JP2006219566A - Molded form and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded form obtained by ring-opening polymerization of a dihydrobenzoxazine compound, low in both dielectric constant and dielectric loss tangent and excellent in tensile strength, elongation and heat distortion resistance in a well-balanced manner, and to provide a method for producing the molded form. <P>SOLUTION: The molded form is characterized by consisting of the ring-opened polymer of a bifunctional dihydrobenzoxazine compound of the formula (1) (wherein, R is a bivalent saturated alicyclic hydrocarbon group, preferably 1,4-cyclohexyl). It is preferable that the ring-opening polymerization be carried out at 165-195°C for 0.3-4 h under heating. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a molded article formed by ring-opening polymerization of a bifunctional dihydrobenzoxazine compound bonded with a divalent saturated alicyclic hydrocarbon group, and a method for producing the same.

  Conventionally, thermosetting resins such as phenolic resin, melamine resin, epoxy resin, unsaturated polyester resin, bismaleimide resin have excellent heat resistance and reliability based on their thermosetting properties, so they are widely used in various industrial fields. Used in.

  However, phenol resins and melamine resins have volatile by-products upon curing, epoxy resins and unsaturated polyester resins are inferior in flame retardancy, and bismaleimide resins are very expensive.

  There are electronic materials for thermosetting resins, but electronic materials such as laminates are required to have low dielectric constant characteristics due to high density electronic devices, high-speed signal transmission, and high frequency compatibility. In particular, the performance of a multilayer substrate such as an IC package is required to have a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.015 or less at 23 ° C., 100 MHz, and 1 GHz.

  Recently, dihydrobenzoxazine compounds in which a dihydrobenzoxazine ring undergoes a ring-opening polymerization reaction and is thermally cured without generation of volatile components have been actively studied in order to eliminate these drawbacks.

For example, a highly heat-resistant and low-dielectric constant thermosetting resin characterized by comprising a compound having a structure represented by the general formula (2) and / or a ring-opening polymer thereof has been proposed (for example, see Patent Document 1). ).
JP 2000-154225 A

（式中、Ｒ₁ は置換もしくは無置換の炭素数５個以上１２個以下の脂環式炭化水素基、あるいは炭素数４個以上１２個以下の直鎖もしくは分岐アルキリデン基または芳香族炭化水素置換アルキリデン基であり、Ｒ₂ 及びＲ₃ は炭素数１０個以下の脂肪族基、フェニル基、またはｔ−ブチル基がオルト位もしくはパラ位に置換されたフェニル基で、互いに同じでも異なっていてもかまわない。）

(In the formula, R ₁ represents a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a linear or branched alkylidene group having 4 to 12 carbon atoms or substituted with an aromatic hydrocarbon. An alkylidene group, wherein R ₂ and R ₃ are an aliphatic group having 10 or less carbon atoms, a phenyl group, or a phenyl group in which a t-butyl group is substituted in the ortho or para position, and may be the same or different from each other; It doesn't matter.)

  The dihydrobenzoxazine compound is a compound in which benzene rings are bonded with an alkylene group, but a compound in which nitrogen atoms in a dihydrobenzoxazine ring are bonded with an alkylene group is also known.

For example, as a compound in which nitrogen atoms in a dihydrobenzoxazine ring are bonded with an alkylene group, a method for producing a compound in which nitrogen atoms in a dihydrobenzoxazine ring are bonded with a 1,4-cyclohexane group is described. It is also described that a compound can be subjected to ring-opening polymerization (see, for example, Patent Document 2).
US Pat. No. 5,543,516

  However, only the dihydrobenzoxazine compound having the above structure is described, and the ring-opening polymerization and the ring-opening polymer have not been studied at all.

  As a result of earnestly examining the ring-opening polymerization of the compound in which the nitrogen atoms of the dihydrobenzoxazine ring are bonded to each other with the divalent alicyclic hydrocarbon group, the present inventors have obtained the dielectric constant of the obtained molded product, and It was discovered that the dielectric loss tangent was very low, leading to the present invention.

