KR20210124178A - Ester compound, resin composition, cured product, and build-up film - Google Patents

Abstract

An object of the present invention is to provide an ester compound that can be used in a resin composition having excellent heat resistance and dielectric properties after curing. Moreover, an object of this invention is to provide the resin composition containing this ester compound, the hardened|cured material of this resin composition, and the buildup film formed using this resin composition.
The present invention is an ester compound having a phenylene ether oligomer structure in the main chain and polycyclic aromatic ring carbonyloxy groups at both terminals.

Description

Ester compound, resin composition, cured product, and build-up film

The present invention relates to an ester compound that can be used in a resin composition having excellent heat resistance and dielectric properties after curing. Moreover, this invention relates to the resin composition containing this ester compound, the hardened|cured material of this resin composition, and the buildup film formed using this resin composition.

Curable resins, such as an epoxy resin which have low shrinkage and are excellent in adhesiveness, insulation, and chemical-resistance, are used for many industrial products. In particular, dielectric properties such as low dielectric constant and low dielectric loss tangent are required for a resin composition used for an interlayer insulating material of a printed wiring board or the like. As a resin composition excellent in such dielectric properties, for example, Patent Documents 1 and 2 discloses a resin composition containing a curable resin and a compound having a specific structure as a curing agent. However, such a resin composition had the problem that it was difficult to make the heat resistance and dielectric characteristic after hardening compatible.

Japanese Laid-Open Patent Publication No. 2017-186551 International Publication No. 2016/114286

An object of the present invention is to provide an ester compound that can be used in a resin composition having excellent heat resistance and dielectric properties after curing. Moreover, this invention aims at providing the resin composition containing this ester compound, the hardened|cured material of this resin composition, and the buildup film formed using this resin composition.

This invention is an ester compound which has a phenylene ether oligomer structure in a principal chain, and has polycyclic aromatic ring carbonyloxy group at both terminals.

Hereinafter, the present invention will be described in detail.

MEANS TO SOLVE THE PROBLEM The present inventors examined adjusting the kind and compounding ratio of curable resin in order to obtain the resin composition which can make the heat resistance and dielectric characteristic after hardening compatible. However, it has been difficult to achieve both heat resistance and dielectric properties after curing only by adjusting the type and blending ratio of the curable resin. Therefore, the present inventors studied the use of a high molecular weight phenylene ether compound as a curing agent in order to improve heat resistance after curing. However, since compatibility with the resin component is poor, the reaction does not proceed sufficiently, and the resulting cured product is In some cases, the dielectric properties deteriorated. Therefore, as a result of further intensive studies by the present inventors, by using an ester compound having a phenylene ether oligomer structure in the main chain and polycyclic aromatic ring carbonyloxy groups at both ends as a curing agent, heat resistance and dielectric properties after curing are improved. It discovered that the outstanding resin composition could be obtained, and came to complete this invention.

The ester compound of this invention has a phenylene ether oligomer structure in a principal chain. By having a phenylene ether oligomer structure in a principal chain, the hardened|cured material of the resin composition obtained becomes the thing excellent in heat resistance.

In addition, in this specification, the said "phenylene ether oligomer structure" means the repeating structure of the phenyleneoxy unit which may be substituted.

The phenylene ether oligomer structure is preferably a repeating structure of a structural unit represented by the following formula (1-1) and/or a repeating structure of a structural unit represented by the following formula (1-2), and the following formula (2-1) It is more preferable that it is a repeating structure of the structural unit represented by ) and/or a repeating structure of the structural unit represented by following formula (2-2).

[Formula 1]

In Formulas (1-1) and (1-2), R ¹ to R ⁴ may be the same or different, respectively, and are a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms.

[Formula 2]

The ester compound of the present invention has polycyclic aromatic ring carbonyloxy groups at both terminals. By having a polycyclic aromatic ring carbonyloxy group at both terminals, compatibility with the resin component becomes excellent, and the hardened|cured material of the resin composition obtained becomes a thing excellent in dielectric properties, such as a low dielectric loss tangent.

The polycyclic aromatic ring carbonyloxy group may be a polycyclic arylcarbonyloxy group or a polycyclic heteroarylcarbonyloxy group. That is, the polycyclic aromatic ring included in the polycyclic aromatic ring carbonyloxy group may be either a polycyclic aryl group or a polycyclic heteroaryl group.

The polycyclic aryl group contained in the polycyclic arylcarbonyloxy group may be substituted or may not be substituted. Moreover, the polycyclic heteroaryl group contained in the said polycyclic heteroarylcarbonyloxy group may be substituted, and may not be substituted.

Examples of the polycyclic aryl group include a naphthyl group and an anthryl group. Among them, a naphthyl group is preferable.

