JP5096668B2 - Thermosetting resin composition - Google Patents

Description

The present invention relates to a thermosetting resin composition having excellent heat resistance and a low dielectric constant and a cured product thereof, and more particularly, suitable for a substrate for electronic components suitable for use in coils, capacitors, semiconductors, and high frequency bands. The present invention relates to a thermosetting resin composition and a cured product thereof.

A molded body using an epoxy resin and a phenol novolac resin as a curing agent is widely used as a semiconductor sealing material and a printed wiring board material.

  In recent years, with the increase in the speed and capacity of electronic devices, higher heat resistance, low dielectric constant, and low dielectric loss tangent of constituent materials are required. It has become difficult to meet this demand with a combination of epoxy resin and phenol novolac resin that has been widely used so far.

In recent years, ring-opening polymerizable benzoxazine resins having excellent performance such as high heat resistance, low dielectric constant, and low water absorption have been reported (Non-patent Documents 1 and 2). For example, in Patent Document 1 and Patent Document 2, the use of a benzoxazine resin in the thermosetting resin composition reduces the absorption rate of the molded article, but the glass transition temperature only slightly increases compared to the comparative example. However, sufficient heat resistance is not obtained.
JP 2001-323047 A JP-A-11-158352 J. et al. Appl. Poly. Sci. 68, 1903 (1998) J. et al. Appl. Poly. Sci. , 74, 2266 (1999)

  In recent years, high-speed and large-capacity electronic devices are progressing, and higher heat resistance and low dielectric properties are increasingly required as materials constituting them. An object of the present invention is to provide a material having a high glass transition temperature, low dielectric constant characteristics, excellent heat resistance, and low dielectric loss tangent.

〔ここで、Ｒ_１〜Ｒ_６、Ｒ_７〜Ｒ_８が水素原子又はメチル基であり、Ｒ_７、Ｒ_８は各々独立して、芳香族を含む炭素数１０以下の炭化水素基である。〕

〔ここで、Ｒ_９〜Ｒ_１２が水素原子又はメチル基であり、Ｒ_１３、Ｒ_１４各々独立して芳香族を含む炭素数１０以下の炭化水素基である。〕 The present invention relates to a benzoxazine compound characterized by containing a structure represented by general formulas (1) and (2).

[Wherein R _{1 to} R ₆ and R _{7 to} R ₈ are a hydrogen atom or a methyl group, and R ₇ and R ₈ are each independently a hydrocarbon group having 10 or less carbon atoms including an aromatic group. ]

[Wherein R _{9 to} R ₁₂ are a hydrogen atom or a methyl group, and R ₁₃ and R _{14 are} each independently a hydrocarbon group having 10 or less carbon atoms including an aromatic group. ]

〔ここで、Ｒ_１〜Ｒ_６が水素原子又はメチル基である。〕

〔ここで、Ｒ_７〜Ｒ_１０が水素原子又はメチル基である。〕
Ｒ_１５ＮＨ_２ （５） Furthermore, the present invention is obtained by reacting a compound having a structure represented by the general formula (3) or (4) with a primary amine compound represented by the general formula (5) in the presence of formaldehyde. Benzoxazine resin.

[Wherein R _{1 to} R ₆ are a hydrogen atom or a methyl group. ]

[Wherein R _{7 to} R ₁₀ are a hydrogen atom or a methyl group. ]
R ₁₅ NH ₂ (5)

Preferably, the benzoxazine resin is obtained by reacting a compound in which R _{1 to} R ₆ in the general formula (3) are hydrogen atoms and R ₁₅ in the general formula (5) is a phenyl group, and formaldehyde.

Preferably, in the benzoxazine resin, R ₁ and R ₄ in the general formula (3) are methyl groups, R ₂ , R ₃ , R ₅ and R ₆ are hydrogen atoms, and R in the general formula (5) ₁₅ is obtained by reacting a phenyl group compound, formaldehyde.

  Furthermore, this invention relates to the thermosetting resin composition formed by containing said benzoxazine resin.

  Furthermore, this invention relates to the molded object obtained by hardening said thermosetting resin composition.

