JP2022134185A - Mono-glycidyl ether having mesogenic skeleton and composition thereof - Google Patents

Abstract

To provide a mono-functional glycidyl ether capable of securing working properties to a bi-functional glycidyl ether having an aromatic ring, such as a bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin and the like which are used in general purpose as a main agent, and capable of applying a cured object excellent in heat radiation property, and a composition in which the same is blended.SOLUTION: There is provided mono-glycidyl ether having a mesogenic skeleton which is expressed by a following formula, in the formula, a nitrogen atom is coupled to any of an ortho position, a meta position and a para position of an aromatic ring, X is one kind selected from, H, CN, F, Cl, Br, I, methoxy group, and ethoxy group.SELECTED DRAWING: Figure 1

Description

The present invention relates to a monoglycidyl ether having a mesogenic skeleton and a composition containing the monoglycidyl ether.

Conventionally, when designing epoxy resin compositions as electrical and electronic materials, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins, which are widely used as bases, are so viscous or solid that they are difficult to handle at work sites. Therefore, it is known that a monofunctional or polyfunctional glycidyl ether is blended as a reactive diluent to be incorporated into the cured product. Moreover, among such monofunctional glycidyl ethers, those having an aromatic ring are also known in order to impart heat dissipation properties that can be used as electrical and electronic materials.

For example, in Patent Document 1, among monofunctional glycidyl ethers having aromatic rings to be blended with bifunctional glycidyl ethers having aromatic rings such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins, It is disclosed that phenylglycidyl ether or the like can be blended as a substance.

JP 2004-75835 A

Patent Document 1 describes phenylglycidyl having an aromatic ring as a reactive diluent that is a monofunctional glycidyl ether that can be blended with a bifunctional glycidyl ether having an aromatic ring such as a bisphenol A type epoxy resin and a biphenyl type epoxy resin. Ethers and the like are disclosed, but there is a demand for monofunctional glycidyl ethers with even better heat dissipation properties.

Therefore, in the present invention, workability is ensured at work sites for bifunctional glycidyl ethers having aromatic rings such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins, which are widely used as main agents. It is an object of the present invention to provide a monofunctional glycidyl ether and a composition containing the same, which can give a cured product having excellent heat dissipation property.

（式中、窒素原子は芳香環のオルト位、メタ位又はパラ位のいずれかに結合しており、Ｘは、Ｈ、ＣＮ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、メトキシ基、エトキシ基から選ばれる１種である。）
で表されるメソゲン骨格を有することを特徴とするモノグリシジルエーテルである。 [1] That is, the present invention is

(Wherein, the nitrogen atom is bound to either the ortho-position, the meta-position or the para-position of the aromatic ring, and X is selected from H, CN, F, Cl, Br, I, a methoxy group and an ethoxy group. 1 species.)
It is a monoglycidyl ether characterized by having a mesogenic skeleton represented by

（Ｘはハロゲン原子またはＣ１～Ｃ５のアルキル基、ａおよびｂは置換基Ｘの個数であって０～４の整数、ＲはＣ１からＣ１０のアルキレン基、アルキリデン基、カルボニル基、スルホニル基、酸素原子又は原子団の存在しない直接結合を示す。）
で表される芳香環を有するジグリシジルエーテルとを有し、前記モノグリシジルエーテルの配合割合が３０重量％以上であることを特徴とするエポキシ樹脂組成物である。 [2] and
The monoglycidyl ether described in [1] above;

(X is a halogen atom or a C1 to C5 alkyl group, a and b are the number of substituents X and are integers of 0 to 4, R is a C1 to C10 alkylene group, alkylidene group, carbonyl group, sulfonyl group, oxygen indicates a direct bond with no atoms or atomic groups.)
and a diglycidyl ether having an aromatic ring represented by the formula, wherein the blending ratio of the monoglycidyl ether is 30% by weight or more.

