KR20170000328A - Method for producing imide group-containing naphthol resin, thermosetting resin composition and cured product and use thereof - Google Patents

Abstract

The present invention relates to a method for preparing an imide group-containing naphthol resin having excellent mechanical properties and useful for a resin material having a high degree of freedom of molded products, a thermosetting resin composition, and a cured product and use thereof. According to the present invention, a step of naphtholization is carried out to link a naphthol compound to a bismaleimide compound. Thus, the bismaleimide compound is used for linkage of the naphthol compound so that it is converted into a naphthol compound. Therefore, it is possible to prevent polymerization of bismaleimide compounds among themselves upon the curing of a thermosetting resin so that the cured product may not become brittle. As a result, it is possible to obtain molded products having excellent mechanical properties.

Description

TECHNICAL FIELD The present invention relates to a naphthol-containing imide-containing naphthol resin, a thermosetting resin composition, a cured product thereof,

The present invention relates to a method for producing an imide group-containing naphthol resin, a thermosetting resin composition, a cured product thereof and a use thereof useful as a raw material for a heat resistant resin having excellent mechanical properties such as tensile modulus, tensile strength and elongation.

There is a demand for a resin material which can be used for an insulating material, an adhesive, a resin for a film raw material, and the like in various fields in the electric and electronic industry. As a resin material having properties required for resin materials for these applications, Patent Document 1 discloses a modified polyimide resin composition. The modified polyimide resin composition is intended to realize high hygroscopicity, mechanical strength and dielectric properties as well as hygroscopicity and adhesiveness. The modified polyimide resin composition comprises (a) a polymaleimide compound and (b) at least two OH And a phenolic resin having at least one naphthalene skeleton and (c) a resin having at least two or more glycidyl groups in the molecule at a predetermined ratio.

Japanese Patent Application Laid-Open No. 2003-73459

However, the modified polyimide resin composition disclosed in Patent Document 1 does not have sufficient mechanical properties such as tensile modulus, tensile strength and elongation. For this reason, in order to obtain a molded article having good mechanical properties by using the modified polyimide resin composition, it is necessary to use a substrate together, and there is a problem that a molded article having good mechanical properties can not be obtained from only the cured product.

Therefore, an object of the present invention is to provide a method for producing an imide-containing naphthol resin useful as a resin raw material having a good mechanical property and a high degree of freedom of a molded article in which a molded article having good mechanical properties can be obtained without using a base material, a thermosetting resin composition, Cargo and purpose of use.

In order to solve the above problems, the present invention is as follows.

(1) a naphtholizing step of reacting 0.10 to 0.40 equivalents of a maleimide group of a bismaleimide compound with 1 equivalent of a hydroxyl group of the naphthol compound to link the naphthol compound to the bismaleimide compound, A method for producing a resin.

(2) The process for producing an imide-containing naphthol resin according to (1), wherein the naphthol compound has at least two hydroxyl groups in the molecule and at least one naphthalene skeleton.

(3) The process for producing an imide-containing naphthol resin according to (1) or (2), wherein the bismaleimide compound has ether bonds and four aromatic rings.

(4) The method for producing an imide-containing naphthol resin according to any one of (1) to (3), wherein the naphtholization step is a step of heating the naphthol compound and the bismaleimide compound in a solvent.

(5) a naphtholization step of reacting the naphthol compound with the bismaleimide compound by reacting 0.10 to 0.40 equivalents of the maleimide group of the bismaleimide compound with respect to 1 equivalent of the hydroxyl group of the naphthol compound; and A process for producing a thermosetting resin curing agent containing a naphthol resin.

(6) The process for producing a thermosetting resin curing agent according to (5), wherein the hydroxyl group equivalent is 250 to 600 g / eq.

(7) A resin composition comprising a bismaleimide compound and a naphthol compound, wherein the maleimide group of the bismaleimide compound is 0.10 to 0.40 equivalent based on 1 equivalent of the hydroxyl group of the naphthol compound, Wherein the naphthol compound has two or more hydroxyl groups and one or two or more naphthalene skeletons in the molecule.

(8) The epoxy resin composition according to any one of the above (1) to (5), further comprising an epoxy resin having at least two glycidyl groups in the molecule, wherein the equivalent of the maleimide group of the maleimide compound and the epoxy equivalent of the epoxy resin The resin composition according to (7), wherein the total amount is 0.8 to 1.5 equivalents.