Examples of the polycyclic heteroaryl group include a quinolyl group, an acridine group, an indolyl group, and a benzothienyl group.

Specific examples of the polycyclic arylcarbonyloxy group include a naphthylcarbonyloxy group and an anthrylcarbonyloxy group. Especially, a naphthylcarbonyloxy group is preferable.

Specific examples of the polycyclic heteroarylcarbonyloxy group include quinolylcarbonyloxy group, acridinecarbonyloxy group, indolylcarbonyloxy group, benzothienylcarbonyloxy group, and the like. can

The ester compound of the present invention preferably has a structure represented by the following formula (3-1) as a structure containing the polycyclic aromatic ring, and more preferably a structure represented by the following formula (3-2). .

[Formula 3]

In formulas (3-1) and (3-2), R ⁵ is a polycyclic aromatic ring, and * is a bonding position. In Formula (3-2), R<^6>-R<^9> may be respectively same or different, and is a hydrogen atom or a C1-C10 alkyl group.

In the formulas (3-1) and (3-2), R ⁵ is a polycyclic aromatic ring. That is, the ^{polycyclic aromatic ring represented by R 5} is a polycyclic aromatic ring of the above-mentioned polycyclic aromatic ring carbonyloxy group.

Moreover, it is preferable that the structure represented by said Formula (3-2) is a structure in which R<^6> and R<^8> are a methyl group, and R<^7> and R<^{9> are a hydrogen atom.}

The ester compound of the present invention may have a structure including an arylene group and two or more carbonyloxy groups in the main chain in addition to the phenylene ether oligomer structure and the polycyclic aromatic ring carbonyloxy group. It is preferable that the two or more carbonyloxy groups are bonded to the different phenylene ether oligomer structures, respectively.

The arylene group may be substituted. Moreover, two or more arylene groups may couple|bond via an oxygen atom etc.

Examples of the group containing the arylene group include a phenylene group, a naphthalene group, a biphenylene group, a diphenylene ether group, and a bisphenylene group. Especially, a diphenylene ether group is preferable.

In particular, it is preferable to have a structure represented by a following formula (4-1), and, as for the ester compound of this invention, it is more preferable to have a structure represented by a following formula (4-2).

[Formula 4]

In formulas (4-1) and (4-2), R ¹⁰ is a group containing an arylene group, and * is a bonding position. In formula (4-2), R ¹¹ to R ¹⁸ may be the same or different, respectively, and are a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms.

The structure represented by the formula (4-2) is a structure in which R ¹² , R ¹⁴ , R ¹⁵ , and R ¹⁷ are a methyl group, and R ¹¹ , R ¹³ , R ¹⁶ , and R ¹⁸ are a hydrogen atom. it is preferable

The minimum with preferable molecular weight of the ester compound of this invention is 500, and a preferable upper limit is 40,000. When the said molecular weight is this range, the ester compound of this invention becomes a thing more excellent in compatibility with a resin component, and the hardened|cured material of the resin composition obtained becomes a thing excellent in dielectric properties, such as a low dielectric loss tangent. The minimum with a more preferable molecular weight of the ester compound of this invention is 1000, and a more preferable upper limit is 15000.

In the present specification, the "molecular weight" is a molecular weight obtained from the structural formula for a compound whose molecular structure is specified, but for a compound with a wide distribution of polymerization degree and for a compound with an unspecified modified site, the number average molecular weight is used. may indicate. In this specification, the said "number average molecular weight" is a value calculated|required by polystyrene conversion by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As a column used when measuring the number average molecular weight by polystyrene conversion by GPC, JAIGEL-2H-A (made by Nippon Analytical Industry Co., Ltd.) etc. are mentioned, for example.

Moreover, the preferable upper limit of the active ester equivalent of the ester compound of this invention is 5000. When the upper limit of the said active ester equivalent is 5000 or less, compatibility with a resin component becomes more excellent, and the hardened|cured material of the resin composition obtained becomes a thing excellent in dielectric properties, such as a low dielectric loss tangent. A more preferable upper limit of the active ester equivalent is 4000, and a more preferable upper limit is 3000. Although the lower limit of the active ester equivalent of the ester compound of this invention is not specifically limited, Usually, it is 250 or more.

In addition, the said "active ester equivalent" means the value obtained by dividing the molecular weight of the ester compound by the number of ester groups contained in the ester compound.