[3] A cured epoxy resin obtained by curing the epoxy resin composition described in [2] above and at least one curing agent selected from amines, acid anhydrides and phenols.

According to the present invention, it is possible to ensure workability at work sites for bifunctional glycidyl ethers having aromatic rings such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, etc., which are widely used as main agents. can be obtained, and a cured product having more excellent heat dissipation can be obtained.

Photographs of the cured products of Example 1 and Comparative Example 1 with a polarizing microscope

Hereinafter, embodiments of the monoglycidyl ether having a mesogenic skeleton and the composition thereof of the present invention will be described in detail. In addition, when there is a notation indicating a range in the description, it includes the upper limit and the lower limit.

（式中、窒素原子は芳香環のオルト位、メタ位又はパラ位のいずれかに結合しており、Ｘは、Ｈ〔水素〕、ＣＮ〔シアノ基〕、Ｆ〔フッ素〕、Ｃｌ〔塩素〕、Ｂｒ〔臭素〕、Ｉ〔ヨウ素〕、メトキシ基、エトキシ基から選ばれる１種である。） In the present invention, the monoglycidyl ether having a mesogenic skeleton, which is a rigid site that exhibits liquid crystallinity, is a monoglycidyl ether represented by the chemical formula (1). By using a monoglycidyl ether represented by the chemical formula of Chemical Formula 1, it was blended with a bifunctional glycidyl ether having an aromatic ring, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, etc., which are widely used as main ingredients. Occasionally, they interact with the aromatic rings contained in the epoxy resin as the main agent, and are stabilized in a stacked arrangement to give a cured product with excellent heat dissipation. In addition, when the epoxy resin of the main agent is a biphenyl-type epoxy resin, the melting point of the biphenyl-type epoxy resin is as high as about 156° C., and workability is not preferable. For this reason, the melting point is considerably lower than that of highly symmetrical biphenyl type epoxy resins. Since the melting point can be lowered by several tens of degrees, workability can be improved.

(Wherein, the nitrogen atom is bonded to either the ortho-position, meta-position or para-position of the aromatic ring, and X is H [hydrogen], CN [cyano group], F [fluorine], Cl [chlorine] , Br [bromine], I [iodine], a methoxy group, and an ethoxy group.)

In addition, in the monoglycidyl ether represented by the chemical formula of Chemical Formula 1, the nitrogen atom is bound to either the ortho-position, the meta-position or the para-position of the aromatic ring. The monoglycidyl ether represented by the chemical formula of chemical formula 3 in which the nitrogen atom is attached to the para position of the aromatic ring, and the chemical formula of chemical formula 4 in which the nitrogen atom is attached to the meta position of the aromatic ring The monoglycidyl ether represented by the formula, and the monoglycidyl ether represented by the chemical formula of chemical formula 5 in which the nitrogen atom is bonded to the ortho position of the aromatic ring are included. In addition, in the monoglycidyl ethers represented by chemical formulas 3, 4, and 5, X is the same as in chemical formula 1.

In Chemical formula 3, specifically, 4-benzylideneaminophenol glycidyl ether, 4-4′-cyanobenzylideneaminophenol glycidyl ether, 4-4′-benzylidene fluorideaminophenol glycidyl ether, 4-4′-benzylideneamino chloride Phenol glycidyl ether, 4-4′-benzylidene bromide aminophenol glycidyl ether, 4-4′-benzylidene iodide aminophenol glycidyl ether, 4-4′-methoxybenzylidene aminophenol glycidyl ether, 4-4′-ethoxybenzylideneamino Phenol glycidyl ether is preferred.

In Chemical formula 4, specifically, 3-benzylideneaminophenol glycidyl ether, 3-4′-cyanobenzylideneaminophenol glycidyl ether, 3-4′-benzylidene fluorideaminophenol glycidyl ether, 3-4′-benzylideneamino chloride Phenol glycidyl ether, 3-4′-benzylidene bromide aminophenol glycidyl ether, 3-4′-benzylidene iodide aminophenol glycidyl ether, 3-4′-methoxybenzylidene aminophenol glycidyl ether, 3-4′-ethoxybenzylidene amino Phenol glycidyl ether is preferred.