  The present invention has been intensively studied in view of the recent demands for high-speed, large-capacity and high-frequency electronic materials. As a result, compounds of the structural formulas represented by the general formulas (1) and (2) and the general formulas (3) and (4) The thermosetting resin composition containing a benzoxazine resin obtained by reacting a primary amine of general formula (5) in the presence of formaldehyde has excellent heat resistance, low dielectric properties, and high glass transition temperature. Further studies have been made and the present invention has been completed.

  By using the thermosetting resin composition of the present invention, an excellent cured product having high heat resistance, low dielectric constant, low dielectric loss tangent and high glass transition temperature can be obtained.

  Hereinafter, the present invention will be described in detail. The benzoxazine resin contained in the thermosetting resin composition of the present invention is obtained by reacting a compound represented by the general formula (3) or (4) with a primary amine of the general formula (5) in the presence of formaldehyde. Can be obtained. Even if the reaction product is a mixture containing a multimer, there is no particular problem in using it as a thermosetting resin.

In the general formula (5), the group constituting R ₁₅ is an aliphatic group, a phenyl group, or a phenyl group in which a methyl group is substituted at the ortho or para position, and preferably has 10 or less carbon atoms. . When the number of carbon atoms is 11 or more, the glass transition point and the thermal decomposition temperature of the obtained resin are lowered, so that it is not suitable for the purpose of the present invention. Examples of such primary amines include aniline, methylamine, ethylamine, n-propylamine, i-propylamine, cyclohexylamine, 2-t-butylaniline, 4-t-butylaniline and the like.

  As formaldehyde, either formalin which is an aqueous formaldehyde solution or paraformaldehyde which is a polymer thereof can be used.

  As the reaction solvent, a single or mixed solvent such as toluene, 1,4-dioxane, 1-propanol, 2-propanol, 1-butanol, ethylene glycol monobutyl ether, and xylene can be used.

  In order to react all phenolic hydroxyl groups, it is desirable to use 1 mol of primary amine and 2 mol or more of formaldehyde with respect to 1 mol of phenolic hydroxyl group. The reaction temperature is desirably 100 ° C. or higher and 130 ° C. or lower. When the reaction temperature is less than 100 ° C, the reaction does not proceed sufficiently. When the reaction temperature exceeds 130 ° C, the once formed benzoxazine ring is opened, and the side reaction is promoted.

  After completion of the reaction, after distilling off the solvent, an alkali washing operation is performed as necessary to remove the unreacted phenolic hydroxyl group-containing compound, amines, and formaldehyde, thereby obtaining a dihydroxybenzoxazine resin.

  The thermosetting resin composition of the present invention contains the benzoxazine resin (1). This benzoxazine resin (1) can be used alone or in a mixture of two or more.

  The thermosetting resin composition may further include (a) a reactive diluent, (b) a resin capable of reacting with benzoxazine, (c) a curing accelerator, (d) an additive, (e ) A solvent or the like may be contained.

  The reactive diluent (a) is a low-viscosity epoxy compound that is added to adjust the viscosity, and a bifunctional or higher functional low-viscosity epoxy compound is particularly preferable. Examples of the reactive diluent include the following compounds: diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cyclohexane dimethanol diglycidyl ether, alkylene diglycidyl ether, polyglycol. Diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, and the like. These reactive diluents can be used alone or in combination of two or more.

  As the resin capable of reacting with the benzoxazine (b), a resin containing a reactive cyclic ether group such as an epoxy resin, an oxetane resin, and an alicyclic epoxy resin can be used. Specific examples of the epoxy resin include biphenyl type epoxy, bisphenol A type epoxy, bisphenol F type epoxy, phenol novolac type epoxy, cresol novolac type epoxy, cycloaliphatic epoxy, fluorene containing epoxy, naphthalene containing epoxy and the like. . Examples of the oxetane resin include carbonate bisoxetane, adipate bisoxetane, xylylene bisoxetane, 3-ethyl-3-hydroxymethyloxetane, and benzyloxetane. As the alicyclic epoxy resin, 2- (3,4-epoxy) cyclohexyl-5,5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxycyclohexylmethyl-3,4- Epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, vinylcyclohexane dioxide, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3 , 4-epoxy-6-methylcyclohexylmethyl) adipate, exo-exobis (2,3-epoxycyclopentyl) ether, endo-exobis (2,3-epoxycyclopentyl) ether, 2,2-bis (4- (2, 3-epoxypropoxy) cyclo Xyl) propane, 2,6-bis (2,3-epoxypropoxycyclohexyl-p-dioxane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene dioxide, 1,2-epoxy- 6- (2,3-epoxypropoxy) hexahydro-4,7-methanoindane, p- (2,3-epoxy) cyclopentylphenyl-2,3-epoxypropyl ether, 1- (2,3-epoxypropoxy) phenyl- 5,6-epoxyhexahydro-4,7-methanoindane, o- (2,3-epoxy) cyclopentylphenyl-2,3-epoxypropyl ether), 1,2-bis [5- (1,2-epoxy) -4,7-hexahydromethanoindanoxyl] ethane, cyclopentenylphenylglycidylate Etc. The. (These are not particularly limited and can be selected singly or in accordance with the purpose of use such as adding two or more kinds. For example, from the balance of Tg and other obtained resin properties, bisphenol A type epoxy, phenol novolac type epoxy or these The combination of is preferable.

