compound represented by the formula (14) is preferred from the viewpoints of compatibility with other materials, solubility in a solvent used for formulation, and flexibility in forming a molded body such as a cured film. It is a compound (4,4._diaminodiphenyl decane) represented by the following formula (8). H'N \_J^CH2 V/~NH2 (8) Specific examples of the monoamine compound are not particularly limited, and examples thereof include: 3(4), 8W, and -bis(amino fluorenyl hydrazine) Cyclobu 2"" 2,6] anthracycline diamine compound of smoldering, 2 5 (6) bis (amino fluorenyl) bicyclo [2.2.1]; i, 2-diaminoethyl 6 1,6-Diaminohexyl 6, u〇-diamine oxime, U2_diaminododecane, 1,14-diaminotetradecane, and hydrazine, 18-diamino 18 a linear aliphatic diamine compound such as an alkane, a branched diamine compound such as tetraf-amino-propanyl-propanone; p-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4- Monoamine 3,3'-monomethyldiphenylmethane, 4,4,-diaminol_3,3,_2 154535.doc •21· 201141949 Ethyldiphenylmethane, 4,4' -diamino-3,3',5,5--tetramethyldiphenylmethane, 4,4'-diamino-3,3,5,5,-tetraethyldiphenylmethane , 4,4,-diaminodiphenyl scale, 2,2·-bis[4-(4-aminophenoxy)phenyl]propane, 4,4,_π,3_phenylene bis(1) -mercapto-ethylidene)]diphenylamine, 4,4,_[Μμ_phenylbis(1-methyl-ethylidene)]diphenylamine, i,3_ (4.Aminophenoxy)benzene, and hydrazine, 4_bis(4-aminophenoxy)benzene, 4,4,-diaminobiphenyl, 4,4|-bis (4-amino group) An aromatic diamine compound such as phenoxy)biphenyl, etc. Among these, from the viewpoint of lowering the coefficient of thermal linear expansion, p-phenylenediamine, diaminodiphenylmethane, and 4,4 are preferable. And diaminobiphenyl, more preferably p-phenylenediamine or 4,4,-diaminodiphenyl decane. These diamine compounds may be used singly or in combination of two or more. The amount of the compound used is preferably 0.1 to 2 mol, more than the total difunctional phenol compound 兔m〇l, more #兔nqe...1 ι> 尺住马υ.3~L8' is preferably 0.5 to 1.5 mol. When only the compound represented by the formula (5) and the compound represented by the formula (6) are used as the difunctional phenol compound, it means a total of 1 m relative to the compound represented by the formula and the compound represented by the formula (6). 1, and the diamine compound

One step to achieve high molecular weight.

The compound of the formula (6) is not a compound of the age of S, and the difunctional phenol compound represented by the formula (5) is used together with (the chelating compound, and the heat of the benzofluorene ring can be synthesized 154535.doc -22. 201141949 In the tree month, at this time, the amount of the difunctional compound represented by the formula (6) is preferably 99 mol%, more preferably 1〇~9〇., especially preferably 10~50 (4) %, particularly preferably 10 to 30 mol%. For the resin obtained by setting the amount of the compound of the bis(4) compound which is not in the formula (6) to the above lower limit value, there is a phase with other materials. The solubility or the solubility in the solvent used for the formulation tends to increase stepwise, and there is a tendency for the flexibility to be further improved when a molded body such as a cured film is formed. For the two shown by (6) When the amount of the functional phenolic compound to be used is less than or equal to the above-mentioned upper limit, the coefficient of thermal linear expansion tends to be further lowered when a molded article such as a cured film is formed. The aldehyde compound is not particularly limited. Is formaldehyde, as a formaldehyde t* as a polymer of tannic acid, or as a water soluble It is used in the form of a sulfalin or the like. X can also be used in the form of a hemiacetal obtained by reacting a acetonide with an alcohol and an alcohol. The alcohol at this time is not particularly limited, and examples thereof include methanol. Ethanol, 1-propanol, isopropanol, butanol, 2-butanol, etc. Among these, from the viewpoint of easiness of distillation removal, methanol is preferred. The alcohol may be used alone or in combination. Further, two or more kinds of the compound are used. The amount of the compound to be used is preferably from 4 to 8 mol', more preferably from 4 to 7 mol', particularly preferably from 4 to 6 mol, based on 1 mol of the diamine compound. It is set to 8 mol or less, which can reduce the impact on the human body and the environment. By setting the amount of the aldehyde compound to 4 m〇l or more, the thermosetting resin having the benzopyrene ring can be further polymerized. In the method for producing a thermosetting resin having a benzofluorene ring, a monofunctional phenol compound may be further added together with a difunctional phenol compound to react. When 154535.doc •23- 201141949, a g of phenolic compound is used to generate a polymer whose reactive end is blocked by a benzopyrene ring. RESULTS: The molecular weight of the polymer can be controlled in the synthesis reaction, and the condensation of the solution can be effectively prevented. Moreover, the retention of the thermosetting resin with benzoxene well can be improved by blocking the reactive end of the polymer. As a result, the thermosetting resin having a benzopyrene ring can be effectively dissolved. The monofunctional phenol compound is not particularly limited, and examples thereof include a phenol, an o-cresol, a m-cresol, and a phthalate. , p-tert-butylphenol, p-octylbenzene, p-cumyl phenyl age, dodecyl benzene, o-phenyl phenyl age, p-phenyl benzene, 1 · naphthalene, 2_Caipan M-methoxy phenyl, p-methoxyphenol, m-ethoxyphenol, p-ethoxyphenol, 3,4·dimethylphenol, 3,5-dimercaptobenzene. As the compound (4), phenol is preferred from the viewpoint of versatility and cost. The monofunctional phenol compound may be used singly or in combination of two or more. The amount of the monofunctional phenol compound used is preferably 0.5 mol or less with respect to the total difunctional phenol compound. By using a monofunctional phenolic compound relative to the total difunctional phenolic compound! Xenopus 1 is set to 〇5 m〇丨 or less, and the thermosetting resin having a structure of 笨 并 十 m can be made higher in the synthesis reaction, and the monofunctional phenol compound can be sufficiently reacted to reduce the monofunctionality. The residual amount of phenol. In the present embodiment, a known solvent can be used as the solvent, and it is preferred to use a solvent containing an internal solvent as a synthetic solvent. By using the solvent, gelation of the reaction solution or non-glutenization of the reaction product does not occur in the synthesis reaction, and the operability at the time of synthesis is good, and the synthesis process can be easily performed. 154535.doc -24· 201141949 The lactone is not particularly limited, and examples thereof include internal vinegar, γ-butane@, β-propanine vinegar, β•butyrol vinegar, and 7 hexidine lacquer. Vinegar--, 3-methyl octyl-based field, / 戍 酸 acid, γ γ - vinegar and other internal vinegar. Among these, the versatile high persuasion dicarboxylic acid is γ-butyrolactone, V Ρ a, , and 5 'preferred 曰 γ-caprolactone, and γ-valerolactone, etc., may be used in combination of two or more. 