In Chemical formula 5, specifically, 2-benzylideneaminophenol glycidyl ether, 2-4′-cyanobenzylideneaminophenol glycidyl ether, 2-4′-benzylidene fluorideaminophenol glycidyl ether, 2-4′-benzylideneamino chloride Phenol glycidyl ether, 2-4′-benzylidene bromide aminophenol glycidyl ether, 2-4′-benzylidene iodide aminophenol glycidyl ether, 2-4′-methoxybenzylidene aminophenol glycidyl ether, 2-4′-ethoxybenzylidene amino Phenol glycidyl ether is preferred.

The monoglycidyl ethers of chemical formulas 3, 4 and 5 contained in chemical formula 1 can be used singly or in combination. Moreover, each specific compound contained in the monoglycidyl ethers of chemical formulas 3, 4, and 5 can be used singly or in combination. For example, 4-benzylideneaminophenol glycidyl ether and 4-4'-cyanobenzylideneaminophenol glycidyl ether in chemical formula 3 can be used in combination.

The diglycidyl ether represented by the chemical formula of Formula 2 is a bifunctional glycidyl ether having an aromatic ring, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, etc., which are widely used as main ingredients.

Specific examples of the diglycidyl ether represented by the chemical formula of Formula 2 include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A epoxy resin, and halogenated bisphenol F diglycidyl. ether, halogenated bisphenol S diglycidyl ether, 4,4'-biphenyldiylbis(glycidyl ether) <hereinafter referred to as 4,4'-biphenyldiglycidyl ether>, 3,3',5,5'-tetramethylbiphenyl -4,4'-Diylbis(glycidyl ether) and the like are preferred. Among these, 4,4'-biphenyldiylbis(glycidyl ether) is more preferable because it can give a cured product having excellent heat dissipation properties.

The epoxy resin composition of the present invention is a composition in which a monoglycidyl ether represented by the chemical formula of Chemical Formula 1 and a diglycidyl ether represented by the chemical formula of Chemical Formula 2 are blended. The monoglycidyl ether represented by the chemical formula of Formula 1 is preferably blended in the epoxy resin composition at 30% by weight or more, more preferably 35 to 65% by weight, and 40 to 60% by weight. Most preferably blended. When the blending ratio of the monoglycidyl ether represented by the chemical formula of Chemical Formula 1 is within this range, workability can be ensured at the work site, and the epoxy resin composition has a temperature range that exhibits liquid crystallinity, so that A cured product with excellent heat dissipation can be obtained.

At least one selected from amines, acid anhydrides, and phenols can be used as a curing agent for the above epoxy resin composition. These curing agents chemically react with the epoxy resin composition under heating to form a cured product having a three-dimensional network structure.

Specific examples of amines that can be used as curing agents include diethylenetriamine <DETA>, triethylenetetramine <TETA>, tetraethylenepentamine <TEPA>, m-xylenediamine <MXDA>, and trimethylhexamethylenediamine < TMD>, 2-methylpentamethylenediamine <2-MPMDA>, diethylaminopropylamine <DEAPA>, isophoronediamine <IPDA>, 1,3-bisaminomethylcyclohexane <1,3-BAC>, bis(4-amino cyclohexyl)methane <PACM>, norbornenediamine <NBDA>, 1,2-diaminocyclohexane <1,2-DCH>, 4,4′-diaminodiphenylmethane <DDM>, metaphenylenediamine <MPDA>, diaminodiphenylsulfone <DDS >, N-aminoethylpiperazine <N-AEP>, and the like. Among these, 4,4'-diaminodiphenylmethane <DDM> is more preferable because it can give a cured product with excellent heat dissipation.