  In view of the above-mentioned drawbacks, an object of the present invention is a molded product obtained by ring-opening polymerization reaction of a dihydrobenzoxazine compound, which has a low dielectric constant and dielectric loss tangent, and excellent balance between tensile strength, elongation, and heat deformability. It is providing the molded object and its manufacturing method.

（式中、Ｒは２価の飽和脂環族炭化水素基である。） The molded article of the present invention is a ring-opening polymer of a bifunctional dihydrobenzoxazine compound represented by the following formula (1).

(In the formula, R is a divalent saturated alicyclic hydrocarbon group.)

  R in the bifunctional dihydrobenzoxazine compound represented by the above formula (1) is a divalent saturated alicyclic hydrocarbon group.

  The divalent saturated alicyclic hydrocarbon group is not particularly limited, and examples thereof include a divalent cyclopentane group, a cyclohexane group, a cycloheptane group, a cyclooctane group, and a cyclodecane group. , 4-Cyclohexane group is well-balanced in terms of tensile strength, elongation, thermal deformation, and the like, and diamine as a raw material is inexpensive and easily available, and can be preferably used.

  In addition, the divalent saturated alicyclic hydrocarbon group may have a hydrogen of the saturated alicyclic hydrocarbon group substituted with an alkyl group, an alkoxy group, or the like, or an alicyclic hydrocarbon group and dihydrobenzoxazine. An alkylene group may be present between the ring nitrogen and nitrogen.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a nonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Can be mentioned.

The hydrogen of the benzene ring in the bifunctional dihydrobenzoxazine compound represented by the above formula (1) may be substituted with an alkyl group or an alkoxy group. Examples of the alkyl group include a methyl group and an ethyl group. , A propyl group, a butyl group, an octyl group, a nonyl group, and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  The bifunctional dihydrobenzoxazine compound is preferably synthesized from a monovalent phenol, a saturated alicyclic hydrocarbon diamine, and formaldehyde.

  The monovalent phenol compound is a compound having one phenolic hydroxyl group and at least one of the ortho positions being hydrogen, such as phenol, cresol, 2-bromo-4-methylphenol, xylenol, nonylphenol, Examples thereof include pt-butylphenol and octylphenol.

  Examples of the saturated alicyclic hydrocarbon diamine include 1,3-diaminocyclopentane, 1,4-diaminocyclohexane, 1,4-diaminocycloheptane, 1,5-diaminocyclooctane, and 1,6-diaminocyclohexane. A decane etc. are mentioned and 1, 4- diaminocyclohexane is used suitably.

  Examples of the formaldehydes include formalin, which is an aqueous formaldehyde solution, and paraformaldehyde, which is a polymer of formaldehyde.

  The bifunctional dihydrobenzoxazine compound is synthesized by reacting 2 molar equivalents of a monovalent phenol, 1 molar equivalent of a saturated alicyclic hydrocarbon diamine and 4 molar equivalents of formaldehydes. The following synthesis method may be adopted.

  For example, it can be easily synthesized by mixing 2 mol of monohydric phenol, 1 mol of saturated alicyclic hydrocarbon diamine and 4 mol of formaldehyde and stirring for 10 minutes to 1 hour while heating to 100 to 130 ° C. Can do.

  Also, halogenated solvents such as chloroform, methylene chloride, dichloroethane, trichloroethane, aromatic solvents such as benzene, toluene, xylene, lower alcohols such as methanol, ethanol, propanol, butanol, 1,4-dioxane, ethylene glycol monomethyl ether Alternatively, it may be synthesized by dissolving in a solvent such as ethylene glycol monoethyl ether or ethylene glycol monobutyl ether.

  In this case, the reaction may be performed for 1 to 20 hours while heating to 50 to 130 ° C., and the solvent is removed after completion of the reaction, and if necessary, by washing with an alkaline aqueous solution, an alcohol such as methanol or ethanol, Unreacted monovalent phenol, saturated alicyclic hydrocarbon diamine and formaldehyde may be removed.