曰 Early use of 1 as a solvent, may be lactone and alcohol The mixed solvent is not limited, and examples thereof include methanol and ethanol, and the like: alcohol, isobutanol, and 2-methoxyethanol ==- 竣 丄 丄 丄 - - - - - - - - - - - - It is preferable to use one type of isobutanol and 2_, or two or more types can be used together. The oxyethanol 1 can be used alone as a mixed solvent of the internal solvent and the alcohol, and there is no particular limitation. Preferably, it is a combination of γ•butyrolactone and isobutanol methoxyethanol. The ratio of the mixture of the glycerol and the isobutanol methoxyethanol is preferably 50% by volume in terms of the effective synthesis reaction. the following. When the ratio of the alcohol is 50% by volume or less, the synthesis reaction of the thermosetting resin having a benzopyrene ring can be carried out in a short time, and the synthesis efficiency can be improved. Further, as a solvent, a lactone and a aryl group can be used. The aromatic non-polar solvent is not particularly limited, and examples thereof include benzene, toluene, xylene, trimellitic acid (state (6) 嶋mene), and mesitylene (hetero-identiene). Among these, from the viewpoint of high versatility and low cost, 5' is preferably toluene or xylene. The aromatic nonpolar solvent may be used singly or in combination of two or more kinds. 154535.doc •25- 201141949 = a mixed solvent of internal vinegar and an aromatic non-polar solvent, and is not particularly limited: γ-butyrolactone and toluene, and γ-butyrolactone and diterpene are preferable from the viewpoint of reaction temperature and the like. The combination of benzene. The aromatic solvent in the mixed solvent of the non-polar solvent is preferably 50% by volume or less from the viewpoint of not lowering the solubility of the raw material. By making the aromatic to the lactone and the aromatic non-polar solvent Proportion, relative to the total solvent mixture In addition, the ratio of the non-polar solvent in the range of 5% by volume or less can be more reliably determined, and the reaction efficiency can be improved. Further, as a solvent, it can be a mixed solvent of an aromatic non-polar solvent and an alcohol. The total amount of the aromatic non-polar solvent and the alcohol is preferably 5% by volume or less based on the total amount of the mixed solvent from the viewpoint of effectively performing the synthesis reaction or not reducing the solubility of the raw material in the solvent. In the form, the amount of the solvent is not particularly limited, and the concentration of the difunctional phenol compound is preferably Μ~5.0 mol/L, more preferably 〇MO m〇1/L, and particularly preferably G.1 to 3.0 m〇1. /L. By making the concentration of the compound (4) compound 〇" mol / L or more, the synthesis reaction rate of the thermosetting resin having a benzofluorene ring can be further promoted, and the reaction efficiency can be improved. When the concentration of the difunctional phenol compound is 5.0 mol/L or less, the synthesis reaction of the thermosetting resin having a benzene p-cultivation ring can effectively inhibit the gelation of the reaction solution, and can prevent the obtained article from being obtained. The insoluble of the thermosetting resin of the benzopyrene ring. In the method for producing a thermosetting resin, the order of adding and mixing the raw materials is not particularly limited. For example, the difunctional phenol compound, the diamine compound, and the compound may be sequentially added to the solvent, but it is preferably added to the mixture. After mixing a compound, a diamine compound, and a solvent to prepare a mixed solution 154535.doc -26·201141949, a mixed aldehyde compound is added to the mixed solution. In other words, the method for producing a thermosetting resin may be prepared by mixing a difunctional phenol compound (a compound represented by the above formula (5) and a compound represented by the above formula (6), a diamine compound, and a solvent). a step of mixing a solution; and further adding a brewing compound to the above mixed solution and reacting the same. In the method for producing the above-mentioned hot m-type resin, 'the reaction efficiency can be improved', and heating can be carried out, and a difunctional phenol compound or the like can be added by a solvent stirring or the like using a search machine or a stir-feed. The reaction can be carried out by using an inert gas such as nitrogen as needed, and is carried out in the presence of an inert gas. The method of heating is not particularly limited, and examples thereof include a method in which a temperature regulator such as an oil bath is used to heat up to a specific temperature and then fixed at this temperature. The specific temperature at the time of the heating treatment is not particularly limited as long as it is a temperature at which the synthesis reaction of the thermosetting resin having a benzofluorene ring can be realized, and the temperature of the reaction solution is preferably 10 to 15 (the range of rc, It is preferably 30 to 1 thief, especially preferably in the range of 5 〇 to 15 代. By making the temperature of the reaction solution above HTC, the synthesis reaction of the thermosetting resin with benzopyrene ring can be effectively promoted, and the reaction can be made. The efficiency is increased by __ step. The gelation of the reaction solution can be effectively suppressed by making the temperature of the reaction solution below, and the insolubilization of the resulting thermosetting resin having a benzo external ring can be effectively prevented. The method for producing the thermosetting resin during heating may further include the step of removing water formed by the reaction. By removing water formed by the reaction, the synthesis reaction time of the thermosetting resin having a benzopyrene ring can be shortened. Further, the efficiency of the reaction can be achieved. The method for removing the water to be removed is not particularly limited, and may be a method of azeotroping with a solvent in a reaction solution, for example, 154535.doc -27·201141949. The generated water is removed from the reaction body by using an isostatic dropping funnel with a cock, a Daisy condenser, a Dean-Stark apparatus, etc. Further, in the reaction step The pressure in the reaction vessel is reduced to remove the generated water to the outside of the system. The duration of the heating is not particularly (4), and is preferably, for example, about hours after the start of heating, more preferably about 2 to 15 hours. After the heating is continued for 20 hours, the reaction solution may be released from contact with a temperature adjuster such as an oil bath to be placed and cooled, or a method of cooling the curable resin may be used, preferably in the form of ==== 6) After the compound, the diamine compound, and the acid compound == step, the step of washing the reaction A by an alkaline aqueous solution is further included: by further including a washing step, the uncut 7 (10) can be obtained. Or a functional compound is effective from the reaction solution:: Γ = liquid, as long as the test compound is dissolved in water, the water is not limited. As an experimental compound, there is no particular limitation of two cases of sodium hydroxide, hydroxide Unloading, hydrating Dance, etc. These two are generally preferred to be sodium hydroxide in terms of versatility. > In the monthly washing step, the alkalinity is better than the steaming water, etc.: after washing with m liquid The nano-ion can be effectively used several times: if the second is cleaned by steaming water, the heat of the ring is 2: = * the ion of the liquid is removed. There is no special limitation, (4) the method of material recovery and the use of bad agent Re-sinking method, concentrated solidification] 54535.doc • 28· 201141949 chemical method (solvent distillation under reduced pressure), spray drying method, etc. In the present embodiment, 