Examples of the method for producing the ester compound of the present invention include a method in which a diol compound having a phenylene ether oligomer structure and a monocarboxylic acid having a polycyclic aromatic ring or an acid halide thereof are reacted. . Also, for example, a method of reacting a diol compound having a phenylene ether oligomer structure, a monocarboxylic acid having a polycyclic aromatic ring or an acid halide thereof, and a polyvalent carboxylic acid having an arylene group or an acid halide thereof, etc. can be heard

As a diol compound which has the said phenylene ether oligomer structure, the compound represented by a following formula (5-1), a compound represented by a following formula (5-2), etc. are mentioned, for example.

[Formula 5]

In Formula (5-1) and Formula (5-2), m and n mean the repeating number of a dimethylphenyleneoxy unit.

Examples of the monocarboxylic acid having a polycyclic aromatic ring include 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid, and 9-anthracenecarboxylic acid. acid, phenanthrene carboxylic acid, pyrene carboxylic acid, and the like. Moreover, as an acid halide of the monocarboxylic acid which has the said polycyclic aromatic ring, the acid chloride of the monocarboxylic acid which has the above-mentioned polycyclic aromatic ring, acid bromide, etc. are mentioned.

Examples of the polyhydric carboxylic acid having an arylene group include 3,3'-oxydibenzoic acid, 4,4'-oxydibenzoic acid, 4,4'-oxydiphthalic acid, and 2,6'-naphthalenedicarboxyl. Acid, 1,7'-naphthalenedicarboxylic acid, isophthalic acid, terephthalic acid, phthalic acid, 5-norbornane-2,3'dicarboxylic acid, 2,4-cyclopentadiene 1,1-dicarboxylic acid and the like. Moreover, as an acid halide of the polyhydric carboxylic acid which has the said arylene group, the acid chloride of the polyhydric carboxylic acid which has an arylene group, acid bromide, etc. which were mentioned above are mentioned.

It is a resin composition containing curable resin and a hardening|curing agent, The resin composition containing the ester compound of this invention as for the said hardening|curing agent is also one of this invention.

By containing the ester compound of this invention, in the resin composition of this invention, hardened|cured material becomes the thing excellent in heat resistance and dielectric characteristic.

The resin composition of this invention may contain another hardening|curing agent in addition to the ester compound of this invention in the range which does not impair the objective of this invention, in order to improve the workability in an unhardened state.

Examples of the other curing agent include a phenol-based curing agent, a thiol-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, a cyanate-based curing agent, and an active ester-based curing agent other than the ester compound of the present invention. Among them, other active ester curing agents and cyanate curing agents other than the ester compound of the present invention are preferable.

As said hardening|curing agent, as for content of the ester compound of this invention in the case of using only the ester compound of this invention, with respect to 1 equivalent of curable resin, a preferable minimum is 0.3 equivalent, and a preferable upper limit is 2.0 equivalent. When only the ester compound of this invention is used as said hardening|curing agent, when content of the ester compound of this invention is this range, the resin composition obtained becomes a thing excellent in heat resistance and dielectric characteristic. When only the ester compound of this invention is used as said hardening|curing agent, the more preferable minimum of content of the ester compound of this invention is 0.6 equivalent, and a more preferable upper limit is 1.5 equivalent.

Moreover, as said hardening|curing agent, as for content of the ester compound of this invention in the case of using together the ester compound of this invention and another hardening|curing agent, with respect to 1 equivalent of curable resin, a preferable lower limit is 0.05 equivalent, and a preferable upper limit is 1.8 equivalent. When using together the ester compound of this invention and another hardening|curing agent as said hardening|curing agent, when content of the ester compound of this invention is this range, the resin composition obtained becomes a thing excellent in heat resistance and dielectric property. The minimum with more preferable content of the ester compound of this invention in the case of using together the ester compound of this invention and another hardening|curing agent as said hardening|curing agent is 0.2 equivalent, and a more preferable upper limit is 1.2 equivalent. In the case of using the ester compound of the present invention and another curing agent in combination as the curing agent, the content of the total of the ester compound of the present invention and the other curing agent has a preferable lower limit of 0.3 equivalents and a preferable upper limit of 2.0 equivalents with respect to 1 equivalent of the curable resin. am.

In addition, content (equivalent) of the ester compound with respect to 1 equivalent of the said curable resin means ratio of content of the active ester group in an ester compound when content of the curable reactive group which curable resin has is set to 1. Content of the said curable reactive group can be calculated|required by dividing the content weight of curable resin by the reactor equivalent of curable resin (for example, when curable resin is an epoxy resin, epoxy equivalent). Content of the said active ester group can be calculated|required by dividing the content weight of an ester compound by the said active ester equivalent.

The resin composition of this invention contains curable resin.