(9) A thermosetting resin composition comprising the thermosetting resin curing agent according to (7) or (8).

(10) The thermosetting resin composition according to (9), further comprising a curing accelerator.

(11) The thermosetting resin composition according to (9) or (10), further comprising an inorganic filler.

(12) A cured product obtained by curing the thermosetting resin composition according to any one of (9) to (11).

(13) An interlayer insulating material comprising the thermosetting resin composition according to any one of (9) to (11).

(14) A prepreg obtained by impregnating a thermosetting resin according to any one of (9) to (11) in a fibrous reinforcement, heating and drying the same, and semi-curing the thermosetting resin.

According to the present invention, there is provided a process for producing an imide-containing naphthol resin, a thermosetting resin composition, a cured product thereof, and a use thereof, which is useful as a resin raw material of a cured product having good dielectric properties and mechanical properties, which is used in various fields do.

Bismaleimide compounds are widely used as raw materials for heat-resistant resins. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-73459) discloses a modified polyimide resin composition obtained by heating and mixing a bismaleimide compound, a specific phenol resin, and an epoxy resin. A heat-resistant molded article is obtained by curing the modified polyimide resin composition.

However, the cured product of the modified polyimide resin composition is fragile, and the mechanical properties such as tensile modulus, tensile strength and elongation are not sufficient. For this reason, the modified polyimide resin composition is required to be used as a molded article to which mechanical properties of the base material have been added by curing in the state of impregnating the substrate such as glass cloth. Thus, a heat-resistant resin raw material which has good mechanical properties as a cured product itself and has high degree of freedom as a molded product is required without using a substrate in combination.

The inventors of the present invention have studied the cause of weakening of the cured product of the imide-containing naphthol resin. As a result, it has been found that the polymerization reaction occurs between the bismaleimide compounds at the time of curing, which is one cause of the deterioration of the mechanical properties of the cured product. By suppressing the polymerization reaction between these bismaleimide compounds and suppressing the influence of the polymerization reaction by using a specific bismaleimide compound, the dielectric constant of the cured product is kept good, and the tensile strength, elongation And a cured product having a greatly improved mechanical properties can be obtained. The present invention is based on this new knowledge.

(Embodiment 1)

In the present embodiment, the embodiment of the present invention will be described on the basis of the knowledge that the mechanical properties of the cured article are greatly improved by suppressing the polymerization reaction between the bismaleimide compounds.

The method for producing an imide group-containing naphthol resin of the present embodiment comprises a naphtholization step of connecting a naphthol compound with a bismaleimide compound. In the imide group-containing naphthol resin produced according to the production method of the present embodiment, the maleimide group of the bismaleimide compound becomes succinimide by the naphtholization step, and the maleimide group remains in the resulting imide group-containing naphthol resin not. Therefore, when the thermosetting resin is cured by using the imide-containing naphthol resin as a curing agent, the polymerization reaction of the bismaleimide compounds does not occur. That is, since the bismaleimide compound is a naphthol compound used for linking the naphthol compound in advance, the bismaleimide compound does not undergo polymerization reaction when the thermosetting resin is cured later.

Therefore, by using the imide group-containing naphthol resin which has undergone the naphtholization step, a cured product of a thermosetting resin having greatly improved mechanical properties such as tensile modulus, tensile strength and elongation can be obtained without lowering the dielectric properties.

In the present embodiment, " connecting a naphthol compound with a bismaleimide compound " refers to reacting a bismaleimide compound with a naphthol compound to link the naphthol compound to both ends of the bismaleimide. The bismaleimide compound is not detected from the imide group-containing naphthol resin obtained by " connecting the naphthol compound with the bismaleimide compound ". The term "no bismaleimide compound" means that the peak of the bismaleimide compound is completely lost when evaluated by Gel Permeation Chromatography (GPC).

Examples of the naphthol compound used in the naphtholization step include naphthol aralkyl resin, naphthol biphenyl aralkyl resin, and the like. Of these naphthol compounds, a naphthol compound having two or more hydroxyl groups and one or two or more naphthalene skeletons in the molecule is preferably used from the viewpoint of improving the mechanical properties while maintaining good dielectric properties of the cured product. Examples of commercially available naphthol compounds (resins) having the above structure include naphthol aralkyl resin, SN-475, SN-485 and SN-495 (trade name: Shinetsu Tetsu Sumikin Kagaku Co., Ltd.) .