  The molded article of the present invention is a ring-opening polymer of a bifunctional dihydrobenzoxazine compound represented by the above formula (1).

  As the ring-opening polymerization method of the bifunctional dihydrobenzoxazine compound, any conventionally known polymerization method may be adopted. Generally, it may be heated at 120 to 260 ° C. for several hours, but the heating temperature is low or the heating time is If the amount is insufficient, curing may be insufficient and mechanical strength may be insufficient. If the heating temperature is too high or the heating time is too long, side reactions such as decomposition may occur and the mechanical strength may be reduced.

  Accordingly, the ring-opening polymerization is preferably performed at 165 to 195 ° C. In addition, the reaction time varies depending on the reaction temperature, and thus cannot be generally described. However, 0.3 to 4 hours is preferable as the time required for sufficient curing and decomposition.

  In order to obtain a molded article having a uniform, good appearance and excellent mechanical strength, it is preferable to preheat at a low temperature before the ring-opening polymerization, and the preheating is performed at 130 ° C. or more and less than 165 ° C. Heating at a temperature of 0.5-5 hours is preferred.

  A curing accelerator may be added when ring-opening polymerization of the bifunctional dihydrobenzoxazine compound. As the curing accelerator, any curing accelerator generally used in ring-opening polymerization of dihydrobenzoxazine compounds can be used. For example, polyfunctional phenols such as catechol and bisphenol A, p-toluene Sulfonic acids such as sulfonic acid and p-phenolsulfonic acid, carboxylic acids such as benzoic acid, salicylic acid, oxalic acid and adipic acid, cobalt (II) acetylacetonate, aluminum (III) acetylacetonate, zirconium (IV) acetylacetate Metal complexes such as nates, metal oxides such as calcium oxide, cobalt oxide, magnesium oxide and iron oxide, calcium hydroxide, imidazole and its derivatives, tertiary amines such as diazabicycloundecene, diazabicyclononene and these Salt, triphenylphosphine, triphenylphosphine -Phosphorus compounds such as benzoquinone derivatives, triphenylphosphine / triphenylboron salts, tetraphenylphosphonium / tetraphenylborate, and derivatives thereof. These may be used as only one kind or as a mixture of two or more kinds.

  The addition amount of the curing accelerator is not particularly limited. However, when added in a large amount, the dielectric constant and dielectric loss tangent may increase or the mechanical properties may be adversely affected. Therefore, the above bifunctional dihydrobenzoxazine compound is generally used. It is 5 parts by weight or less, preferably 3 parts by weight or less with respect to 100 parts by weight.

  Since the molded body has a rigid alicyclic hydrocarbon group between the ring-opened benzoxazine and the ring-opened benzoxazine, a molecular gap is secured, and the cured body has a low density as a whole. Therefore, the dielectric constant and dielectric loss tangent can be reduced, and the obtained molded product has a dielectric constant in the range of 2.3 to 3.2 at 23 ° C., 100 MHz and 1 GHz, and the dielectric loss tangent is 0.0001 to 0. The range is 0.005.

  Electronic materials such as laminates are required to have low dielectric constant characteristics due to high density of electronic equipment, high-speed signal transmission, high-frequency compatibility, etc. Especially as performance of multilayer substrates such as IC packages The lower the dielectric constant at 23 ° C., 100 MHz, and 1 GHz, the better.

  Specifically, the values of dielectric constant and dielectric loss tangent that can be preferably used vary depending on the application, and thus cannot be generally described. However, for example, the dielectric constant is 3.5 or less and the dielectric loss tangent is 0.015 or less. Preferably there is. Therefore, the said molded object can be used conveniently for such a use.

In the present invention, the dielectric constant and dielectric loss tangent are measured as follows.
A sheet-like molded body having a thickness of 1 mm obtained by ring-opening polymerization of a bifunctional dihydrobenzoxazine compound is cut into 15 mm × 15 mm, supplied to a dielectric constant measuring apparatus, measured at 23 ° C. by a capacitance method, and 100 MHz And the dielectric constant and dissipation factor at 1 GHz were read.