As said curable resin, an epoxy resin, a cyanate resin, a phenol resin, an imide resin, a maleimide resin, a benzoxazine resin, a silicone resin, an acrylic resin, a fluororesin etc. are mentioned, for example. Especially, it is preferable that the said curable resin contains at least 1 sort(s) selected from the group which consists of an epoxy resin, a cyanate resin, a phenol resin, an imide resin, a maleimide resin, and a benzoxazine resin, and an epoxy resin It is more preferable to include The said curable resin may be used independently and may be used in combination of 2 or more types.

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, 2,2'-diallylbisphenol A epoxy resin, hydrogenated bisphenol Epoxy resin, propylene oxide-added bisphenol A epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin , fluorene type epoxy resin, naphthylene ether type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol no A rock-type epoxy resin, a glycidylamine-type epoxy resin, an alkyl polyol-type epoxy resin, a rubber-modified epoxy resin, a glycidyl ester compound, etc. are mentioned.

It is preferable that the resin composition of this invention contains a hardening accelerator. By containing the said hardening accelerator, hardening time can be shortened and productivity can be improved.

Examples of the curing accelerator include an imidazole-based curing accelerator, a tertiary amine-based curing accelerator, a phosphine-based curing accelerator, a photobase generator, and a sulfonium salt-based curing accelerator. Especially, an imidazole-type hardening accelerator and a phosphine-type hardening accelerator are preferable from a viewpoint of storage stability and sclerosis|hardenability.

The said hardening accelerator may be used independently and may be used in combination of 2 or more types.

As for content of the said hardening accelerator, with respect to 100 weight part of said curable resin, a preferable minimum is 0.01 weight part, and a preferable upper limit is 5 weight part. When content of the said hardening accelerator is this range, the effect of shortening hardening time becomes more excellent, without worsening the adhesiveness of the resin composition obtained. A more preferable lower limit of content of the said hardening accelerator is 0.05 weight part, and a more preferable upper limit is 3 weight part.

It is preferable that the resin composition of this invention contains an inorganic filler.

By containing the said inorganic filler, the resin composition of this invention becomes a thing more excellent in moisture absorption reflow resistance, plating resistance, and workability, maintaining the outstanding adhesiveness and long-term heat resistance.

It is preferable that the said inorganic filler is at least any one of silica and barium sulfate. By containing at least any one of silica and barium sulfate as said inorganic filler, the resin composition of this invention becomes a thing excellent in moisture absorption reflow resistance, plating resistance, and workability.

Examples of the inorganic filler other than the silica and the barium sulfate include alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, carbon fiber, and inorganic ion exchanger. .

The said inorganic filler may be used independently and may be used in combination of 2 or more types.

The preferable minimum of the average particle diameter of the said inorganic filler is 50 nm, and a preferable upper limit is 20 micrometers. When the average particle diameter of the said inorganic filler is this range, the resin composition obtained becomes what is more excellent in applicability|paintability and workability. A more preferable minimum of the average particle diameter of the said inorganic filler is 100 nm, and a more preferable upper limit is 10 micrometers.

As for content of the said inorganic filler, when using the solvent mentioned later, a preferable minimum is 10 weight part with respect to a total of 100 weight part of the resin composition excluding the solvent, and a preferable upper limit is 1000 weight part. When content of the said inorganic filler is this range, the resin composition obtained becomes more excellent in moisture absorption reflow tolerance, plating tolerance, and workability. A more preferable lower limit of the content of the inorganic filler is 20 parts by weight.

The resin composition of the present invention may contain a flow regulator for the purpose of improving the applicability to an adherend in a short period of time and shape retentivity.

As said flow regulator, fumed silica, such as aerosil, a layered silicate, etc. are mentioned, for example.

The said flow regulator may be used independently and may be used in combination of 2 or more types.

Moreover, as said flow regulator, the thing with an average particle diameter of less than 100 nm is used preferably.

As for content of the said flow regulator, with respect to 100 weight part of said curable resin, a preferable minimum is 0.1 weight part, and a preferable upper limit is 100 weight part. When content of the said flow regulator is this range, the effect of improving the applicability|paintability with respect to a to-be-adhered body in a short time and shape retentivity becomes more excellent. A more preferable lower limit of the content of the flow regulator is 0.5 parts by weight, and a more preferable upper limit thereof is 50 parts by weight.

The resin composition of this invention may contain an organic filler for the purpose of stress relaxation, toughness provision, etc.

Examples of the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, and core shell particles thereof. can Especially, polyamide particle|grains, polyamideimide particle|grains, and polyimide particle|grains are preferable.

The said organic filler may be used independently and may be used in combination of 2 or more types.

