Compound, composition, cured product, and method for producing compound

Abstract

Provided are: a compound which maintains excellent heat resistance and has a low coefficient of thermal expansion (CTE); a composition; a cured product; and a method for producing the compound. A compound represented by formula (1). In formula (1), the dashed line moieties each independently represent *-CH-CH2-or *-C = CH-, and * is bonded to the side adjacent to an oxygen atom contained in the ring. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a compound, a composition, a cured product and a method for producing the compound. Background Art

[0002] Bismaleimide resin is widely used in the fields of molding materials, composite materials, electric / electronic components, etc. as commonly known high heat-resistant thermosetting resin. In recent years, in the field of electric / electronic components, the development of microelectronics is remarkable. Especially, in large computers, the high-speed transmission of signals when adopting multilayer circuit substrates is indispensable, but when the dielectric constant of substrate materials is large, the transmission of signals is delayed, becoming an obstacle of high speed. Bismaleimide is applied to the interlayer insulating film of multilayer wiring structure, but for these reasons, the necessity of bismaleimide with low dielectric constant that can maintain heat resistance increases gradually.

[0003] Patent Document 1 discloses the following bismaleimide resin as a bismaleimide resin suitable for electronic material use: In the following structural formula, X and Y are structures containing a predetermined aromatic ring, and a and b represent an integer of 0 to 100, at least one of which is not 0.

[0004]

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2010-018791 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] Although the bismaleimide resins are excellent materials, the functionality of maleimide compounds has been further required as the field of electronic materials has been demanded to be more advanced in recent years, and maleimide compounds with high heat resistance and low coefficient of thermal expansion (CTE) are particularly required.

[0010] An object of the present invention is to solve the above-mentioned problems and to provide a maleimide compound having a low coefficient of thermal expansion (CTE) while maintaining excellent heat resistance, and a composition, a cured product, and a method for producing the compound.

[0011] Solutions for solving problems

[0012] The present inventors have conducted research based on the above problems and have solved the above problems by the following means.

[0013] <1> A compound represented by formula (1).

[0014]

[0015] In the formula (1), the dotted line parts each independently represent *—CH—CH 2 — or *—C═CH—, and * is bonded to the side adjacent to the oxygen atom contained in the ring.

[0016] <2> according to <1> The compound, wherein the compound represented by formula (1) is a compound represented by formula (2).

[0017]

[0018] <3> A compound represented by formula (4).

[0019]

[0020] In formula (4), the dotted line parts each independently represent *—CH—CH 2 — or *—C═CH—, and * is bonded to the side adjacent to the oxygen atom contained in the ring.

[0021] <4> A composition comprising <1> or <2> The compound.

[0022] <5> A solidified material comprising <4> The composition is formed.

[0023] <6> <1> or <2> The method for producing the compound comprises the step of using the intermediate represented by formula (4).

[0024]

[0025] In formula (4), the dotted line parts each independently represent *—CH—CH 2 — or *—C═CH—, and * is bonded to the side adjacent to the oxygen atom contained in the ring.

[0026] Effects of the Invention

[0027] According to the present invention, a compound having a low coefficient of thermal expansion (CTE) while maintaining excellent heat resistance, as well as a composition, a cured product, and a method for producing the compound can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This figure shows the NMR spectrum of the intermediate synthesized in Example 1.

[0029] Figure 2 The NMR spectrum of the compound represented by formula (2) in Example 1 is shown. DETAILED DESCRIPTION

[0030] Hereinafter, a mode for implementing the present invention (hereinafter, simply referred to as "this embodiment") will be described in detail. It should be noted that the following this embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment.

[0031] In addition, in this specification, "to" is used to mean that the numerical values ​​described before and after it are included as a lower limit and an upper limit.

[0032] In this specification, various physical property values ​​and characteristic values ​​are values ​​at 23° C. unless otherwise specified.

[0033] In this specification, the relative dielectric constant represents the ratio of the dielectric constant of a substance to the dielectric constant of a vacuum. In addition, in this specification, the relative dielectric constant may be simply referred to as "dielectric constant".

[0034] When the standards shown in this manual differ in measurement methods etc. depending on the year, unless otherwise specified, they are based on the standards as of January 1, 2022.

[0035] <Compound represented by formula (1)>

[0036] The compound of the present embodiment is represented by formula (1). When such a compound is made into a cured product, it is possible to effectively achieve a low coefficient of thermal expansion (CTE) while maintaining excellent heat resistance.