The molded article of the present invention preferably has a glass transition temperature of 160 to 220 ° C. When the glass transition temperature is 160 to 220 ° C., the glass transition temperature can be suitably used even in a use environment requiring heat resistance such as an automobile or an electronic material.
In the present invention, the glass transition temperature is measured by the DSC method.

The structure of the molded body of the present invention is as described above. Since the molded body is a ring-opened polymer of the bifunctional dihydrobenzoxazine compound represented by the general formula (1), the dielectric at 23 ° C., 100 MHz, and 1 GHz is used. The rate is 2.3 to 3.2, and the dielectric loss tangent is 0.0001 to 0.005. Accordingly, the molded body can be suitably used for applications such as laminates, sealants, adhesives, etc., which are required for low dielectric constant characteristics of electronic materials, particularly multilayer substrates such as IC packages.

  In addition, it has excellent heat resistance, reliability, flame retardancy, etc. based on the property of thermosetting, and since the glass transition temperature is as high as 160 to 220 ° C., it can also be used for parts where stress is applied, movable parts, And since a volatile by-product is not generated at the time of superposition | polymerization, a volatile by-product does not remain in a molded object, but it is preferable also on hygiene.

  Since the structure of the manufacturing method of the molded body of the present invention is as described above, the obtained molded body is uniform and has a good molded appearance, a high glass transition temperature, and excellent heat resistance.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

Example 1
1 mol of 1,4-diaminohexane, 2 mol of phenol, 4 mol of paraformaldehyde and 1500 g of chloroform were mixed. This mixture was heated to 60 ° C. with stirring, and reacted for 2 hours after chloroform began to circulate. After completion of the reaction, the reaction mixture was transferred to a separatory funnel, washed with a 1N aqueous sodium hydroxide solution, and then washed with ion-exchanged water. After the chloroform phase was dried with anhydrous sodium sulfate, chloroform was distilled off by a rotary evaporator to obtain a bifunctional dihydrobenzoxazine compound in which R in the formula (1) is a 1,4-cyclohexane group.

  The obtained bifunctional dihydrobenzoxazine compound is supplied to a press machine, applied with a pressure of 3 MPa, heated at 140 ° C. for 1 hour, then at 160 ° C. for 1 hour, and finally at 180 ° C. for 1 hour to perform ring-opening polymerization. To obtain a sheet-like molded body having a length of 100 mm, a width of 25 mm, and a thickness of 1 mm.

  The obtained sheet-like molded body was cut into 15 mm squares, supplied to a dielectric constant measuring apparatus (trade name “RF Impedance / Material Analyzer E4991A” manufactured by AGILENT Co., Ltd.), and subjected to dielectric constant and dielectric at 23 ° C. by a capacitance method. Tangent was measured.

  The dielectric constant at 100 MHz was 3.04 and the dielectric loss tangent was 0.00217. The dielectric constant at 1 GHz was 3.03 and the dielectric loss tangent was 0.00094.

  The glass transition temperature was 188 ° C.

Claims (4)

A molded article, which is a ring-opening polymer of a bifunctional dihydrobenzoxazine compound represented by the following formula (1):

(In the formula, R is a divalent saturated alicyclic hydrocarbon group.)   The molded article according to claim 1, wherein R is a 1,4-cyclohexyl group. The bifunctional dihydrobenzoxazine compound represented by the following formula (1) is subjected to ring-opening polymerization by heating at 165 to 195 ° C for 0.3 to 4 hours. The manufacturing method of the molded object of description.

(In the formula, R is a divalent saturated alicyclic hydrocarbon group.)   4. Molding according to claim 3, characterized in that it is preheated at 130 ° C. or more and less than 165 ° C. for 0.5 to 5 hours before ring-opening polymerization by heating at 165 to 195 ° C. for 0.3 to 4 hours. Body manufacturing method.