As for content of the said organic filler, when using the solvent mentioned later, a preferable upper limit is 300 weight part with respect to a total of 100 weight part of the resin composition excluding the solvent. When content of the said organic filler is this range, toughness etc. become more excellent in the hardened|cured material of the resin composition obtained, maintaining the outstanding adhesiveness etc. A more preferable upper limit of the content of the organic filler is 200 parts by weight.

The resin composition of this invention may contain a flame retardant.

Examples of the flame retardant include metal hydrates such as boehmite-type aluminum hydroxide, aluminum hydroxide, and magnesium hydroxide, halogen-based compounds, phosphorus-based compounds, and nitrogen compounds. Among them, boehmite-type aluminum hydroxide is preferable.

The said flame retardant may be used independently and may be used in combination of 2 or more types.

As for content of the said flame retardant, with respect to 100 weight part of said curable resin, a preferable minimum is 2 weight part, and a preferable upper limit is 300 weight part. When content of the said flame retardant is this range, it becomes the thing excellent in a flame retardance, maintaining the adhesiveness etc. which were excellent in the resin composition obtained. A more preferable lower limit of the content of the flame retardant is 5 parts by weight, and a more preferable upper limit thereof is 250 parts by weight.

The resin composition of this invention may contain a thermoplastic resin in the range which does not impair the objective of this invention. By using the above-mentioned thermoplastic resin, the resin composition of the present invention has more excellent flow properties, it is easier to achieve both filling properties and leaching prevention properties during thermocompression bonding, and further excellent in bending resistance after curing. .

Examples of the thermoplastic resin include a polyimide resin, a phenoxy resin, a polyamide resin, a polyamideimide resin, a polyvinyl acetal resin, and a bismaleimide resin. Especially, a polyimide resin, a phenoxy resin, and a bismaleimide resin are preferable at the point of heat resistance and handleability.

The said thermoplastic resin may be used independently and may be used in combination of 2 or more types.

The minimum with preferable number average molecular weight of the said thermoplastic resin is 2000, and a preferable upper limit is 100,000. When the said number average molecular weight of the said thermoplastic resin is this range, the resin composition obtained becomes a thing more excellent in flow characteristics and bending resistance after hardening. The minimum with a more preferable number average molecular weight of the said thermoplastic resin is 5000, and a more preferable upper limit is 50,000.

As for content of the said thermoplastic resin, with respect to 100 weight part of said curable resins, a preferable minimum is 0.5 weight part, and a preferable upper limit is 120 weight part. When content of the said thermoplastic resin is 0.5 weight part or more, the resin composition obtained becomes a thing more excellent in flow characteristics and bending resistance after hardening. When content of the said thermoplastic resin is 120 weight part or less, the resin composition obtained becomes a thing excellent in adhesiveness and heat resistance. A more preferable lower limit of the content of the thermoplastic resin is 1 part by weight, and a more preferable upper limit is 80 parts by weight.

The resin composition of this invention may contain a solvent from viewpoints, such as coatability.

The solvent is preferably a nonpolar solvent having a boiling point of 160°C or lower or an aprotic polar solvent having a boiling point of 160°C or lower from the viewpoints of coatability and storage stability.

Examples of the non-polar solvent having a boiling point of 160°C or less or an aprotic polar solvent having a boiling point of 160°C or less include, for example, a ketone-based solvent, an ester-based solvent, a hydrocarbon-based solvent, a halogen-based solvent, an ether-based solvent, and a nitrogen-containing solvent. and the like.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

As said ester solvent, methyl acetate, ethyl acetate, isobutyl acetate, etc. are mentioned, for example.

As said hydrocarbon solvent, benzene, toluene, normal hexane, isohexane, cyclohexane, methylcyclohexane, normal heptane etc. are mentioned, for example.

Examples of the halogen-based solvent include dichloromethane, chloroform, and trichloroethylene.

Examples of the ether-based solvent include diethyl ether, tetrahydrofuran, 1,4-dioxane, and 1,3-dioxolane.

As said nitrogen-containing solvent, acetonitrile etc. are mentioned, for example.

Among them, at least selected from the group consisting of ketone solvents having a boiling point of 60° C. or higher, ester solvents having a boiling point of 60° C. or higher, and ether solvents having a boiling point of 60° C. or higher from the viewpoint of handleability and solubility of the curing agent. 1 paper is preferred. Examples of such a solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, isobutyl acetate, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, and the like. can

In addition, the said "boiling point" means a value measured under the condition of 101 kPa, or a value converted to 101 kPa in a boiling point conversion chart or the like.

The minimum with preferable content of the said solvent in 100 weight part of resin compositions of this invention is 10 weight part, and a preferable upper limit is 80 weight part. When content of the said solvent is this range, the resin composition of this invention becomes a thing excellent in coatability etc. more. A more preferable lower limit of the content of the solvent is 20 parts by weight, and a more preferable upper limit thereof is 70 parts by weight.