As the bismaleimide compound used in the naphtholization step, bis (4-maleimide phenyl) methane, bis (4-maleimide phenyl) ether, bis Diene-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis (4- Methylphenoxy) phenyl) propane and the like. Among these bismaleimide compounds, from the viewpoint of improving the mechanical properties while keeping good dielectric properties of the cured product, it is preferable to use an ether bond and a bismaleimide having four aromatic rings, which are excellent in compatibility with the thermosetting resin A compound is preferably used. Examples of the bismaleimide compound having such a structure include 2,2'-bis- [4- (4-maleimidophenoxy) phenyl] propane. Examples of commercially available products having the above structure include BMI-4000 (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and BMI-80 (trade name, available from Kay Keisei Co., Ltd.).

In the naphtholization step, the naphthol compound is coupled with a bismaleimide group by heating a solution prepared by dissolving the naphthol compound and the bismaleimide compound. The temperature at this time is preferably 80 to 180 占 폚, more preferably 100 to 160 占 폚, and even more preferably 120 to 150 占 폚, from the viewpoint of suppressing the polymerization reaction between the maleimide groups.

The blending amount of the bismaleimide compound and the naphthol compound used in the naphtholization step is such that the naphthol compound is excessively added to the bismaleimide compound. As a result, in the naphtholization step, all of the bismaleimide compounds are used for linking the naphthol compound, and the bismaleimide compound is not detected from the obtained imide group-containing naphthol resin. Therefore, it is possible to prevent the bismaleimide compounds from reacting with each other in the curing reaction of the epoxy resin or the like to lower the mechanical properties of the cured product.

From the viewpoint that the bismaleimide compound is not detected from the obtained imide group-containing naphthol resin, the amount of the maleimide compound is preferably 0.10 to 0.40 equivalents based on 1 equivalent of the hydroxyl group of the naphthol compound, More preferably 0.15 to 0.35 equivalents, and still more preferably 0.20 to 0.30 equivalents of the maleimide group.

As described above, whether or not the naphthol compound is excessive with respect to the bismaleimide compound is determined by comparing the hydroxyl equivalent and the maleimide group equivalent. However, if a bismaleimide compound having a specific structure and a naphthol compound are present, the preferable mixing ratio of the bismaleimide compound and the naphthol compound can be specified by mass.

For example, when a naphthol compound having two or more hydroxyl groups in the molecule and one or more naphthalene skeletons is linked with an ether bond and a bismaleimide compound having four aromatic rings, the bismaleimide compound 100 The amount of the naphthol compound to be used for the mass portion is preferably 200 to 1000 parts by mass, more preferably 250 to 800 parts by mass, and still more preferably 300 to 600 parts by mass.

The solvent used in the naphtholization step can be a temperature of 120 ° C or higher and a solvent having good solubility of the bismaleimide compound and the naphthol compound is used. Examples of the solvent having such properties include propylene glycol monomethyl ether, cyclohexanone, cyclopentanone, diglyme, triglyme, N, N-dimethylformamide (DMF), N, Amide (DMAc), N-methyl-2-pyrrolidone (NMP),? -Butyrolactone, propylene glycol 1-monomethyl ether 2-acetate (PGMEA) and the like.

As described above, according to the method for producing an imide group-containing naphthol resin of the present embodiment, an imide group-containing naphthol resin containing a bismaleimide compound as a naphthol compound is obtained by a naphtholization step. Therefore, in the thermal curing reaction using the imide group-containing naphthol resin as the curing agent for the thermosetting resin, the polymerization reaction of the bismaleimide compounds does not occur. As a result, a cured product having good dielectric properties and improved mechanical properties such as tensile modulus, tensile strength and elongation, compared to conventional cured products, can be used alone as a molded product such as a sheet, A thermosetting resin curing agent is obtained.

The imide group-containing naphthol resin of the present embodiment can be used as a thermosetting resin curing agent for thermosetting a thermosetting resin such as an epoxy resin. The thermosetting resin curing agent includes both a part containing an imide group-containing naphthol resin and a part thereof all of which is an imide group-containing naphthol resin.

The imide group-containing naphthol resin of the present embodiment is preferably represented by the following general formula (1) from the viewpoint that the cured product has good mechanical properties.