'reaction can be carried out after the reaction, as required The thermosetting resin having a benzopyrene ring is subjected to high molecular weight, and the thermosetting resin is heated in the presence of a substrate or a lyophilic resin (described later), thereby making the crosslinking density higher. A shaped body or a hardened body. The molded body or the cured body can not only greatly reduce the coefficient of thermal linear expansion of the α2 region, but also improve physical properties such as heat resistance and flexibility. The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC, Gel Permeation Chromatography) having a stupid and whistle-ring thermosetting resin is not particularly limited. Preferably, it is from 2000 to 300,000, more preferably from 4000 to 200,000, especially preferably from 4000 to 100,000 'extra is from 4000 to 50000, and most preferably from 4000 to 30000. Here, the term "polymerized thermosetting resin having a benzofluorene ring" means a prepolymer type thermosetting resin having a benzofluorene ring, that is, a benzo P No. 5 well in a repeating unit. The thermosetting resin of the structure of the ring means that its weight average molecular weight is controlled to about 2000 to 3 Torr. By making the weight average molecular weight of the thermosetting resin 2 Å or more, the heat resistance and flexibility of the molded body or the cured body obtained by the subsequent ring-opening reaction can be further improved. Further, the recovery workability at the time of production of the thermosetting resin having a benzofluorene ring can be improved, and the yield can be improved. By using the weight average molecular weight of 300,000 or less, the solubility of the benzo-bonded thermosetting resin obtained in the synthesis in various organic solvents can be ensured, so that the thermosetting resin composition can be easily prepared. 154535.doc •29· 201141949 As a method for controlling the weight average molecular weight of the thermosetting resin, for example, a part of the reaction solution is collected in the synthesis reaction, and the molecular weight of the solution is measured by Gpc, and the weight average molecular weight of the thermosetting resin is controlled. The thermosetting resin of the benzoic acid ring can be made into a structure which does not have a halogen atom, and can also be produced by using a solvent which does not contain a toothing compound as an impurity, so that it can be made substantially free of a toothed product. Thermosetting resin. <Difunctional or higher epoxy resin> The thermosetting resin composition of the present embodiment contains a difunctional or higher epoxy resin. Thereby, the crosslinking density can be further increased, so that it is particularly possible to reduce the coefficient of thermal linear expansion of the above α2 region. The difunctional or higher epoxy resin (hereinafter sometimes abbreviated as "polyfunctional epoxy resin") may be an oligomer or a polymer, and has at least two or more epoxy groups in the molecule. The number of epoxy groups in the epoxy resin may be two or more per molecule, and more preferably three or more per molecule. When the knives use only a monofunctional epoxy resin, the heat is fixed to the thermosetting resin composition

The epoxy resin is used without particular limitation. If it has two or more epoxy groups. For example, an aromatic epoxy resin, an aliphatic epoxy resin, an alicyclic epoxy resin or the like can be used. 154535.doc 201141949 More specifically, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol fluorene epoxy resin, dicyclopentene Epoxy resin, naphthalene epoxy resin, phenol·biphenyl type epoxy tree sap, cresol novolac epoxy resin, phenol aralkyl epoxy resin, alicyclic epoxy resin, tetrabromobisphenol A type epoxy resin, amino phenol type epoxy resin, amine based three tillage type epoxy resin, and the like. Commercially available products can also be used for one or more of the epoxy resins. As a specific example, the product name "RE-410S" (manufactured by Nippon Kayaku Co., Ltd.) or the product name "zx_1627 j (manufactured by Tohto Kasei Co., Ltd.) or the product name "EPICLON 840" (DIC company) Manufactured, bisphenol F-type epoxy resin, trade name "EPICL〇N83〇S" (manufactured by mc), and naphthalene-type epoxy resin, trade name "EPICL〇N_Hp_4〇32" (manufactured by dic company) biphenyl type The product name of the "oxygen resin" is "jER_YX4〇〇〇" (manufactured by Sakamoto Epoxy Co., Ltd.), and the trade name of phenyl fluorocarbon type epoxy resin is "ζχ_助" (manufactured by Tohto Kasei Co., Ltd.). The epoxy tree above shame is preferably an epoxy resin of two or more Å. The structure of the trifunctional or higher epoxy resin is not particularly limited, and may be an epoxy resin having three or more epoxy groups. Among these, among the trifunctional or higher epoxy resins, from the viewpoint of further increasing the crosslinking density, an epoxy resin having a trivalent or higher epoxy equivalent is more preferable. Further, when it is the same epoxy equivalent, it is more preferably an I functional epoxy resin. A commercially available product can also be used as the epoxy resin having a trifunctional or higher epoxy group. As a specific example, a trifunctional amine-based benzophenone-based epoxy tree Z 154535.doc -31 . 201141949 The product name "jER-630" (manufactured by Nippon Epoxy Co., Ltd.) and a trifunctional three-pronged skeleton ring Oxygen resin product name "TEPIC-sp" (manufactured by Daisei Chemical Industry Co., Ltd.), trade name of "tri-functional aromatic epoxy resin" "TECHMORE ^G310l" (manufactured by Printec), trade name of tetrafunctional aromatic epoxy resin _ GTR 1 800" (manufactured by Nippon Kayaku Co., Ltd.), modified varnish type = oxygen resin product name "EPICLON_N54〇" (manufactured by DIC Corporation), and dicyclopentadiene type epoxy resin trade name "EpiCL〇 N Hp72〇〇H 75M" (manufactured by DIC), the trade name "EPICLON-N660" (made by DIC) of cresol novolac type epoxy resin, and the trade name "jER- of phenyl phthalic acid varnish type epoxy resin" 152" (made by Nippon Epoxy Co., Ltd.), the trade name of epoxy resin containing biphenyl skeleton, rNC3〇〇〇" (manufactured by Nippon Kayaku Co., Ltd.), "NC3000H" (manufactured by Nippon Kayaku Co., Ltd.), "nc3〇〇 〇l" (made by Nippon Kayaku Co., Ltd.) The product of the naphthalene type epoxy tree is "ESN.·" (made by Dongdu Chemical Co., Ltd.). The above-mentioned difunctional or higher epoxy resin may be used alone or in combination of two or more. It is preferred to use two or more kinds of difunctional or higher epoxy resins in combination. By using two or more kinds of polyfunctional epoxy resins, the crosslinking density can be further increased, and the coefficient of thermal linear expansion can be further reduced, and the heat resistance or mechanical properties can be further improved. When the thermosetting resin composition of the present embodiment contains two or more kinds of epoxy resins having two or more functional groups, the combination of the epoxy resins is not particularly limited, and at least one of them is preferably a liquid epoxy resin. Here, the "liquid epoxy resin" is preferably an epoxy resin having a viscosity at room temperature, and more preferably an epoxy resin having a viscosity of 20 mPa. 3 or less under hi. When two or more kinds of 154535.doc •32·201141949 two or more epoxy resins are used, as the functional epoxy resin (liquid), the car is good for the two-year-old A-type epoxy or the double-F type, as other A multifunctional epoxy resin, preferably a