The resin composition of this invention may contain a reactive diluent in the range which does not impair the objective of this invention.

The reactive diluent is preferably a reactive diluent having two or more reactive functional groups in one molecule from the viewpoint of adhesion reliability.

The resin composition of this invention may contain additives, such as a coupling agent, a dispersing agent, a storage stabilizer, a bleed prevention agent, a flux agent, and a leveling agent further.

As a method of manufacturing the resin composition of this invention, the method of mixing curable resin, the ester compound of this invention, and the solvent etc. added as needed using a mixer, etc. are mentioned, for example.

As said mixer, a homodisper, a universal mixer, a Banbury mixer, a kneader etc. are mentioned, for example.

By coating and drying the resin composition of this invention on a base film, the resin composition film which consists of the resin composition of this invention can be obtained, the resin composition film can be hardened, and hardened|cured material can be obtained. The hardened|cured material of the resin composition of this invention is also one of this invention.

As for the resin composition of this invention, a preferable minimum of the glass transition temperature of hardened|cured material is 100 degreeC, and a preferable upper limit is 250 degreeC. When the glass transition temperature of the cured product is within this range, the resin composition of the present invention has more excellent mechanical strength and long-term heat resistance of the cured product. A more preferable minimum of the glass transition temperature of the said hardened|cured material is 130 degreeC, and a more preferable upper limit is 220 degreeC.

In addition, in this specification, the said "glass transition temperature of hardened|cured material" uses a dynamic viscoelasticity measuring apparatus, and temperature increase condition from -0 to 300 degreeC at a temperature increase rate of 10 degreeC/min, a frequency of 10 Hz, and a chuck distance of 24 mm. It can be obtained as the peak temperature of the tan δ curve obtained when measured at . As said dynamic viscoelasticity measuring apparatus, the Leo Vibron dynamic viscoelasticity automatic measuring machine DDV-GP series (made by A&D company) etc. are mentioned, for example. The hardened|cured material which measures the said glass transition temperature can be obtained by heating the said resin composition film which made thickness about 400 micrometers at 190 degreeC for 30 minutes.

When it contains a biphenyl-type epoxy resin as said curable resin, the resin composition of this invention has a preferable lower limit of the linear expansion coefficient in the temperature range from 40 degreeC to 120 degreeC of hardened|cured material 5 ppm/degreeC, and a preferable upper limit is 100 ppm/°C. As for the resin composition of this invention, hardened|cured material becomes a thing excellent in heat resistance. A more preferable lower limit of the coefficient of linear expansion is 10 ppm/°C, and a more preferable upper limit thereof is 80 ppm/°C.

In addition, in this specification, the said "coefficient of linear expansion" represents a value measured by the TMA method under conditions of a temperature increase rate of 10°C/min and a force of 50 N. Moreover, the hardened|cured material used for the measurement of the said coefficient of linear expansion can be obtained by heating the said resin composition film which made thickness about 200 micrometers at 190 degreeC for 30 minutes, for example.

When it contains a biphenyl type epoxy resin as said curable resin, as for the resin composition of this invention, the preferable upper limit of the dielectric loss tangent in 23 degreeC of hardened|cured material is 0.015. When the dielectric loss tangent in 23 degreeC of the said hardened|cured material is 0.015 or less, the resin composition of this invention can be used suitably for interlayer insulating materials, such as a multilayer printed wiring board. The more preferable upper limit of the dielectric loss tangent in 23 degreeC of the said hardened|cured material is 0.01.

In addition, the "dielectric loss tangent" is a value measured under the condition of 5 GHz using a dielectric constant measuring device and a network analyzer. The cured product for measuring the "dielectric loss tangent" can be obtained by heating the resin composition film having a thickness of about 40 µm to about 200 µm at 190°C for 90 minutes.

Although the resin composition of this invention can be used for a wide use, it can be used suitably for the electronic material use especially high heat resistance is calculated|required. For example, it can be used for the die attach agent in aviation, the electric control unit (ECU) use for vehicle installation, and the power device use using SiC or GaN, etc. In addition, for example, adhesives for power overlay packages, adhesives for printed wiring boards, adhesives for coverlays of flexible printed circuit boards, copper clad laminates, adhesives for semiconductor bonding, interlayer insulation materials, prepregs, encapsulants for LEDs, structures It can also be used for adhesives for materials and the like.

Especially, since hardened|cured material has a low dielectric constant and a low dielectric loss tangent, and is excellent in a dielectric characteristic, the resin composition of this invention can be used suitably for a build-up film. The build-up film formed using the resin composition of this invention is also one of this invention.