(In the general formula (1), 1 and m are from 1 to 10, and n is an integer from 0 to 3)

In the imide group-containing naphthol resin represented by the general formula (1), the naphthol compound is linked by a bismaleimide compound. Therefore, when the curable resin is cured, the polymerization reaction of the bismaleimide compounds does not occur. Thus, the cured product is not weakened, the shape of the molded product and the degree of freedom of use are high, and a cured product having good mechanical properties is obtained.

X in the general formula (1) is preferably represented by the general formula (2), which has good compatibility with the thermosetting resin from the viewpoint of improving the mechanical properties while keeping the dielectric property of the cured product to good.

(In the general formula (2), Y represents -CZ ₂ -, -CO-, -O-, -S- or -SO ₂ -, and in the formulas (2) and -CZ ₂ - Z represents -CH ₃ , -CF ₃ , -C ₂ H ₅ , -F or -H, and Z in the general formula (2) and Z in -CZ ₂ - may be the same Za represents a number of 0 to 4 in Z, respectively)

The hydroxyl group equivalent of the imide group-containing naphthol compound of the general formula (1) is preferably from 250 to 600 g / eq, more preferably from 300 to 550 g / eq, from the viewpoint of providing heat resistance, tensile strength, , And more preferably 350 to 500 g / eq.

The present invention can also be embodied as a thermosetting resin composition containing a thermosetting resin curing agent. An example of the thermosetting resin included in the thermosetting resin composition is an epoxy resin. Examples of the epoxy resin include, but not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, Epoxides of aralkyl resins such as aralkyl type epoxy resins, xylenes such as phenol and naphthol, glycidyl ethers such as dicyclopentadiene type epoxy resins, dihydroxynaphthalene type epoxy resins and triphenolmethane type epoxy resins Type epoxy resin, glycidyl ester-type epoxy resin, glycidylamine-type epoxy resin, and other epoxy compounds having two or more epoxy groups in one molecule. These epoxy resins may be used alone or in combination of two or more.

The thermosetting resin composition containing the epoxy resin as the thermosetting resin preferably has an epoxy group of 0.8 to 1.5 equivalents, more preferably 0.9 to 1.2 equivalents, per epoxy equivalent of the hydroxyl group of the imide group-containing naphthol resin contained in the thermosetting resin curing agent Is more preferable.

In curing the epoxy resin, it is preferable to use a curing accelerator in combination. As such a curing accelerator, a known curing accelerator for curing the epoxy resin with a phenolic curing agent can be used. For example, a tertiary amine compound, quaternary ammonium salt, imidazoles, phosphine compounds, . More specifically, there may be mentioned triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo Methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole Phosphine compounds such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine and tri (nonylphenyl) phosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium Phthalocyanine compounds such as tetraphenylphosphonate and tetranaphthoylborate, and beta phosphorus organic phosphorus compounds such as triphenylphosphonio phenolate, and a reaction product of benzoquinone and triphenylphosphine. From the viewpoint of smoothly curing by the aryloxysilane compound, use of a tertiary amine compound, imidazoles, a phosphonium salt, or a beta phosphoric organic phosphorus compound is preferable.

The compounding ratio in the thermosetting resin composition containing the epoxy resin to the thermosetting resin curing agent of the present embodiment is preferably such that the equivalent ratio of the reactive functional group of the epoxy resin curing agent to the epoxy group of the epoxy resin is in the range of 0.5 to 1.5, particularly 0.8 to 1.2 . The curing accelerator is preferably used in a range of 0.1 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

The thermosetting resin composition of the present invention depends on the blending component and the composition ratio thereof, but hardening proceeds in the temperature range of, for example, 100 to 250 캜, similarly to the curing temperature in the case of using a known phenolic curing agent.

The present invention can also be embodied as a cured product obtained by curing a thermosetting resin composition. Since the cured product of the present embodiment has both a high glass transition temperature and low dielectric loss tangent, it is suitable as various insulating materials requiring a low dielectric loss and heat resistance. As a preferred embodiment of the present invention, for example, an interlayer insulating material of a multilayer printed circuit board can be mentioned.