varnish type epoxy resin. By this combination, the formability and mechanical properties (tensile elongation at break) of the molded body can be further improved. <Inorganic filler> The thermosetting resin composition of the present embodiment preferably further contains an inorganic filler. By this, dimensional stability can be improved. As the inorganic filler, and particularly limited, various inorganic fillers can be used. For example, it can be listed as: $2, sulphur dioxide, sulphate, sulphate, sulphuric acid, carbon _, potassium titanate, carbon carbide, nitriding stone, nitriding, oxidizing, oxidizing, oxidizing, olive Stone, block slip B mullite - powder such as titanium oxide, or such spheroidized beads, glass fibers, and the like. These may be used alone or in combination of two or more. From the viewpoint of the cost of the low coefficient of thermal expansion, and the ease of obtaining, it is preferably a bismuth dioxide slurry. The chrysanthemum sorbent may be a solvent which is dispersed in a solvent such as methyl ethyl hydrazine, bis-decylamine (DMf) or cyclohexanone. The method for producing the nitric oxide ceramsite is not limited, and the quasi-injury can be carried out by a known method. The method of subjecting the corrosive stone to a surface treatment and dispersing it to the organic solvent or the like is preferred. Further, as a slurry, the separator is preferably dispersed in a solvent of monomethylformamide or cyclohexanone from the viewpoint of dispersibility of the inorganic filler in the thermosetting resin. Particularly preferred is that the thermosetting resin composition of the present embodiment comprises the above-mentioned thermosetting resin having benzene 154535.doc -33- 201141949 and a cultivating ring, two or more kinds of polyfunctional epoxy resins, inorganic fillers, phenol curing agents, and Hardening accelerator. By including these components, it is possible to achieve a reduction in the coefficient of thermal linear expansion of not only the α2 region but also a wide region of the region, and it is also possible to improve heat resistance or mechanical properties. <Phenol Curing Agent> The phenol curing agent is excellent in compatibility with the thermosetting resin or epoxy resin having a benzofluorene ring used in the present embodiment, and thus a uniform thermosetting resin composition can be obtained. The phenol curing agent is not particularly limited, and a known one can be used. Examples of the phenol curing agent include a novolac type novolac type indophenol resin and an aralkyl type phenol resin. Further, from the viewpoint of reduction in heat absorption rate or heat resistance, it is preferred to use a phenol road varnish type benzoate resin having a biphenyl skeleton. The so-called age resin is a resin having age (four). Preferably, the hardener has a pull electron basis. The curing temperature of the _ resin composition can be achieved by using a hardener having a pulling electron; the low is a pull electron; preferably a substituent such as a ketone group or a continuation base. As the sclerosing agent, for example, di-diphenylbenzene (10) fluorene can be used: bis(4-(tetra)phenyl) hard (biguanide 8) or the like. As the bismuth hardening agent, one type may be used in combination of two or more kinds. <hardening accelerator>

As a solid 灭 Μ Μ 四 四 四 四 四 四 四 四 四 四 四 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 154 154 •34· 201141949

Among the secondary and tertiary amines, trisylphosphine I, among them, a hardening accelerator of t-seat and A derivative is preferred. These hardening accelerators may be used alone or in combination of two or more. In the present embodiment, when two or more kinds of polyfunctional epoxy resins, inorganic fillers, hardening agents, and curing accelerators are contained in the above-mentioned thermosetting resin having a benzo ring, the amount of each component is not particularly increased. The amount of the limiting filler is preferably from the total weight of the thermosetting resin, the epoxy resin and the hardener of the crucible, preferably from 200 parts by weight to 350 parts by weight. , especially good for 2 〇〇 ~ 3 〇〇 by weight. When the amount of the inorganic filler to be added is not less than the above-mentioned lower limit, the hot-wire expansion joint of the obtained molded article can be further reduced to the above upper limit value, whereby the moldability and mechanical properties of the molded article can be suppressed from being lowered. . The total content of the epoxy resin is preferably from 2 to 4% by weight, more preferably from 25 to 40% by weight, based on the total of the thermosetting resin, the epoxy resin and the phenolic hardener having a benzofluorene ring. It is 3〇~4〇% by weight. The content of the phenolic hardener is preferably from 1 to 25% by weight, more preferably from 15 to 25% by weight, particularly preferably 2, based on the total of the thermosetting resin having a benzofluorenyl ring, an epoxy resin and a phenol curing agent. 〇 ~25% by weight. By adding 1 to the above lower limit value or more, the curing temperature can be lowered. Therefore, the curing can be further promoted, and by lowering the upper limit or less, the deterioration of the mechanical properties can be further suppressed. The thermosetting resin composition of the present palladium form may be formulated with other additives than the above-mentioned % oxygen resin or inorganic filler, as needed. For example, it can be listed as: hardener, flame retardant, mold release agent, adhesion imparting agent, interface activity 154535.doc • 35· 201141949 agent, coloring sword, coupling remaining, leveling agent, and the like. Into the resin and so on. Adding other thermosetting 乍 as a coupling agent, a binder coupling agent can be used as a surface treatment agent for the machine filler.傕 , . , Relative to ^埴^ _ No special restrictions, sub, machine filler! 00 parts by weight, 〇" to 3 parts by weight can be used. In addition, in order to reduce the inorganic filling of the generation step, it is also possible to use a thermosetting resin composition which has been subjected to surface treatment in the form of a tenter in advance, and may further contain an alcohol solvent, an internal r: a dextran solvent, and a ketone solvent. , aromatic non-polar solvents, lactones and organic solvents. Sterol, ethanol, propanol, 2-2-butanol, tert-butanol, ethylenediethyl ether, ethyl propyl ether, ethyl ethion, dimethyl mystery, diethylene glycol, as an alcohol solvent, for example Examples thereof include propanol, 2·methyl-1·propanol, and i-butanol. Examples of the ether solvent include dibutyl ether, tetrahydrofuran, 1,4-di, alkyl dimethyl ether and the like. As a brewing amine solvent, you 丨t 1 is called dimercaptoacetamide II: enumeration: N, N bisindenyl (10), catalyzed amine, hexamethylenephosphoric amine. , ketone ketone, N-methyl-ε•hexene as a ketone solvent 'e.g., keto ketone' fluorenyl isobutyl hydrazine 】 acetone, diethyl ketone, mercapto ethane Λ ^ cyclopentanone, Cyclohexanone and the like. Examples of the non-exclusive toluene and the - 〇 〇 of the scented scented group include benzene, methyl bromide, dimethylform, dimethylformene, and mesitylene. As the lactone, for example, γ-caprolactone, γ-valerolactone, γ-butane 154535.doc -36 - 201141949 ester, β-propanine vinegar, β-butyrolactone, s_pentene Vinegar, s_hexine vinegar, ε_hexine vinegar, 3-methyl octyl hydrazine _4-endo vinegar, heart-based -3-pentenoic acid γ-ene vinegar, etc. The thermosetting resin composition of the present yoke form can be obtained by a production method comprising a step (mixing step) of mixing the above-mentioned benzotriene thermosetting resin or a difunctional or higher epoxy resin. The method of mixing is not particularly limited, and a known method can be employed. Further, when the inorganic filler, the phenol curing agent, the curing accelerator, the other filler, the thermosetting resin, the solvent or the like is mixed, the order of mixing and the like is not limited, and may be appropriately mixed by a preferred order and conditions. The mixing method and the like are also not particularly limited. A preferred method can be suitably employed. For example, a thermostatic tree 2 with a benzopyrene ring can be mixed with a solvent using a rotation/revolution mixer (for example, ΤΗΙΝΚγ mimr, manufactured by Baji) or each (four) mixing device, and then further mixed with a hardening agent, etc., as needed. The above inorganic filler, other filler or thermosetting resin is mixed. <Formed body, etc.