[0037]

[0038] In the formula (1), the dotted line parts each independently represent *—CH—CH 2 — or *—C═CH—, and * is bonded to the side adjacent to the oxygen atom contained in the ring.

[0039] In the compound represented by formula (1), the dotted line parts each independently represent *—CH—CH 2 — or *—C═CH—.

[0040] In this embodiment, the compound represented by formula (1) is represented by the following formula (2) or formula (3), and is preferably represented by formula (2).

[0041]

[0042] <Method for producing the compound represented by formula (1)>

[0043] The compound represented by formula (1) can be produced, for example, by reacting 2,5-bis(aminomethyl)tetrahydrofuran (hereinafter sometimes referred to as aminomethylfuran A) and / or 2,5-bis(aminomethyl)furan (hereinafter sometimes referred to as aminomethylfuran B) with maleic anhydride in a solvent. In this case, a catalyst may be used.

[0044] Examples of the catalyst include toluenesulfonic acid hydrate, phosphoric acid, sulfuric acid, and the like, and toluenesulfonic acid hydrate is preferred.

[0045] As the solvent, for example, aromatic hydrocarbon solvents, amide solvents, ether solvents, alcohol solvents, halogen solvents, etc. can be listed, preferably aromatic hydrocarbon solvents, amide solvents, more preferably N-methyl-2-pyrrolidone, toluene. These organic solvents can be used alone or in combination of two or more.

[0046] An example of a specific method for producing the compound represented by formula (1) is described below.

[0047] Aminomethylfuran A and / or aminomethylfuran B and maleic anhydride are dissolved in solvents, respectively, and the aminomethylfuran A and / or aminomethylfuran B solution is added (for example, dropped) to the maleic anhydride solution to produce an intermediate represented by the following formula (4).

[0048]

[0049] In formula (4), the dotted line parts each independently represent *—CH—CH 2 — or *—C═CH—, and * is bonded to the side adjacent to the oxygen atom contained in the ring.

[0050] The upper limit of the reaction temperature when aminomethylfuran A or aminomethylfuran B is reacted with maleic anhydride to produce the intermediate of the formula (4) is preferably 60°C or less, more preferably 50°C or less. The lower limit of the reaction temperature is preferably 0°C or more, more preferably 10°C or more.

[0051] Furthermore, the reaction time is preferably 0.5 hours to 100 hours, more preferably 5 hours to 48 hours.

[0052] Next, the obtained intermediate is heated for a certain period of time in the presence of a catalyst to produce the compound represented by formula (1).

[0053] The upper limit of the reaction temperature when producing the compound represented by formula (1) from the intermediate of formula (4) is preferably 250°C or lower, more preferably 200°C or lower. The lower limit of the reaction temperature is preferably 25°C or higher, more preferably 100°C or higher.

[0054] Furthermore, the upper limit of the reaction time is preferably 24 hours or less, more preferably 15 hours or less. In addition, the lower limit of the reaction time is preferably 1 hour or more.

[0055] The reaction solution obtained above can be purified after the reaction is completed, so as to purify the compound represented by formula (1).

[0056] As aminomethylfuran A and / or aminomethylfuran B, a substance obtained by the synthesis method described in paragraphs 0011 to 0016 of International Publication No. 2019 / 073987 can be used, and the content thereof is incorporated into this specification. In addition, commercially available products can also be used.

[0057] <Composition containing a compound represented by formula (1)>

[0058] The composition of the present embodiment contains the compound represented by formula (1).

[0059] The upper limit of the content of the compound represented by formula (1) in the composition is preferably 100 parts by mass or less relative to 100 parts by mass of the resin solid content, and the lower limit of the content is preferably 0.1 parts by mass or more.

[0060] The composition of the present embodiment may contain only one compound represented by formula (1), or may contain two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0061] It should be noted that the resin solid content refers to components other than fillers and solvents, and includes the compound represented by formula (1) and other resin additive components (additives such as flame retardants, etc.).

[0062] The composition of this embodiment may contain a thermosetting compound other than the compound represented by formula (1). Examples of the thermosetting compound include epoxy resins, oxetane resins, compounds having polymerizable unsaturated groups, cyanate compounds, benzoxazine resins, and phenol compounds.

[0063] As specific thermosetting compounds, reference may be made to the compounds described in paragraphs 0034 to 0039 of JP-A-2010-018791 and paragraphs 0047 to 0056 of WO2021 / 172317, the contents of which are incorporated herein.