The prepreg refers to a thermosetting resin composition of the present embodiment as a varnish, impregnated with a fibrous reinforcement (substrate), and heated or dried to be semi-cured. As the base material, glass cloth, carbon fiber, or the like is used. By using the thermosetting resin composition as a varnish and impregnating the fibrous reinforcement with a prepreg, the handling property is improved and the properties of the fibrous reinforcement are imparted to the cured molding to improve the mechanical properties of the cured product.

In the imide group-containing naphthol compound contained in the thermosetting resin composition of the present embodiment, the naphthol compound is linked with the bismaleimide compound. Therefore, the polymerization reaction of bismaleimide, which is one cause of weakening of the cured product, does not occur. Therefore, when a thermosetting resin composition is used, a molded product having good dielectric properties and good mechanical properties such as tensile modulus, tensile strength and elongation can be formed without using a substrate such as a fibrous reinforcement together. That is, the thermosetting resin composition of the present embodiment has a high degree of freedom of a molded product of a cured product obtained by curing, and is therefore favorable as a raw material resin such as a resin film having no substrate.

The cured product obtained by curing the thermosetting resin composition of the present embodiment has good mechanical properties. For this reason, for example, a molded product having a high glass transition temperature comprising a cured product can be obtained without adding a thermoplastic resin. For example, according to the thermosetting resin composition of the present embodiment, a molded article having a glass transition temperature of 200 ° C or higher can be obtained.

In the thermosetting resin composition of the present embodiment, an inorganic filler, a coupling agent, a releasing agent, a coloring agent, a flame retardant, a low stress agent, and the like may be added as necessary, or they may be used in advance in advance.

 Examples of the inorganic filler include amorphous silica, crystalline silica, alumina, glass, calcium silicate, magnesia, clay, talc, mica, magnesia and barium sulfate. Static silica is preferred. When it is desired to increase the compounding amount of the inorganic filler while maintaining excellent moldability, it is preferable to use a spherical inorganic filler having a wide particle size distribution enabling fine filling.

Examples of the coupling agent include silane coupling agents such as mercaptosilane type, vinylsilane type, amino silane type and epoxy silane coupling agents and titanium coupling agents; examples of releasing agents include carnauba wax and paraffin wax; Respectively. Examples of the flame retardant include phosphorus compounds and metal hydroxides, and examples of the low stress agent include silicone rubber, modified nitrile rubber, modified butadiene rubber, and modified silicone oil.

As described above, in the method for producing an imide group-containing naphthol resin of the present embodiment, a naphtholization step for connecting a naphthol compound with a bismaleimide compound is used to prepare an imide group-containing naphthol resin not containing a bismaleimide compound. This makes it possible to prevent the polymerization reaction between the bismaleimide compounds from occurring in the curing reaction of the thermosetting resin. Therefore, it is possible to obtain a cured product having good dielectric properties and good mechanical properties such as tensile modulus, tensile strength and elongation It is possible to provide a useful imide-containing naphthol resin.

(Embodiment 2)

In the present embodiment, in order to suppress the influence of the polymerization reaction between the bismaleimide compounds, the blending ratio of the bismaleimide compound and the naphthol compound contained in the resin composition is specified, and the ratio of the bismaleimide compound and the naphthol compound The case of carrying out the invention will be described.

The resin composition of the present embodiment causes an excessive amount of the naphthol compound to the bismaleimide compound in order to suppress the polymerization reaction between the bismaleimide compounds. From this viewpoint, the equivalence ratio of the maleimide group of the bismaleimide compound / the hydroxyl group of the naphthol compound is preferably 0.10 to 0.40, and more preferably 0.20 to 0.30.

It is preferable to use a bismaleimide compound having an ether bond from the viewpoint of suppressing the brittleness (embrittlement) of the cured product even if a polymerization reaction of the bismaleimide compounds occurs. The use of the bismaleimide compound having an ether bond suppresses the embrittlement of the cured product due to the polymerization reaction between the bismaleimide compounds formed by thermosetting the resin composition not subjected to the naphtholization step as a raw material, , Tensile strength, elongation, and other mechanical properties can be obtained.

From the viewpoint of obtaining a cured product having good mechanical properties such as tensile modulus, tensile strength and elongation, the bismaleimide compound has four aromatic rings and the phenolic resin compound has two or more hydroxyl groups in the molecule and one or two Or more of the naphthalene skeleton. This makes it possible to obtain a cured product having good mechanical properties by using the resin composition not subjected to the naphtholization step as a raw material.