> The molded article of the present embodiment is obtained by partially or hardening the above-mentioned thermosetting resin composition as needed. That is, the thermosetting resin composition of the present embodiment may be formed into a molded body or may be formed into a cured body. In the hardened body of the present embodiment, since the tamping resin having the benzophenan structure has moldability before curing, it can be cured by applying heat after being formed before the temporary curing (hardened molded body). It may be a hardened body (hardened body) at the same time as molding (hereinafter, these are collectively referred to as 'hardened body'). Further, the size or shape thereof is not particularly limited, and examples thereof include a film shape, a sheet shape (plate shape), a block shape, and the like, and may have other parts (for example, an adhesive layer). The curing method of the present embodiment is not particularly limited, and any conventionally known curing method can be used, which is usually 120 to 26 Torr. When the heating temperature is lower or the heating time is insufficient, the curing may be insufficient and the mechanical strength may be insufficient. Further, if the heating temperature is further circulated or the heating time is too long, depending on the case, a sub-reaction such as decomposition may occur, and the mechanical strength may be improperly lowered. Therefore, it is preferred to select an appropriate condition corresponding to the characteristics of the thermosetting resin composition of the present embodiment. When it is assumed that curing is performed by using pressurized heating steam, and when heat curing is performed by other methods such as electric wires, the curing temperature is preferably hardenable and low in temperature from the viewpoint of energy saving. Specifically, it is preferably 190 C or less hardening. More preferably, it is less than or equal to the hardness of the crucible. The lower limit of the hardening time is preferably 1 Gmin or more, more preferably more than minutes, and more preferably (four) minutes or more. . In terms of productivity, the upper limit of the hard time is preferably 10 hours or less, more preferably 5 hours or less and 3 hours or less. The filament or hard (four) obtained by forming or hardening the thermosetting resin combination of the present embodiment by the method of "." can be preferably used as an electronic 3 1 two-electron device and a material thereof for use in requiring low heat line expansion. The coefficient of "plate; ^ laminated board 胄 sealant, sticky money Ρ is particularly suitable as a layer-edge display device, vehicle equipment can be cited: mobile phones, juice computers, communication equipment. In addition, it can also be widely used in aircraft components, automotive components, building components, etc. 154535.doc -38· 201141949. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the examples. Further, the raw materials, evaluation methods and measurement methods used in the examples are as follows. I. Research on thermosetting resin composition containing thermosetting resin and epoxy resin with benzoxene ring (raw material) Bifunctional epoxy resin • Double F-type epoxy resin (trade name "EPICLON830S", manufactured by DIC Corporation, Epoxy equivalent 165~177 g/eq, viscosity 3〇〇〇~45〇〇mpa · s(25〇C )) • Bisphenol A type epoxy resin (trade name "RE-410S", manufactured by Nippon Kayaku Co., Ltd.) , ring enthalpy equivalent 170~190 g / eq, viscosity 7 〇〇〇 ~ 12000 mPa · s (25 〇 C)). Multifunctional epoxy resin (trifunctional or higher epoxy resin) Modified novolac epoxy resin (trade name "EPICLON-N540", manufactured by DIC, epoxy equivalent j 69 g/eq) • Difunctional three Epoxy resin of the spray frame (trade name "TEPIC_SP (high purity, fine powder grade)", manufactured by Nissan Chemical Industries, Ltd., epoxy equivalent <105 g/eq) • Epoxy resin containing biphenyl skeleton (trade name " NC3〇〇〇L (low molecular weight grade)" manufactured by Sakamoto Chemical Co., Ltd., epoxy equivalent 272 g/eq). (Determination of the coefficient of thermal linear expansion) 154535.doc •39· 201141949 The coefficient of thermal expansion is based on “TMA/SS6100” manufactured by SII NanoTechnology, Inc., with a load of 5 mN and a heating rate of 5° in a nitrogen atmosphere. The measurement was performed at C/min. The sample was obtained by cutting the obtained hard body into a width of 4 mm and a length of 20 mm, and setting the distance between the heads to be 10 mm. The coefficient of thermal linear expansion of the α2 region (the region above the inflection point temperature of the TMA measurement data) in the temperature region above the glass transition temperature (Tg) was evaluated. (Measurement of Weight Average Molecular Weight (Mw)) High Performance Liquid Chromatograph System (manufactured by Shimadzu Corporation)

System Controller: SCL-10A VP Liquid Feeding Unit: LC-10AD VP degasser: DGU-12A Differential Refractometer (RI) Detector: RID-10A Autoinjector: SIL-10AD VP Column Drying: CTO-IOAS VP Column: SHODEXKD803 (excluding the limit molecular weight of 70000) x 2 (serial) Column temperature: 50 ° C Flow rate: 0.8 mL / min Dissolution: Dimercaptocarhamamine (DMF; Wako Pure Chemical Industries, Inc., without stability For HPLC, 10mmol/L LiBr (lithium bromide)) Sample: 0.1% by weight

Detector: RI by the above measurement conditions, by Mw is 20000, 14000, 10000, 8000, 6000 '4000 '3000, 2000, 1500, 1000, 900 > 154535.doc -40- 201141949 600, 400, 300, A standard polyethylene glycol (Pure Chemical Company) of 200 made a calibration curve. The weight average molecular weight (Mw) of the polyethylene glycol equivalent value obtained by GPC measurement was measured by standard polyethylene glycol conversion. "Measurement of H-NMR" Measurement was carried out at a sample concentration of 1.3% by weight using the following measuring apparatus and solvent. Measuring apparatus: manufactured by JEOL, ECX400 (400 MHz) Solvent: containing 0.05% by volume of TMS (tetramethyl decane) DMSO (dimethyl sulfoxide; manufactured by Sigma-Aldrich Co., Ltd.) or an atmosphere containing 0.05% by volume of TMS (manufactured by CambRidge Isotope Labo RatoRies Co., Ltd.) (manufacture of thermosetting resin having benzopyrene ring) [Production Example 1] (Manufacture of DHBP70-BisA30-PDA) In a 300 mL flask, 200 mL of γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.) and 4,4·-dihydroxydibenzophenone (hereinafter referred to as DHBP) were placed. 