Specific examples of acid anhydrides that can be used as curing agents include phthalic anhydride <PA>, hexahydrophthalic anhydride <HHPA>, tetrahydrophthalic anhydride <THPA>, and methyltetrahydrophthalic anhydride <Me-THPA. >, maleic anhydride, succinic anhydride <SA>, dodecynylsuccinic anhydride <DDSA>, methylnadic anhydride <NMA>, pyromellitic anhydride <PMDA>, methylhexahydrophthalic anhydride <Me-HHPA>, trianhydride Melitic acid <TMA> and the like are preferred. Among these, phthalic anhydride <PA> is more preferable because it can give a cured product having excellent heat dissipation properties.

Specific examples of phenols that can be used as curing agents include bisphenol A <BPA>, hydroquinone <HQ>, resorcinol <RES>, bisphenol F <BPF>, biphenol <BIP>, tetrabromobisphenol A <TBBA >, naphthalenediol, phenol novolak resin, cresol novolak resin, and the like.

The above curing agents can be used singly or in combination of two or more. The blending ratio of the cured product is 0.3 to 1 equivalent of the epoxy group of the epoxy resin containing the monoglycidyl ether represented by the chemical formula of Chemical Formula 1 and the dimonoglycidyl ether represented by the chemical formula of Chemical Formula 2. It is preferable to add 0.2 equivalents. More preferably, it is 0.5 equivalents to 1.1 equivalents. As a result, uncured portions are less likely to occur, and a cured product having appropriate mechanical strength can be obtained.

The epoxy resin cured product of the present invention can be blended with a curing accelerator in advance in addition to the above components within a range that does not impair the physical properties of the cured product. By adding this curing accelerator, the curing speed can be increased and the productivity can be improved.

Compounds that can be used as curing accelerators are not particularly limited, but 2-ethyl-4-methylimidazole <2E4MZ>, 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole <2E4MZ-CN>, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine <2MZ-A>, 2-phenylimidazoline <2PZL> 2,3-dihydro-1H- imidazoles such as pyrrolo[1,2-a]benzimidazole <TBZ>, tris(dimethylaminomethyl)phenol <DMP-30>, benzyldimethylamine <BDMA>, 1,8-diazabicyclo(5,4,0) Known compounds include tertiary amines such as undecene-7 <DBU>, organic phosphine compounds such as triphenylphosphine, tertiary amine salts, quaternary ammonium salts, phosphonium salts, and metal salts such as tin octylate. These accelerators are appropriately selected according to the requirements for the resin composition, such as the time required for curing and pot life.

For the curing accelerator, if necessary, colorants, antioxidants, leveling agents, surfactants, ultraviolet absorbers, silane coupling agents, inorganic fillers, resin particles, wettability improvers, etc. are added in advance to the epoxy resin composition. It can be added to the product or curing agent.

Hereinafter, the details of the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

<Example 1>
As monoglycidyl ethers, 8.90 g (32 mmol) of 4-benzylideneaminophenol glycidyl ether (component A1 in Table 1) and 4.05 g (component A2 in Table 1) of 4-4′-cyanobenzylideneaminophenol glycidyl ether ( 16 mmol) was used, and 15.51 g (52 mmol) of 4,4'-biphenyl diglycidyl ether was used as diglycidyl ether. After melting and degassing for 5 minutes, an epoxy resin composition was obtained. Then, 7.48 g of 4,4′-diaminodiphenylmethane (equivalent to 0.5 times the epoxy equivalent of the epoxy resin composition) of 4,4′-diaminodiphenylmethane was mixed with the epoxy resin composition and heated on a hot plate at 135° C. and mixed uniformly. After that, a mixture of the epoxy resin composition and 4,4′-diaminodiphenylmethane was placed in a heating device, heated at 70° C. for 2 hours, heated at 80° C. for 2 hours, and heated at 90° C. for 2 hours. , 100° C. for 2 hours, and 110° C. for 2 hours to obtain a final cured product.