The resin composition may further include an epoxy resin having two or more glycidyl groups in the molecule. When the resin composition further contains an epoxy resin, the total amount of the maleimide group of the maleimide compound and the epoxy group of the epoxy resin is preferably 0.8 to 1.5 equivalents relative to 1 equivalent of the hydroxyl group of the naphthol compound, more preferably 0.9 to 1.2 More preferably in an equivalent amount.

As described above, since the blending amount of the naphthol compound in the resin composition is excessive relative to the maleimide compound, and the use of the specific maleimide compound and the naphthol compound suppresses embrittlement caused by polymerization of the maleimide compound, A good cured product is obtained.

For example, by curing a resin composition containing an epoxy resin, a cured product having good mechanical properties can be obtained. Therefore, the resin composition of the present embodiment has a high degree of freedom of a molded product of a cured product obtained by curing, similar to the thermosetting resin composition of the first embodiment, and is favorable as a raw material resin such as a resin film having no substrate.

The above-described embodiments are described for the purpose of facilitating understanding of the present invention, and are not described for limiting the present invention. For this reason, each element disclosed in each of the above embodiments is intended to include all design modifications and equivalents falling within the technical scope of the present invention.

[Example]

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto. In the following examples and comparative examples, percentages other than the elongation percentage indicate% by weight.

(Example 1)

(SN-485, hydroxyl equivalent of 215 g / eq, Shin-Nettetsu Sumikin Kagaku Co., Ltd.) was added to a 300-ml four-necked flask equipped with a thermometer and a stirrer, 54.0 g of propylene glycol monomethyl ether was added, and the temperature was raised to 100 ° C to dissolve. Next, 28.53 g of 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane (trade name: BMI-4000, available from Daiwa Kasei Kogyo Co., Ltd.) And reacted for 47 hours. Thereafter, the solution was cooled to room temperature to obtain an imide group-containing naphthol resin solution (A-1, a solution of an imide group-containing naphthol resin) having a hydroxyl group equivalent of 429 g / eq and a solid content of 65.2%.

(Example 2)

(SN-485, hydroxyl equivalent of 215 g / eq, Shin-nettetsu Sumikin Kagaku Co., Ltd.), 143.33 g of naphthol aralkyl resin (trade name: SN-485, propylene glycol monomethyl 102.8 g of ether was added, and the temperature was raised to 100 캜 and dissolved. Then, 47.55 g of 2,2'-bis- [4- (4-maleimidophenoxy) phenyl] propane (trade name: BMI-4000, available from Daiwa Kasei Kogyo Co., Ltd.) And reacted for 30 hours. Thereafter, the solution was cooled to room temperature to obtain an imide-containing naphthol resin solution (A-2, solution of an imide group-containing naphthol resin) having a hydroxyl group equivalent of 382 g / eq and a solid content of 65.3%.

(Examples 3 to 4 and Comparative Example 1)

To each of the imide group-containing naphthol resin solutions (A-1 to A-2) obtained in Examples 1 and 2 was added a biphenyl aralkyl type epoxy resin (trade name: NC-3000H, epoxy equivalent: 290 g / eq; Nippon Kayaku Co., (2E4MZ) were mixed to prepare a resin composition varnish (Examples 3 to 4, a thermosetting resin curing agent, a thermosetting resin Composition).

Propylene glycol monomethyl ether (PGM) solution having a solid content of naphthol aralkyl resin of 65% was used in place of the naphthol resin solutions (A-1 to A-2) containing imide groups, To prepare a resin composition varnish (Comparative Example 1). The blending amounts of Examples 3 to 4 and Comparative Example 1 were as shown in Table 1. Further, a resin composition varnish was applied to a copper foil-lined surface, followed by drying at 100 占 폚 for 8 minutes and curing at 200 占 폚 for 6 hours. After curing, the film was peeled off from the copper foil to obtain a cured film (cured product) having a thickness of about 80 탆.

(Measurement of glass transition point)

The cured films obtained in Examples 3 to 4 and Comparative Example 1 were cut (cut out) to a predetermined size to obtain glass transition point measurement samples. The glass transition temperature of the sample was measured under the following conditions.