  As for the compounding quantity of a hardening | curing agent, 0.5-2.0 mol of epoxy is preferable with respect to 1 mol of hydroxyl groups, More preferably, it is 0.8-1.3 mol.

  A well-known thing can be used as a hardening accelerator of said (c). For example, amines (including tertiary amines) such as triethylamine, tributylamine, 1,8-diazacyclo (5.4.0) undecene-7 and phenol salts thereof, phenol novolak salts, carbonate salts, formate salts and derivatives thereof 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxy Examples thereof include imidazoles such as imidazole, or a mixture thereof.

  As the additive (d) used in the present invention, a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, a flame retardant, A colorant such as carbon black, a silicone flexible agent, or the like can be used.

  The blending amount of such a curing catalyst is preferably 0.05 to 1.0 part by weight, more preferably 0.08 to 0.5 part by weight in the composition.

  Examples of the solvent (e) include the following solvents: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Glycol ethers such as dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, 3-methoxybutyl-1 -Acet Alkylene glycol monoalkyl ether acetates such as toluene; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3- Esters such as methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate. These solvents may be used alone or in a combination of two or more.

  Although the thermosetting resin according to the present invention is cured by heating as it is, it is practically preferable to use an epoxy resin and a curing accelerator in combination. In addition, various fillers and additives known to those skilled in the art may be used as necessary for use in semiconductor sealing materials, circuit boards, and the like.

  Examples of the additive include a reinforcing material or filler, a colorant, a pigment, a release agent, a flame retardant, and a silane coupling agent. As the filler, a powdery or fibrous reinforcing agent or filler is used. Examples of the powdery reinforcing agent or filler include materials made of the following materials. Metal oxides such as aluminum oxide and magnesium oxide; metal carbonates such as calcium carbonate and magnesium carbonate; silicon compounds such as diatomaceous earth powder, basic magnesium silicate, calcined clay, fine powder silica, fused silica and crystalline silica; water Metal hydroxides such as aluminum oxide; kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc. Examples of the fibrous reinforcing agent or filler include the following materials: glass fiber, ceramic fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, polyester fiber, polyamide fiber, and the like. Examples of the colorant, pigment, or flame retardant include titanium dioxide, iron black, molybdenum red, bitumen, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, a bromine compound, and triphenyl phosphate. Examples of the mold release agent include montanic acid ester wax and carnauba wax. As the silane coupling agent, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-mercaptopropyltrimethoxysilane can be used. These additives can be used alone or in combination of two or more.

  The thermosetting resin of the present invention is useful, for example, as a printed wiring board material for electronic components, and can also be used as a sealant for semiconductor chips, transistors, capacitors, coils, and the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

  The thermal decomposition temperature, glass transition temperature, and dielectric constant were measured for each of the synthesized samples for characteristic evaluation. The measurement method for each characteristic was as follows, and the measurement results are collectively shown in Table 1.

  Thermal decomposition temperature In the presence of air, the temperature was increased at a rate of 10 ° C./min, and the temperature when the weight decreased by 5% was defined as the thermal decomposition temperature.

  Glass transition temperature: Measured dynamic viscoelasticity by applying strain of frequency 1 Hz while increasing the temperature of a cured resin processed to a width of 15 mm and a thickness of 2 mm at a rate of 3 ° C./min. The peak value of tan δ From this, the glass transition temperature (Tg) was determined.