ADVANTAGE OF THE INVENTION According to this invention, the ester compound which can be used for the resin composition excellent in the heat resistance and dielectric characteristic after hardening can be provided. Moreover, according to this invention, the resin composition containing this ester compound, the hardened|cured material of this resin composition, and the buildup film formed using this resin composition can be provided.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited only to these Examples.

(Synthesis Example 1 (Preparation of ester compound A))

20 parts by weight of the compound represented by the formula (5-1) and 7 parts by weight of triethylamine were dissolved in 100 parts by weight of tetrahydrofuran. 7.5 parts by weight of 2-naphthalenecarboxylic acid chloride was added to the obtained solution, and the mixture was stirred at room temperature for 6 hours to proceed with the esterification reaction. As the compound represented by the formula (5-1), OPE (manufactured by Mitsubishi Gas Chemical Company) having a number average molecular weight of about 1000 was used. After the reaction, the precipitate was removed by filtration, and tetrahydrofuran was removed from the resulting solution in an evaporator. Furthermore, after washing|cleaning with pure water, vacuum drying was performed and the ester compound A was obtained.

Moreover, by ^<1> H-NMR, GPC, and FT-IR analysis, it confirmed that the ester compound A was represented by following formula (6). Moreover, the number average molecular weight of the ester compound A was 2150.

[Formula 6]

In Formula (6), m and n mean the repeating number of a dimethylphenyleneoxy unit.

(Synthesis Example 2 (Preparation of ester compound B))

30 parts by weight of the compound represented by the formula (5-1) and 12 parts by weight of triethylamine and 4.5 parts by weight of 4,4'-oxydibenzoic acid chloride were dissolved in 150 parts by weight of tetrahydrofuran. 6 parts by weight of 2-naphthalenecarboxylic acid chloride was added to the obtained solution, and the mixture was stirred at room temperature for 10 hours to proceed with the esterification reaction. As the compound represented by the formula (5-1), OPE (manufactured by Mitsubishi Gas Chemical Company) having a number average molecular weight of about 1000 was used. After the reaction, the precipitate was removed by filtration, and tetrahydrofuran was removed from the resulting solution in an evaporator. Furthermore, after washing|cleaning with pure water, vacuum drying was performed and the ester compound B was obtained.

Moreover, it confirmed that the ester compound B was represented by following formula (7) by <^{1>H-NMR, GPC, and FT-IR analysis.} Moreover, the number average molecular weight of the ester compound B was 4100.

[Formula 7]

In Formula (7), m, n, o, and p mean the repeating number of a dimethylphenyleneoxy unit.

(Synthesis Example 3 (Preparation of ester compound C))

Except having changed 7.5 weight part of 2-naphthalenecarboxylic acid chlorides into 5.1 weight part of cyclohexanecarboxylic acid chlorides, it carried out similarly to the synthesis example 1, and obtained the ester compound C.

Moreover, by ^<1> H-NMR, GPC, and FT-IR analysis, it confirmed that the ester compound C was represented by following formula (8). Moreover, the number average molecular weight of the ester compound C was 1930.

[Formula 8]

In Formula (8), m and n mean the repeating number of a dimethylphenyleneoxy unit.

(Synthesis Example 4 (Preparation of ester compound D))

Except having changed 7.5 weight part of 2-naphthalenecarboxylic acid chlorides into 4.2 weight part of isobutyric acid chlorides, it carried out similarly to the synthesis example 1, and obtained the ester compound D.

Moreover, it confirmed that the ester compound D was represented by following formula (9) by <^{1>H-NMR, GPC, and FT-IR analysis.} Moreover, the number average molecular weight of the ester compound D was 1780.

[Formula 9]

In Formula (9), m and n mean the repeating number of a dimethylphenyleneoxy unit.

(Synthesis Example 5 (Preparation of ester compound E))

Except having changed 7.5 weight part of 2-naphthalenecarboxylic acid chlorides into 5.6 weight part of benzoic acid chlorides, it carried out similarly to the synthesis example 1, and obtained the ester compound E.

Moreover, it confirmed that the ester compound E was represented by following formula (10) by <^{1>H-NMR, GPC, and FT-IR analysis.} Moreover, the number average molecular weight of the ester compound E was 2010.

[Formula 10]

In Formula (10), m and n mean the repeating number of a dimethylphenyleneoxy unit.