  Measuring equipment: Rigakushuze Thermal Mechanical Analyzer TMA8310evo

  Sample dimensions: width 5 mm length 15 mm thickness 0.080 mm (80 m)

  Atmosphere: Nitrogen

  Measuring temperature: 25 to 300 DEG C

  Heating rate: 10 占 폚 / min.

  Measurement mode: Tensile

(Measurement of tensile modulus, tensile strength and elongation)

The cured films obtained in Examples 3 to 4 and Comparative Example 1 were cut into a predetermined size to obtain samples for measurement. The tensile modulus, tensile strength and elongation of the sample were measured under the following conditions.

  Measuring instrument: Shimazu Seisakusho Co., Ltd. Autograph AG-Xplus

  Tensile speed: 5 mm / min.

  Sample dimensions: width 10 mm x length 150 mm x thickness 0.080 mm (80 m)

(Evaluation of Dielectric Properties)

The cured film thus produced was cut into a predetermined size to obtain a sample for measurement. Using the following measuring instrument, the dielectric properties of the sample were measured under the following conditions.

  Measuring instrument: Key Site Technology Co., Ltd. Network analyzer E5071C Kanto Denshi Yoga Ikatsusha cavity Resonator Pulsation method Permittivity measurement device

  Frequency: 1GHz

  Sample dimensions: width 2 mm x length 100 mm x thickness 0.080 mm (80 m)

  [Table 1]

In Table 1, the blending amount is a solid content conversion value, and the unit is parts by weight.

As shown in Table 1, the cured films of Examples 3 and 4, in which the thermosetting resin composition containing the imide group-containing naphthol resin as the thermosetting resin of Examples 1 and 2 was cured, all had dielectric properties (dielectric constant, dielectric loss tangent) And mechanical properties (tensile modulus, tensile strength, elongation). Also, the glass transition temperature was as high as 200 占 폚 or higher and was good.

(Example 5)

82.69 g of a PGM solution having a solid content of 65% of a naphthol aralkyl resin (SN-485, a hydroxyl group equivalent of 215 g / eq, Shin-Nettetsu Sumikin Kagaku Co., Ltd.), 2,2'-bis [4- (Trade name: NC-3000H, epoxy equivalent: 290 g / eq, manufactured by Nippon Kayaku Co., Ltd.), 17.83 g of a bisphenol- ) Were mixed and dissolved at room temperature while adding N, N-dimethylacetamide to obtain a resin composition varnish (B-1, resin composition).

(Example 6)

82.69 g of a PGM solution having a solid content of 65% of a naphthol aralkyl resin (trade name SN-485, a hydroxyl group equivalent of 215 g / eq, Shin Nitetsu Sumikin Kagaku Co., Ltd.), bis (4-maleimidophenyl) , And 87.00 g of a 75% MEK solution of biphenyl aralkyl type epoxy resin (trade name NC-3000H, epoxy equivalent 290 g / eq, Nippon Kayaku Co., Ltd.) were mixed, N, N-dimethylacetamide was added and dissolved at room temperature to obtain a resin composition varnish (B-2, resin composition).

(Example 7)

53.75 g of a naphthol aralkyl resin (trade name: SN-485, hydroxyl group equivalent: 215 g / eq, Shin Nitetsu Shukin Kagaku Co., Ltd.), 100 g of bis (4- (Trade name: NC-3000H, epoxy equivalent: 290 g / eq, available from Nippon Kayaku Co., Ltd.): 65.25 (trade name: BMI-H, available from Kayagasei Co., Ltd.) And 86.8 g of MEK were charged and heated to 80 캜 while being dissolved. The mixture was kept at a temperature of 80 캜 for 6 hours and then cooled to room temperature to obtain a resin composition varnish (B-3, resin composition).

(Comparative Example 2)

15.0 g of a naphthol aralkyl resin (trade name: SN-485, hydroxyl group equivalent: 215 g / eq, Shin Nitetsu Shukin Kagaku Co., Ltd.), 0.35 g of bis (4- (Trade name: NC-3000H, epoxy equivalent: 290 g / eq, available from Nippon Kayaku Co., Ltd.): 25.0 (trade name: BMI-H manufactured by KAYA CHEMICAL Co., g and 66.7 g of MEK were charged and heated to 80 캜 while being dissolved. The mixture was maintained at a temperature of 80 캜 for 17 hours and then cooled to room temperature to obtain a resin composition varnish (B-4).