18.12 g (0.084 mol, manufactured by Wako Pure Chemical Industries, Ltd.), bisphenol A (hereinafter referred to as Bis A) 8.22 g (0.036 mol, manufactured by Ge Plastics Japan Co., Ltd.), p-phenylenediamine (hereinafter referred to as PDA) 12.99 g (0.12 mol, manufactured by Daxin Chemical Industry Co., Ltd.), nitrogen flushing (flow rate 15 mL/min) was started in the system. The reaction solution was stirred at 100 ° C for 1 hour, and it was confirmed that DHBP, BisA, and PDA were dissolved. Formaldehyde (hereinafter referred to as PFA) 18.87 g (0.58 mol, Mitsubishi Gas Manufactured by Mitsubishi Gas Chemical Co., Ltd., purity 91.60%) 154535.doc -41 - 201141949 Add to the above flask and react for 4 hours. The reaction solution thus obtained is cooled to room temperature, filtered and injected into 1 L. In the decyl alcohol, the product precipitates and precipitates. The precipitated solid precipitated is dried under reduced pressure to obtain a thermosetting resin having a benzofluorene ring. The weight average molecular weight of the obtained thermosetting resin having a benzofluorene ring (Mw) is 7000. The structure A of the obtained thermosetting resin (hereinafter referred to as resin a) having a benzofluorene ring obtained by 1H-NMR: structure B (refer to formula (1) and formula (2)) (Morby ratio) is about 70: 30. The 1H-NMR spectrum of the resin a is shown in Fig. 1. (1H-NMR of DHBP70-BisA30-PDA) DHBP_PDA's methylene group at the 2nd position of the tillage ring 11 Proton peak: 5.44 ppm Methylene proton peak at position 4 of p-cultivation ring: 4.61 ppm Methylene proton peak at position 2 of the slogan of the cultivating ring of the BisA_PDA: 5.26 ppm Methylene group at position 4 of the p-well ring of the 17th p Proton peak: 4.46 ppm Proton peak derived from BisA thiol: 1.48 ppm [Manufacturing Example 2] (DHBP50-BisA5 Manufacture of 0-PDA) Into a 300 mL flask, 200 mL of γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.), DHBP 12.94 g (0.06 mol, manufactured by Wako Pure Chemical Industries, Ltd.), and BisA 13.70 g (0.06 mol, Manufactured by Ge Plastics Japan Co., Ltd., PDA 12.99 g (0.12 mol, manufactured by Daxin Chemical Industry Co., Ltd.), nitrogen flushing (flow rate 15 mL/min) was started in the system. The reaction solution was stirred at 154535.doc -42 - 201141949 100 ° C for 1 hour, and after confirming that DHBP, BisA, and PDA were dissolved, PFA 18.87 g (0-5 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd., purity 91.60%) was added to The inside of the flask was allowed to react for 5 hours. The reaction solution thus obtained was cooled to room temperature, filtered, and poured into 1 L of methanol to precipitate a product. The weight average molecular weight (Mw) of the thermosetting resin obtained from the thermosetting resin having a benzoxene ring was obtained by dehydrating the precipitated solid under reduced pressure to obtain a thermosetting resin having a benzoxene ring. The structure A of the obtained thermosetting resin having benzocyclohene ring (hereinafter referred to as resin b) was confirmed by 1H-NMR: the ratio of the structure B (refer to the formula (1) and the formula (2)) (Mohr ratio) was About 5〇: 5〇. The 1H-NMR spectrum of the resin b is shown in Fig. 2 . (1H-NMR of DHBP50-BisA50-PDA) DHBP_PDA 噚 唠 唠 唠 唠 2 2 2 曱 曱 : : : : : 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 The methylene proton peak at the 2 position of the tillage ring 1 : 5.25 ppm The methylene proton peak at the 4 position of the tillage ring: 4 45 ppm The methyl proton peak from BisA:! 48 ppm [Examples 1 to 1] (Production of thermosetting resin composition) According to the composition and the amount shown in Tables 1 and 2, a thermosetting resin having a benzofluorene ring and an epoxy resin and dimethyl group The amine (DMF) is mixed to obtain a thermosetting resin composition. Adjust the solid content concentration to 55~6〇 weight 154535.doc -43· 201141949 %. Stirring and defoaming are carried out using a self-rotating/revolving mixer (THINKY MIXER, manufactured by Nippon Steel Co., Ltd.). The obtained thermosetting resin composition was applied onto a PET film using an applicator, heated at 80 ° C for 10 minutes, heated at 150 ° C for 10 minutes, heated at 180 ° C for 30 minutes, and heated at 190 ° C. A hardened body was obtained in 60 minutes. The physical properties of the obtained hardened body were measured. The results are shown in Tables 1 and 2. Further, "BO" in the table indicates a thermosetting resin having a benzofluorene ring (the same applies hereinafter). [Comparative Example 1] A cured body was produced in the same manner as in Example 1 except that the above-mentioned thermosetting resin (DHBP70-BisA300-PDA) was used without using an epoxy resin. The results are shown in Table 1. [Comparative Example 2] A cured body was produced in the same manner as in Example 4 except that the epoxy resin was not used, and only the above-mentioned thermosetting resin (DHBP50-BisA50-PDA) was used. The results are shown in Table 2. [Table 1] Raw material Example 1 Example 2 Example 3 Example 7 Example 8 Comparative Example 1 BO DHBP70-BisA30-PDA 2.4 g 2.4 g 2.4 g 2.4 g 2.4 g 3.0 g DHBP50-BisA50-PDA - - - Ring Oxygen resin 830S (difunctional) 0.6 g - - - RE-410S (difunctional) - 0.6 g - - - N540 (multifunctional) - - 0.6 g - - TEHC (multifunctional) - - - 0.6 g - - NC3000L ( Multifunctional) 0.6 g Hardening Condition Hardening Temperature 190 °C 190 °C 190 °C 190 °C 190 °C 190 °C Measurement Results (ppm/°C) Thermal Expansion Coefficient (α2) 477 491 232 367 360 541 154535.doc • 44- 201141949 It can be confirmed from Table 1 that the coefficient of thermal linear expansion of the α2 region of Comparative Example 1 in which the epoxy resin was not formulated was 541 ppm/°C, and a polyfunctional epoxy resin having a difunctional or higher functionality was prepared. The coefficient of thermal linear expansion of the α2 region of Examples 1 to 3, 7, and 8 was greatly reduced. It was confirmed that the coefficient of thermal expansion of the α2 region of Examples 3, 7, and 8 in which the trifunctional or higher functional epoxy resin was blended was further greatly reduced. [Table 2] Raw material Example 4 Example 5 Example 6 Example 9 Example 10 Comparative Example 2 ΒΟ DHBP70-BisA30-PDA - - - - - DHBP50-BisA50-PDA 2.4 g 2.4 g 2.4 g 2.4 g 2.4 g 3.0 g Epoxy resin 830S (difunctional) 0.6 g - - - - RE-410S (difunctional) - 0.6 g - - - N540 (polyfunctional) - - 0.6 g - . - TEHC (multifunctional) - - - 0.6 g - - NC3000L (multi-functional) 0.6 g Hardening condition Hardening temperature 190 °C 190 °C 190 °C 190 °C 190"C 190 °C Measurement result (ppmTC) Thermal coefficient of thermal expansion (α2) 554 568 287 163 510 1260 According to the table As shown in Fig. 2, it was confirmed that the coefficient of thermal linear expansion of the α2 region of the second example of the unbonded epoxy resin was 1260 ppm/°C, whereas in the fourth embodiment, the epoxy resin having a polyfunctional or higher functional group was prepared. The coefficient of thermal linear expansion of the α2 region of ~6, 9, and 10 is greatly reduced. Among them, it was confirmed that the coefficient of thermal linear expansion of the α2 region of Examples 6, 9, and 10 in which the trifunctional or higher functional epoxy resin was blended was further lowered. II. Research on thermosetting resin composition containing thermosetting resin, epoxy resin, phenol curing agent, and hardening accelerator with benzene 11 ring (raw material) 154535.doc -45- 201141949 (1) Difunctional ring Oxygen resin • Bisphenol F epoxy resin (trade name “EPICLON 830S”, manufactured by DIC, epoxy equivalent 165~177 g/eq, viscosity 3000~4500 mPa · s(25〇C)) • Bisphenol A ring Oxygen resin (trade name "RE-41 OS", manufactured by Sakamoto Chemical Co., Ltd., epoxy faint 170~190 g/eq, viscosity 7000~12000 mPa·s (25 °C)). (2) Polyfunctional epoxy resin (trifunctional epoxy resin) • Epoxy resin containing biphenyl skeleton (manufactured by Nippon Kayaku Co., Ltd., trade name "NC3000H (high molecular weight grade)", epoxy equivalent 280~300 g/eq, softening point 65~75 ° C, solid at room temperature). (3) Phenol hardener • Phenol hardener containing biphenyl skeleton (manufactured by Mingwa Chemical Co., Ltd., trade name “MEH-7851-SS (low molecular grade)”, OH equivalent 201~205 g/eq, softening point 64~69 °C) • 4,4'-dihydroxydibenzophenone, Wako Pure Chemical Industries, industrial manufacture. (4) Hardening accelerator ・Imidazole-based hardening accelerator (manufactured by Shikoku Chemicals Co., Ltd., trade name "2P4MZ", 2-phenyl-4-methylimidazole). (5) Inorganic filler • Use of vinyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-1003") for cerium oxide (manufactured by Admatechs, trade name "SOC2": average particle diameter 0.5 Μηη) is a surface treatment and is dispersed in cyclohexanone (CHN) to obtain a cerium oxide slurry (solid content 70 weight 154535.doc -46 - 201141949 〇 / 〇). (6) Benzoindole resin • The bisphenol A_aniline type as a monomeric benzopyrene resin is stupid and ploughed (manufactured by Shikoku Chemical Industries, Ltd., B_a type). (Measurement of hot-line expansion coefficient) The coefficient of thermal expansion was measured by using "TMA/SS6100" manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere at a load of 5 mN and a temperature increase rate of 5 ° C /min. In the measurement sample, the obtained hardened body was cut into a width of 4 mm and a length of 20 mm, and the distance between the chucks was set to 1 〇mm. The αΐ region (the region below the recurve temperature of the TMA measurement data) was separately evaluated. The coefficient of thermal linear expansion and the coefficient of thermal linear expansion of the α2 region (the region above the inflection point temperature of the measured data). (Measurement of Glass Transfer Point (Tg)) The glass transition point (Tg) of the hardened body was measured using a "DMS6100" manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere at a frequency of 1 Hz and a temperature increase rate of 2 ° C / min. . The sample was measured by cutting the obtained hardened body into a width of 4 mm and a length of 50 mm by a distance of 20 mm between the chucks. (Measurement of Tensile Breaking Strength, Elongation, and Elastic Modulus) The tensile strength at break, the elongation, and the modulus of elasticity were obtained by using the "automatic stereographer AG-5000B" manufactured by Shimadzu Corporation. The measurement was carried out at a tensile speed of 5 mm/min. In the measurement sample, the obtained hardened body was cut into a width of 10 mm and a length of 100 mm, and the distance between the chucks was set to 60 mm. 154535.doc • 47· 201141949 (Comparative Manufacturing Example 1: Manufacture of BisA-BAPP) 2,2'-bis(4-hydroxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into the gas to be 13.7 8 (〇.〇) 6111〇1), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (manufactured by Tokyo Chemical Industry Co., Ltd.) 25.13 g (0.06 mol), p-furfural (manufactured by Wako Pure Chemical Industries, Ltd.) 8.05 g (〇.25 mol), the reaction was carried out for 6 hours while removing the generated water. The solution after the reaction was poured into a large amount of methanol to precipitate a product. Then, the product was separated by filtration separation and washed with decyl alcohol. The benzoin resin is obtained by drying the washed product under reduced pressure. In the measurement of the molecular weight of the obtained resin by GPC, the weight average molecular weight was 8,900. [Examples 11 and 12] (Production of thermosetting resin composition) Benzene hydrazine resin and epoxy resin, phenol curing agent, and hardening accelerator were mixed according to the composition and the amount shown in Table 3; An inorganic filler (cerium oxide slurry) and N,N-didecylguanamine were used to obtain a thermosetting resin composition. The solid content concentration was adjusted to 7 〇 to 75% by weight. The mixing and defoaming system is a self-rotating/revolution mixer (manufactured by THInky Co., Ltd., "THINKY MIXER"). The obtained thermosetting resin composition was applied onto a release-treated PET film (thickness: 5 μm, manufactured by UNTEC Co., Ltd.) using an applicator, and heated at 80 ° C for 10 minutes and heated at 15 ° t. After 〇 minutes, heating at 18 (TC for 30 minutes, and heating at 19 (rc for 9 〇 minutes) to obtain a hardened body having a thickness of 3 〇 to 4 〇μπ ΐ 2 was measured. The physical properties of the obtained hardened body were measured. The results are shown in Table 3. In addition, the total amount of the resin components shown in Table 3 was 1 part by weight. 154535.doc • 48·201141949 [Comparative Example 3] In Comparative Example 3, monomeric benzoic acid was used. A hardened body was produced in the same manner as in Example 11 except that the resin was used. The results are shown in Table 4. The total amount of the resin components shown in Table 4 was 100 parts by weight. [Comparative Example 4 In Comparative Example 4, a hardened body was produced in the same manner as in Example 11 except that a benzopyrene resin (Comparative Production Example 1) of a BisA-BAPP structure was used. The results are shown in Table 4. 3] Example 11 Example 12 BO Resin DHBP70-BisA3 0-PDA 38 BO Resin DHBP50-BisA50-P DA 38 Resin Composition (% by weight) (total 100 parts by weight) Epoxy Resin RE-41 OS 35 35 Epoxy Resin 830S Epoxy Resin NC3000H 3 3 Phenolic Resin MEH-7851SS 9 9 Test Compound DHBP 15 15 Additive (Weight Parts) Hardening accelerator 2P4MZ 1 1 Inorganic filler (parts by weight) 185 185 Thermal expansion coefficient (al) ppm/°C 17 17 Thermal expansion coefficient (α2) ppm/°C 97 99 Evaluation of glass transition point (Tg) °c 201 198 Tensile strength at break MPa 127 121 Tensile elongation at break % 3.1 2.5 Tensile modulus of elasticity GPa 9 9 154535.doc -49- 201141949 [Table 4] Comparative Example 3 Comparative Example 4 Preparation of resin component (% by weight) ( Total 100 parts by weight) BO resin Ba 38 BO resin BisA_BAPP 38 Epoxy resin RE-41 OS 35 35 Epoxy resin NC3000H 3 3 Phenolic resin MEH-7851SS 9 9 Phenolic compound DHBP 15 15 Additive (parts by weight) Hardening accelerator 2P4MZ 1 1 Inorganic filler (parts by weight) 185 185 Evaluation of coefficient of thermal expansion (al) ppm/°C 17 21 Thermal expansion coefficient (α2) ppm/°C 120 115 Glass transfer point (Tg) °c 175 179 Tensile strength at break MPa 114 97 stretching Elongation at break % 2.0 2.3 Tensile modulus of elasticity GPa 10 8 As shown in Tables 3 and 4, the coefficient of thermal linear expansion of the α2 region of Comparative Examples 3 and 4 was 201 ppm/°C and 198 ppm wide C. The coefficient of thermal linear expansion of the α2 region of Examples 11 and 12 was 97 ppm/°C and 99 ppm/°C. From these, it was confirmed that the coefficient of thermal linear expansion of the α2 region of Examples 11 and 12 was largely lowered. Further, it was confirmed that the coefficient of thermal linear expansion of the αΐ region of Examples 11 and 12 was also lowered. Further, the Tg of Examples 11 and 12 was 198 ° C or higher, whereas the Tg of Comparative Examples 3 and 4 was 179 ° C or lower. Further, the tensile breaking strength of Examples 11 and 12 was 121 to 127 MPa, and the elongation at break was 2.5% or more. On the other hand, the tensile breaking strength of Comparative Examples 3 and 4 was 114 MPa or less, and the elongation at break was 2.3. %the following. 