  Dielectric constant: width 15 mm, thickness 2 mm, a cured resin plate cut into corners was sandwiched between electrodes, and measurement was performed according to JIS-K-6911.

  [Example 1] A flask was charged with 180 parts by weight of dioxane, 180 parts by weight of toluene, and 66 parts by weight of paraformaldehyde, and 98 parts by weight of aniline was added. Further, 175 parts by weight of bisphenolfluorene was added. The temperature was gradually raised to the reflux temperature and the reaction was continued for 40 hours. Thereafter, the resultant was washed with a 5% alkaline solution and crystallized with methanol to obtain the desired thermosetting resin (1). A predetermined amount of novolak resin (manufactured by Dainippon Ink & Chemicals, Inc .; trade name “DIC Phenolite TD-2131”) and 2-ethyl-4-ethylimidazole were mixed with the obtained thermosetting resin with a stirrer. This was sandwiched between two iron plates set at an interval of 2 mm, and heated and pressed at 170 ° C. and 100 Kg / cm 2 for 30 minutes. Further, it was cured by heating at 180 ° C. for 12 hours. A test piece having a predetermined size was cut out from the cured resin, and the thermal decomposition temperature, glass transition temperature (dynamic viscoelasticity), and dielectric constant were measured.

  [Example 2] A flask was charged with 380 parts by weight of dioxane, 380 parts by weight of toluene, and 114 parts by weight of paraformaldehyde, and 149 parts by weight of aniline was added. Further, 288 parts by weight of biscresol fluorene was added. The temperature was gradually raised to the reflux temperature, and the reaction was continued for 40 hours. Thereafter, the desired thermosetting resin (2) was obtained by rinsing with 5% alkali solution and crystallization with methanol. This resin was combined with a predetermined amount of a novolak type epoxy resin (Dainippon Ink Chemical Co., Ltd .; trade name “DIC Phenolite TD-2131”), 1,8-diazacyclo (5.4.0) undecene-7. And cured by heating to prepare a test piece for evaluation.

  [Example 3] A flask was charged with 250 parts by weight of dioxane, 250 parts by weight of toluene, and 66 parts by weight of paraformaldehyde, and 129 parts by weight of p-anisidine was added. Further, 175 parts by weight of bisphenolfluorene was added. The temperature was gradually raised to the reflux temperature, and the reaction was continued for 40 hours. Thereafter, after washing with 5% alkaline solution and crystallization with methanol, the desired thermosetting resin (3) was obtained. This resin was heat-cured and evaluated in the same manner as a predetermined amount of novolak type epoxy resin (Dainippon Ink Chemical Co., Ltd .; trade name “DIC phenolite TD-2131”) and 2-phenyl-4-methylimidazole. A test piece was prepared.

  [Example 4] A flask was charged with 250 parts by weight of dioxane, 250 parts by weight of toluene and 66 parts by weight of paraformaldehyde, and 112 parts by weight of p-toluidine was added. Further, 175 parts by weight of bisphenolfluorene was added. The temperature was gradually raised to the reflux temperature, and the reaction was continued for 40 hours. Then, after washing with 5% alkali solution and crystallizing with methanol, the desired thermosetting resin (4) was obtained. This resin was heat cured together with a predetermined amount of bisphenol A type epoxy resin (manufactured by Asahi Kasei Corporation; trade name “AER260”) and 1,8-diazacyclo (5.4.0) undecene-7 for evaluation. A test piece was prepared.

  Example 5 A flask was charged with 380 parts by weight of dioxane, 380 parts by weight of toluene, and 114 parts by weight of paraformaldehyde, and 149 parts by weight of t-butylaniline. Further, 288 parts by weight of biscresol fluorene was added. The temperature was gradually raised to the reflux temperature, and the reaction was continued for 40 hours. Thereafter, the resultant was washed with a 5% alkaline solution and crystallized with methanol to obtain the desired thermosetting resin (5). This resin was heat-cured together with a predetermined amount of biphenyl type epoxy resin (trade name “Epicoat YX-4000H” manufactured by Yuka Shell Co., Ltd.), 1,8-diazacyclo (5.4.0) undecene-7, and evaluated. A test piece was prepared.