[0064] The composition of the present embodiment may contain other components except the thermosetting compound. As other components, for example, resin additives such as fillers, solvents, thermoplastic resins (including thermoplastic elastomers), and light and / or thermal polymerization initiators, photosensitizers, curing agents, coupling agents, coloring pigments, defoamers, surface conditioners, flame retardants, dispersants, curing accelerators, ultraviolet absorbers, antioxidants, and flow regulators can be listed.

[0065] As specific other components, the compounds described in paragraphs 0040 to 0051 of JP-A-2010-018791 and paragraphs 0061 to 0076 of International Publication No. 2021 / 172317 can be referred to, and the contents thereof are incorporated into the present specification.

[0066] Examples of the solvent include ketones, cellosolves, esters, amides, aromatic hydrocarbons, etc. For specific solvents, reference can be made to paragraph 0077 of International Publication No. 2021 / 172317, the contents of which are incorporated herein.

[0067] <Cured material formed from a composition containing a compound represented by formula (1)>

[0068] The cured product of the present embodiment can be obtained by curing the above-mentioned composition according to a known method, for example, by a curing method of heat, ultraviolet rays and electron beams. When heat is used to cure, the composition can be filled into a mold, etc. within a temperature range of a molten state, and then the composition is heated to more than a specified polymerization temperature, and a cross-linking reaction is performed to obtain the composition. When ultraviolet rays are used to cure, as a light source of ultraviolet rays, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp or a metal halide lamp, etc. can be used.

[0069] The curing time of the composition when obtaining the cured product of the present embodiment is preferably 0.1 hours to 5 hours. In addition, the curing temperature is preferably 100° C. to 300° C.

[0070] The glass transition temperature (Tg) of the cured product of this embodiment is preferably 150°C or higher, more preferably 250°C or higher, according to DMA (dynamic mechanical measurement). Such a high glass transition temperature is mainly achieved by using the compound represented by formula (1). The upper limit of the glass transition temperature is, for example, 400°C or lower in practice.

[0071] The glass transition temperature (Tg) is measured by the method described in Examples below.

[0072] The cured product of this embodiment preferably has a low coefficient of thermal expansion (CTE). Specifically, when formed into a cured plate with a thickness of 1 mm, the linear thermal expansion coefficient in the direction perpendicular to the surface measured by the TMA method specified in JIS C 6481 5.19 is preferably 100 ppm / °C or less, and more preferably 80 ppm / °C or less. Regarding the lower limit, 0 ppm / °C is ideal, but 50 ppm / °C or more is practical.

[0073] The CTE was measured by the method described in the Examples below.

[0074] The compound represented by formula (1) thus obtained, the above-mentioned composition, or the above-mentioned cured product is useful in various applications such as insulating materials for printed circuit boards, resins for resists, semiconductor packaging materials, semiconductor sealing resins, adhesives for printed circuit boards, laminated board materials, resins for fiber-reinforced plastics, sealing resins for liquid crystal display panels, resins for liquid crystal color filters, coatings, various coating agents, adhesives, etc.

[0075] Example

[0076] The present invention will be described in more detail by way of the following examples. The materials, amounts used, ratios, treatment details, treatment steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0077] When it is difficult to obtain the measuring equipment, etc. used in the examples due to production suspension, etc., other equipment with equivalent performance can be used for measurement.

[0078] <Synthesis Example of H-AMF>

[0079] The tetrahydrofuran (H-AMF, molecular weight 130.19) used in this example was synthesized according to paragraph 0033 of International Publication No. 2019 / 073987.

[0080] <Example 1>

[0081] 45.19 g of maleic anhydride (manufactured by Fujifilm Wako Pure Chemical Corporation, molecular weight 130.19), 80 mL of N-methyl-2-pyrrolidone (NMP, manufactured by Kanto Chemical Co., Inc.), and 80 mL of toluene (manufactured by Kanto Chemical Co., Inc.) were added to a 200 mL flask and stirred. Then, 20.00 g of the above-synthesized H-AMF was dissolved in 40 mL of NMP and added dropwise to the above flask over 70 minutes, and stirred at room temperature overnight.

[0082] After overnight, sampling was carried out, and the NMR of the purified solid was obtained to confirm the formation of the intermediate. The NMR of the obtained intermediate is shown in Figure 1 .