154535.doc •50· 201141949 According to the above, it is confirmed that the hardened body obtained from the thermosetting resin composition in which the epoxy resin, the phenol curing agent, and the hardening accelerator are blended in the above-mentioned thermosetting resin having a stupid and ploughing ring, The reduction in the coefficient of thermal expansion can be achieved not only in the core region but also in the α1 region, and the heat resistance and mechanical properties are also excellent. This application is based on the Japanese patent application filed on March 31, 2010 to the Patent Office (Japanese Patent Application No. 20 10-080458) and September 29, 2010. The application (Japanese Patent Application No. 2010-219634), and the Japanese Patent Application No. 2011-042809, filed on Sep. 28, 2011, the entire contents of Introduced. [Industrial Applicability] The thermosetting resin composition of the present invention, a molded body thereof, and a cured body are industrially available in the field of electronic materials such as a laminate or a semiconductor sealing material, a friction material, or a bonding material such as a grindstone. The usability can be preferably used as various electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a proton nuclear magnetic resonance spectrum (CH-NMR spectrum) of a thermosetting resin having a benzofluorene 4 ring produced in Production Example 1. Fig. 2 is a proton nuclear magnetic resonance spectrum (H-NMR spectrum) of a thermosetting resin having a stupid and ploughed ring produced in Production Example 2. 154535.doc -51-

Claims (1)

201141949 VII. Patent application scope: 1. Sexual heat-type thermosetting resin composition, which comprises a thermosetting resin with a benzopyrene ring and a difunctional epoxy resin, the above-mentioned solidity of the benzo-xene well ring The resin includes the structure A represented by the following formula (1) and the structure B represented by the following formula (7): [Chemical Formula 1] In the formula, R1 to R4 each independently represent hydrogen or an organic group having 1 to 20 carbon atoms, and X represents an aliphatic or aromatic group having a linear, branched or cyclic structure which may contain a hetero atom. The organic group of the group, y1 and Y2 respectively represent an organic group having a linear, branched or cyclic structure of an aliphatic or aromatic diamine residue having a carbon number of 1 to 20 , n&m respectively represent an integer from 1 to 500; further, * denotes a bonding portion. 2. The thermosetting resin composition of claim 1, wherein R1 and R2 of the above structure A in the above thermosetting resin having a benzo-rhodium ring are hydrogen. 3. The thermosetting resin composition of claim 1 or 2, wherein R1 and R2 of the above structure 热 in the thermosetting resin having a benzofluorene ρ well ring, and R3 and R4 of the above structure B are both hydrogen . 4. The thermosetting resin composition according to any one of claims 1 to 3, wherein the ratio of the content of the above structure A to the content of the above structure B in the thermosetting resin having a benzoin ring is (A/B; The ear ratio is 1/99 to 99/1. 5. The thermosetting resin composition according to any one of the items 4 to 4, wherein at least one of the above γ or the above γ 2 in the thermosetting resin having a benzofluorene ring is represented by the following formula (3) Structure: [Chemical 3] ...(3) where * indicates the bonding portion. 6. If = item! In the thermosetting resin composition according to any one of the above-mentioned items, at least one of the above Υ1 or the above γ 2 is a structure represented by the following formula (4): [Chemical 4] ...(4) where * indicates the bonding portion. As in the claims 1 to 6, any one of the items 1 to 6 has a stupid and tenth ring of the field..., the solid resin composition 'at least one of the groups formed thereon: the X is selected from the group G 154535.doc 201141949 [5] G1a: In the group G1 a '* denotes a bonding site. 8. The thermosetting resin composition according to any one of the items 1 to 7, wherein the above-mentioned thermosetting resin having a benzo% is a compound represented by the following formula (5), and a formula (6) A thermosetting resin obtained by reacting a compound, a diamine compound, and an aldehyde compound: [Chemical 6] ΟΗ (5) where R 1 and R 2 independently represent hydrogen or an organic group having 1 to 20 carbon atoms; Wherein R 3 and R 4 each independently represent hydrogen or an organic group having 1 to 20 carbon atoms, and X represents a carbon number of 1 to 2 Å which may contain a heterocyclic element having a linear chain, a bond, or a 154535.doc 201141949 cyclic structure. Aliphatic, or aromatic, organic group. The thermosetting resin composition according to any one of claims 1 to 9, wherein the epoxy resin is a trifunctional or higher epoxy resin. . The thermosetting resin composition according to any one of the preceding claims, wherein the epoxy resin comprises two or more kinds of difunctional or higher epoxy resins. The thermosetting resin composition according to any one of the above items, which further comprises an inorganic filler. The thermosetting resin composition according to any one of 12, which further comprises a phenol hardener and a hardening accelerator. 14. The thermosetting resin composition of claim 13, wherein the phenolic hardener has an electron withdrawing group. The thermosetting resin composition according to any one of claims 13 to 15, wherein the thermosetting resin composition, the epoxy resin, and the phenolic curing agent are contained in an amount of 100 parts by weight based on 100 parts by weight of the thermosetting resin, the epoxy resin, and the phenolic curing agent. The inorganic filler is 200 to 400 parts by weight. 16. The thermosetting resin composition according to any one of claims 13 to 18, wherein the content of the above epoxy resin in the total of the above-mentioned thermosetting resin having a benzoxene ring, the above epoxy resin, and the above-mentioned expectant hardener a method for producing a thermosetting resin composition of 2 〇 to 4 〇, which is an ancient and/or a thermosetting resin having a cumbersome ploughing ring and a difunctional or higher epoxy resin. The thermosetting resin of the ring contains the structure of the following formula (1) and the structure of the following formula (2): 154535.doc -4· - (1) 201141949 [Chem. 8] ___* Π [Chemistry 9] Wherein RLR4 independently represents hydrogen or an organic group having 1 to 20 carbon atoms, and X represents an aliphatic or aromatic group having a linear, branched or cyclic structure which may contain a hetero atom. The organic group, Y1 and Y2, respectively, represent an organic group having a linear, branched or cyclic structure of an aliphatic or aromatic diamine residue having a carbon number of 1 to 20, η and m Each of them represents an integer of 1 to 50,000, respectively; and '* denotes a bonding portion. A molded article obtained by the thermosetting resin composition according to any one of claims 1 to 16, or a thermosetting resin composition obtained by the method of claim 17. A hardened body which is obtained by hardening a shaped body according to claim 18. 20. An electronic device comprising a shaped body as claimed in claim 18 or a hardened body such as the desired item 19. 154535.doc