Comparative Example 1 A flask was charged with 200 parts by weight of dioxane, 200 parts by weight of toluene, and 75 parts by weight of paraformaldehyde, and 98 parts by weight of aniline was added. Further, 114 parts by weight of bisphenol A was added. The temperature was gradually raised to the reflux temperature and the reaction was continued for 40 hours. Thereafter, the desired thermosetting resin (6) was obtained by rinsing with 5% alkali solution and crystallization with methanol. This resin was combined with a predetermined amount of a novolak type epoxy resin (Dainippon Ink Chemical Co., Ltd .; trade name “DIC Phenolite TD-2131”), 1,8-diazacyclo (5.4.0) undecene-7. And cured by heating to prepare a test piece for evaluation.
A test piece having a predetermined size was cut out from the obtained cured resin, and the thermal decomposition temperature, glass transition temperature (dynamic viscoelasticity), and dielectric constant were measured.

Comparative Example 2 A flask was charged with 200 parts by weight of dioxane, 200 parts by weight of toluene, and 75 parts by weight of paraformaldehyde, and 98 parts by weight of aniline was added. Further, 114 parts by weight of bisphenol S was added, the temperature was gradually raised to the reflux temperature, and the reaction was continued for 40 hours. Thereafter, it was washed with a 5% alkaline solution and crystallized with methanol to obtain the desired thermosetting resin (7). This resin is heat-cured with a predetermined amount of biphenyl type epoxy resin (manufactured by Yuka Shell Co., Ltd .; trade name “Epicoat YX-4000H”) and 1,8-diazacyclo (5.4.0) undecene-7. A test piece for evaluation was prepared.
A test piece having a predetermined size was cut out from the obtained cured resin, and the thermal decomposition temperature, glass transition temperature (dynamic viscoelasticity), and dielectric constant were measured.

  As is clear from the results shown in Table 1, the benzoxazine resins of the general formulas (1) and (2) or the compounds of the general formulas (3) and (4) are converted to primary amines of the general formula (5) in the presence of formaldehyde. With a thermosetting resin composition containing a benzoxazine resin obtained by reacting with benzoxazine resin without compromising excellent heat resistance and low dielectric constant characteristics, benzoxazine resin obtained from bisphenol A and bisphenol S Compared with the thermosetting resin composition containing, the glass transition temperature was able to be made remarkably high.

The thermosetting resin composition of the present invention is suitable for prepreg and printed wiring. Furthermore, it is suitably used as a protective film forming material for various electronic components (coils, capacitors, semiconductors, liquid crystal display devices (LCD), solid-state imaging devices (CCD), electroluminescence (EL)), and the like.

Claims (5)

A thermosetting resin composition comprising a benzoxazine resin, an epoxy resin, and a curing accelerator having a structure represented by the general formula (1).

[Wherein, R ₁ to R ₆ is a hydrogen atom or a methyl group, at least R _7, R ₈ are each independently a phenyl group or a methyl group, is selected from the group consisting of a methoxy group and butyl group One type is a phenyl group substituted at the para position . ] Benzoxazine resin, epoxy resin, and curing obtained by reacting a compound having a structure represented by general formula (3) with a primary amine compound represented by general formula (5) in the presence of formaldehyde A thermosetting resin composition comprising an accelerator.

[Here, R < ₁ > -R < ₆ > is a hydrogen atom or a methyl group. ]
R ₁₅ NH ₂ (5)
[R ₁₅ is a phenyl group or a phenyl group in which at least one selected from the group consisting of a methyl group , a methoxy group, and a butyl group is substituted at the para position . ] The benzoxazine resin is obtained by reacting a compound in which R _{1 to} R ₆ in the general formula (3) are hydrogen atoms with a compound in which R ₁₅ in the general formula (5) is a phenyl group in the presence of formaldehyde. The thermosetting resin composition according to claim 2, wherein the thermosetting resin composition is obtained. The benzoxazine resin includes a compound in which R ₁ and R ₄ in the general formula (3) are methyl groups, and R ₂ , R ₃ , R ₅ , and R ₆ are hydrogen atoms, and R ₁₅ in the general formula (5). The thermosetting resin composition according to claim 2, which is obtained by reacting a compound wherein is a phenyl group in the presence of formaldehyde.   The molded object obtained by hardening the thermosetting resin composition of any one of Claim 1 to 4.