[0083] Next, 5.84 g of p-toluenesulfonic acid hydrate (manufactured by Fujifilm Wako Pure Chemical Corporation, molecular weight 190.2) was put into the flask and heated at 140 °C for 6.5 hours. After natural cooling, it was left overnight, liquid separation was carried out, dehydrated with magnesium sulfate, and dried to obtain 18.34 g of a yellow solid (yield 41.1%). The NMR of the obtained yellow solid was obtained to confirm the formation of the compound represented by formula (1) (hereinafter, sometimes referred to as H-AMF-BMI). The NMR of the obtained compound is shown in Figure 2 .

[0084] <Example 2>

[0085] The yellow solid was heated to 220°C at a rate of 5°C / min using a 70 mm x 30 mm SUS (Steel Use Stainless) mold using a vacuum press, and then kept at 250°C for 3 hours. The pressing was performed at 2 MPa to obtain a cured product with a thickness of 1 mm.

[0086] <Measurement Method and Evaluation Method>

[0087] (1) Glass transition temperature (Tg)

[0088] The glass transition temperature is as follows: For a sample obtained by miniaturizing the obtained cured product to 12.7 mm × 30 mm, a dynamic viscoelasticity measuring apparatus is used to measure the dynamic viscoelasticity in a nitrogen atmosphere at a starting temperature of 30°C, an ending temperature of 300°C, a heating rate of 5°C / min, a measuring frequency of 1 Hz, in accordance with JIS-K7244-4:1999 (Plastics - Test methods for dynamic mechanical properties - Part 4: Tensile vibration - Non-resonance method), and the temperature at which the loss tangent (Tanδ) obtained at this time reaches a maximum value is taken as the glass transition temperature.

[0089] As a dynamic viscoelasticity measuring apparatus, EXSTAR6000DMS6100 manufactured by Seiko Instruments Co., Ltd. was used.

[0090] (2) Coefficient of linear Thermal Expansion (CTE)

[0091] The obtained cured product was measured for its thermal expansion coefficient by the TMA method (Thermo-Mechanical Analysis) specified in JIS C 6481 5.19. Specifically, for a sample obtained by miniaturizing the obtained cured product to 5 mm × 5 mm, a thermomechanical analyzer (manufactured by TA Instruments) was used to raise the temperature from 30°C to 340°C at a rate of 10°C per minute, and the linear thermal expansion coefficient (CTE(Z)) in the direction perpendicular to the surface at 30°C to 300°C was measured (unit: ppm / °C). Ppm is a volume ratio. For other details, the above-mentioned JIS C 6481 5.19 is used as a reference.

[0092] <Comparative Example 1>

[0093] The yellow solid in Example 2 was replaced with an equal amount of 4,4′-bismaleimidodiphenylmethane (BMI-H, manufactured by KI Chemicals Co., Ltd.), and the remainder was carried out in the same manner.

[0094] <Comparative Example 2>

[0095] The same procedures were followed except that the yellow solid in Example 2 was replaced with an equal amount of 1,6′-bismaleimide-(2,2,4-trimethyl)hexane (BMI-TMH, manufactured by Yamato Chemical Industries, Ltd.).

[0096] [Table 1]

[0097] Example 2 Comparative Example 1 Comparative Example 2 Bismaleimide H-AMF-BMI BMI-H BMII-TMH Tg Above 300℃ 146℃ Above 300℃ CTE 60-11 54-6 116-1

[0098] As shown in Table 1, the cured products of Examples have a low coefficient of thermal expansion (CTE) while maintaining excellent heat resistance.

Claims

1. A compound represented by formula (1), In the formula (1), the dotted line parts each independently represent *—CH—CH 2 — or *—C═CH—, and * is bonded to the side adjacent to the oxygen atom contained in the ring.

2. The compound according to claim 1, wherein The compound represented by formula (1) is a compound represented by formula (2), 3. A compound represented by formula (4), In formula (4), the dotted line parts each independently represent *—CH—CH 2 — or *—C═CH—, and * is bonded to the side adjacent to the oxygen atom contained in the ring. A composition comprising the compound according to claim 1 or 2. A cured product formed from the composition according to claim 4.

6. A method for producing a compound according to claim 1 or 2, comprising the step of using an intermediate represented by formula (4), In formula (4), the dotted line parts each independently represent *—CH—CH 2 — or *—C═CH—, and * is bonded to the side adjacent to the oxygen atom contained in the ring.

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