<Comparative Example 1>
The final final product was obtained in the same manner as in Example 1 except that 7.87 g (48 mmol) of m,p-cresyl glycidyl ether, which is a mixture of m-cresyl glycidyl ether and p-cresyl glycidyl, was used as the monoglycidyl ether. A cured product was obtained.

Using these cured products, the thermal conductivity was measured in order to investigate the heat dissipation properties of the cured products. Thermal conductivity is a value that indicates the ease with which heat flows through a substance. It is measured by an unsteady method calculated from values such as thermal diffusivity obtained by measuring changes over time. Among these, the unsteady method, which has various measurement methods such as the laser flash method, is preferable. Using the laser flash method, which is an unsteady method, the thermal conductivity ( W/m·k) was measured twice, and the average thermal conductivity was calculated. A higher value of this thermal conductivity means that the heat is more easily transferred and the heat dissipation is superior.

Table 1 shows the formulation and performance for Example 1 and Comparative Example 1.

1 shows photographs of the cured products of Example 1 and Comparative Example 1 taken with a polarizing microscope. The scale is as shown in each photograph.

As shown in Table 1, by using 4-benzylideneaminophenol glycidyl ether (component A1 in Table 1) and 4-4′-cyanobenzylideneaminophenol glycidyl ether (component A2 in Table 1) as monoglycidyl ethers, Compared to the system using m,p-cresyl glycidyl ether, it was confirmed that the thermal conductivity of the cured product of the epoxy resin composition was improved with a significant difference, and it was found that the heat dissipation was superior. As monoglycidyl ethers, 4-benzylideneaminophenolglycidyl ether (component A1 in Table 1) and 4-4′-cyanobenzylideneaminophenolglycidyl ether (component A2 in Table 1) have aromatic rings that are monoglycidyl ether and It is considered that the interaction with the aromatic rings of the amines is caused and the respective aromatic rings are piled up to be more stabilized. Another major factor is that the monoglycidyl ether is more likely to move during the curing process when heat is applied, and to interact more easily with the aromatic rings of the monoglycidyl ether and amines. As shown in the polarizing microscope photograph in FIG. 1, the cured product of Example 1 was confirmed to have anisotropy due to the partially crystallized structure, whereas the comparative example The cured product of No. 1 is supported by the fact that anisotropy is not observed at all.

Thus, 4-benzylideneaminophenolglycidyl ether (component A1 in Table 1), 4-4'-cyanobenzylideneaminophenolglycidyl ether (component A2 in Table 1), etc. are represented by the chemical formula of Chemical Formula 1. By using monoglycidyl ether, workability is ensured at work sites for bifunctional glycidyl ethers with aromatic rings, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and biphenyl type epoxy resin, which are widely used as base resins. In addition, it was found that a cured product with more excellent heat dissipation can be obtained, and it was found that it is useful in fields such as electrical and electronic materials that require heat dissipation.

Claims (3)

(Wherein, the nitrogen atom is bound to either the ortho-position, the meta-position or the para-position of the aromatic ring, and X is selected from H, CN, F, Cl, Br, I, a methoxy group and an ethoxy group. 1 species.)
Monoglycidyl ether characterized by having a mesogenic skeleton represented by. a monoglycidyl ether according to claim 1;

(X is a halogen atom or a C1 to C5 alkyl group, a and b are the number of substituents X and are integers of 0 to 4, R is a C1 to C10 alkylene group, alkylidene group, carbonyl group, sulfonyl group, oxygen indicates a direct bond with no atoms or atomic groups.)
and a diglycidyl ether having an aromatic ring represented by
An epoxy resin composition, wherein the blending ratio of the monoglycidyl ether is 30% by weight or more. The epoxy resin composition according to claim 2;
A cured epoxy resin cured from at least one curing agent selected from amines, acid anhydrides and phenols.

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