(Examples 1 to 6, Comparative Examples 1 to 5)

Methyl ethyl ketone was added as a solvent to each material of the compounding ratio of Table 1, and it stirred at 1200 rpm using a stirrer for 4 hours, and obtained the resin composition. In addition, when the molecular weight of the compound represented by the said Formula (5-1) is regarded as 1000, by dividing the theoretical molecular weight calculated|required from the structure of the said Formula (6)-(10) by the number of each ester group, ester compound A- The active ester equivalent of E was determined. As a result, the active ester equivalent of compound A was 651, the active ester equivalent of compound B was 630, the active ester equivalent of compound C was 607, the active ester equivalent of compound D was 567, and the active ester equivalent of compound E was 601. In addition, in the composition of Table 1, it described about the solid content except a solvent.

Using the applicator, the obtained resin composition was coated on the mold release treatment surface of a 25-micrometer-thick PET film. As the PET film, XG284 (manufactured by Toray Corporation) was used. Then, the non-hardened laminated|multilayer film which has a 40-micrometer-thick resin composition layer on PET film and this PET film was obtained by drying for 5 minutes in 100 degreeC gear oven and volatilizing a solvent.

<Evaluation>

The following evaluation was performed about each non-hardened laminated|multilayer film obtained by the Example and the comparative example. The results are shown in Table 1.

(Glass transition temperature of the cured product)

The base PET film was peeled from each uncured laminated|multilayer film obtained in the Example and the comparative example, the resin composition layer was superposed|stacked using the laminator, and the laminated body of about 400 micrometers in thickness was obtained. The obtained laminate was heated at 190 degreeC for 90 minutes, and hardened|cured material was obtained. With respect to the obtained cured product, using a dynamic viscoelasticity measuring device, the peak temperature of the tanδ curve obtained when the temperature was raised from 0°C to 300°C under the conditions of a temperature increase rate of 10°C/min, a frequency of 10 Hz, and a distance between chucks of 24 mm was determined as the glass transition. It was calculated|required as temperature. As the dynamic viscoelasticity measuring apparatus, Leo Vibron DDV-25GP (manufactured by A&D Corporation) was used.

(Coefficient of linear expansion)

The base PET film was peeled from each uncured laminated|multilayer film obtained in the Example and the comparative example, the resin composition layer was superposed|stacked using the laminator, and the laminated body of about 400 micrometers in thickness was obtained. The obtained laminate was heated at 190 degreeC for 90 minutes, and hardened|cured material was obtained. About the obtained hardened|cured material, using the TMA apparatus, the coefficient of linear expansion in the temperature range from 40 degreeC to 120 degreeC was measured under the conditions of a temperature increase rate of 10 degreeC/min and a force of 50N. As the TMA apparatus, TMA7100 (manufactured by Hitachi High-Tech Sciences) was used.

(hereditary tangent)

Each uncured laminated|multilayer film obtained by the Example and the comparative example were cut out to the magnitude|size of width 2mm and length 80mm. The base PET film was peeled from the resin composition film after cutting, the resin composition layer was superposed|stacked using the laminator, and the about 200-micrometer-thick laminated body was obtained. The obtained laminate was heated at 190 degreeC for 90 minutes, and hardened|cured material was obtained. About the obtained hardened|cured material, using the cavity resonance perturbation method dielectric constant measuring apparatus and a network analyzer, the dielectric loss tangent was measured by the cavity resonance method under the conditions of 23 degreeC and frequency of 5 GHz. As the cavity resonance perturbation method dielectric constant measuring device, CP521 (manufactured by Kanto Electronics Application Development Co., Ltd.) was used, and as the network analyzer, N5224A PNA (manufactured by Keysight Technologies) was used.

Industrial Applicability

ADVANTAGE OF THE INVENTION According to this invention, the ester compound which can be used for the resin composition excellent in the heat resistance and dielectric characteristic after hardening can be provided. Moreover, according to this invention, the resin composition containing this ester compound, the hardened|cured material of this resin composition, and the buildup film formed using this resin composition can be provided.

Claims (7)

An ester compound having a phenylene ether oligomer structure in the main chain and polycyclic aromatic ring carbonyloxy groups at both terminals. The method of claim 1,
The ester compound wherein the polycyclic aromatic ring carbonyloxy group is a naphthylcarbonyloxy group. 3. The method according to claim 1 or 2,
In addition to the phenylene ether oligomer structure and the polycyclic aromatic ring carbonyloxy group, the phenylene ether has a structure including an arylene group and two or more carbonyloxy groups in the main chain, and the two or more carbonyloxy groups are different from each other. An ester compound bound to an oligomeric structure. A resin composition comprising a curable resin and a curing agent, comprising:
The said hardening|curing agent is a resin composition containing the ester compound of Claim 1, 2, or 3. 5. The method of claim 4,
The said curable resin is a resin composition containing an epoxy resin. A cured product of the resin composition according to claim 4 or 5. The buildup film formed using the resin composition of Claim 4 or 5.