(Examples 8 to 10 and Comparative Example 3)

To each of the resin composition varnishes (B-1 to B-3) obtained in Examples 5 to 7, 0.3 phr of curing accelerator 2E4MZ was added to the resin composition varnish solid content and mixed. The blending amount was as shown in Table 2. Further, a resin composition varnish was applied to a copper foil-lined surface, followed by drying at 100 占 폚 for 8 minutes and curing at 200 占 폚 for 6 hours. After curing, the film was peeled off from the copper foil to obtain a cured film having a thickness of about 80 탆 (Examples 8 to 10).

The resin composition varnish (B-4) obtained in Comparative Example 2 was used in place of the resin composition varnishes (B-1 to B-3) obtained in Examples 5 to 7, A cured film of about 80 탆 was obtained (Comparative Example 3).

[Table 2]

In Table 2, the blending amount is a solid content conversion value, and the unit is parts by weight. Inability to measure indicates that the cured product was weak and could not be subjected to a tensile test.

As shown in Table 2, Examples 8 to 10, which are resin compositions containing a bismaleimide compound and a naphthol compound whose content was adjusted so that the hydroxyl group relative to the maleimide group was excessive, all exhibited good dielectric properties and mechanical properties. Among these examples, in particular, a cured film, which is a cured product of the resin composition of Example 8 including a bismaleimide compound having an ether bond and four aromatic rings, has a good tensile modulus and a high glass transition point , And has high performance as a heat-resistant molded article.

The imide group-containing naphthol resin and thermosetting resin composition provided by the present invention are useful as insulating materials in various fields in the electric and electronic industry. The cured product obtained by curing the thermosetting resin composition is useful as a raw material for forming various molded articles having sufficient mechanical properties without using a substrate because the dielectric property and the mechanical properties are good.

Claims (14)

Containing naphthol resin having a naphtholization step of reacting 0.10 to 0.40 equivalents of a maleimide group of the bismaleimide compound with 1 equivalent of the hydroxyl group of the naphthol compound to thereby link the naphthol compound to the bismaleimide compound Way. The method according to claim 1,
Wherein the naphthol compound is an imide group-containing naphthol resin having at least two hydroxyl groups in the molecule and at least one naphthalene skeleton. 3. The method according to claim 1 or 2,
Wherein the bismaleimide compound is an imide group-containing naphthol resin having an ether bond and four aromatic rings. 4. The method according to any one of claims 1 to 3,
Wherein the naphtholization step is a step of heating the naphthol compound and the bismaleimide compound in a solvent in the presence of an imide group. Containing naphthol resin having an imide group-containing naphthol resin having a naphtholization step of reacting 0.10 to 0.40 equivalents of a maleimide group of the bismaleimide compound with 1 equivalent of the hydroxyl group of the naphthol compound to thereby link the naphthol compound to the bismaleimide compound By weight based on the total weight of the thermosetting resin curing agent. 6. The method of claim 5,
Wherein the equivalent of hydroxyl groups is from 250 to 600 g / eq. A bismaleimide compound and a naphthol compound,
The maleimide group of the bismaleimide compound is 0.10 to 0.40 equivalents relative to 1 equivalent of the hydroxyl group of the naphthol compound,
Wherein the bismaleimide compound has an ether bond and four aromatic rings,
Wherein the naphthol compound has at least two hydroxyl groups and at least one naphthalene skeleton in the molecule. 8. The method of claim 7,
Further comprising an epoxy resin having at least two glycidyl groups in the molecule,
Wherein the maleimide group equivalent of the maleimide compound and the epoxy equivalent of the epoxy resin are 0.8 to 1.5 equivalents based on 1 equivalent of the hydroxyl group of the naphthol compound. 9. A thermosetting resin composition containing the resin composition according to claim 7 or 8. 10. The method of claim 9,
Wherein the thermosetting resin composition further comprises a curing accelerator. 11. The method according to any one of claims 9 to 10,
Wherein the thermosetting resin composition further comprises an inorganic filler. A cured product obtained by curing the thermosetting resin composition according to any one of claims 9 to 11. An interlayer insulating material comprising the thermosetting resin composition according to any one of claims 9 to 11. A prepreg obtained by impregnating a thermosetting resin according to any one of claims 9 to 11 with a fibrous reinforcement, heating and drying the same, and semi-curing the thermosetting resin.