WO2006077862A1

WO2006077862A1 - Epoxy resin composition and optical material using same

Info

Publication number: WO2006077862A1
Application number: PCT/JP2006/300608
Authority: WO
Inventors: Hironobu Morishita
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2005-01-24
Filing date: 2006-01-18
Publication date: 2006-07-27
Also published as: JPWO2006077862A1; TW200635977A

Abstract

Disclosed is an epoxy resin composition containing a fluorine-substituted adamantanediol represented by the general formula (1) below. Also disclosed are an optical material, optical waveguide, LED member and electronic circuit using such an epoxy resin composition. A cured product of such an epoxy resin composition which contains the fluorine-substituted adamantanediol as a curing agent is excellent in optical characteristics, heat resistance, electrical characteristics, mechanical strength and the like, and thus suitably used for various optical materials such as optical waveguides, LED sealing resins, sealing agents for displays and adhesives for electronic circuits. (In the formula, n represents an integer of 1-14.)

Description

Specification

Epoxy resin composition and optical material using the same

Technical field

[0001] The present invention relates to an optical waveguide, an LED sealing resin, a sealant for display, an adhesive for electronic circuits, a reflector, an epoxy resin composition used for an optical communication device, and an optical material using the same. , Optical waveguides, LED materials, electronic circuits.

Background art

[0002] In recent years, illumination and lights using white LEDs have been proposed and put into practical use, and are expected to be used in home lighting and automobiles in the future. In addition, optical fibers and optical waveguides due to the increase in capacity and speed of electronic information have become widespread. As their performance increases, the required characteristics of resins required for these devices are becoming stricter.

For example, in the case of white LEDs expected for lighting applications, ultraviolet light resistance and heat resistance are required more and more due to the shorter wavelength and higher energy of light emitted from light emitting elements. The phenol A type epoxy resin and polycarbonate resin cannot sufficiently satisfy the above requirements, and aliphatic resins or silicone resins are used.

On the other hand, the wavelength of light used in optical fibers and optical waveguides is around 1300 nm and 1500 nm, and ordinary hydrocarbon resins have the problem of absorption in the wavelength region and increased optical loss. In response to these issues, thermosetting or UV curable siloxane resins containing epoxy groups or acrylic groups, or amorphous properties, because they are superior in transparency in the ultraviolet and near infrared regions. Application of fluororesin is being studied.

These resins have problems such as heat resistance, mechanical strength, and adhesiveness, which are other required characteristics required for the devices used, such as transparency, light resistance, and excellent strength.

Furthermore, in recent years, research and development of basic materials such as liquid crystal materials and light-emitting materials for organic EL have been conducted in order to achieve higher definition, higher viewing angle, and higher image quality of flat panel displays using liquid crystal and organic EL. However, resins such as coating materials and sealing materials used with these materials are also highly resistant, such as heat resistance, transparency, refractive index, and moisture resistance. Intensification is also being considered.

As described above, various thermosetting resins, photo-curing resins, or thermoplastic resins are used as coating materials for optical and electronic parts and encapsulating materials, and these resins are resistant to heat alone. Applied according to properties such as transparency, solubility, and adhesion

[0003] Acrylic acid esters and methacrylic acid esters having an adamantane skeleton are excellent in heat resistance by polymerizing them, and are excellent in mechanical strength and optical characteristics such as impact resistance and surface hardness. It is known that a polymer can be obtained (for example, see Patent Document 1).

In this Patent Document 1, diatalylate or dimetatalylate having a halogen atom or a hydroxyl group at positions 5 and 7 of the adamantane skeleton and polymers thereof are proposed. In addition, acrylic resins and methacrylic resins having such structural units are useful as materials for optical devices such as lenses and prisms, photosensitive materials, optical fibers, and optical disks that are colorless and transparent and have high surface hardness. In addition, the acrylic resin can be used as a heat-resistant coating forming material for methacrylic resin moldings because the melting point and surface hardness are much higher than the commonly used acrylic resins. It is highly useful. However, this acrylic resin has a drawback that transparency is not sufficient in a low wavelength region. For this reason, it has been proposed to use perfluoroadamantyl acrylates as raw materials for functional resins (see, for example, Patent Document 2).

[0004] Patent Document 1: Japanese Patent Application Laid-Open No. 63-307844

Patent Document 2: JP 2004-123687 A

Disclosure of the invention

[0005] From the above situation, the present invention is suitable as an optical waveguide, an LED sealing resin, a display material, a reflective material, an optical resin such as an optical communication device, or a coating agent for an electronic circuit. Another object of the present invention is to provide an epoxy resin composition that provides a cured resin excellent in optical properties, heat resistance, electrical properties, and mechanical strength.

[0006] As a result of intensive studies to achieve the above-mentioned object, the present inventors have maintained the heat resistance and strength, which are the above-mentioned problems, by substituting fluorine with adamantane having excellent heat resistance and strength. It can be further improved in transparency and light resistance, and the dielectric constant can be lowered by replacing the adamantane structure with fluorine. As a resin that supports higher frequency and integration of electrical circuits, etc. Alternatively, it is useful as an adhesive, a substrate film, and the like. Furthermore, by reacting fluorine-substituted adamantane with a diol, it can be reacted and cured with an epoxy resin. By blending the dioli in an epoxy resin, It was found that an epoxy resin composition giving a cured resin excellent in heat resistance, optical properties, electrical properties and mechanical strength can be obtained. The present invention has been completed on the basis of force and knowledge.

That is, the present invention provides the following epoxy resin composition, optical material, optical waveguide, electronic circuit, and LED member.

(1) An epoxy resin composition comprising a fluorine-substituted adamantanediol represented by the general formula (1) as a curing agent.

[0008] [Chemical 1]

(Where n is an integer from:! To 14)

[0009] (2) An optical material comprising the epoxy resin composition according to (1).

(3) An optical waveguide using the epoxy resin composition according to (1).

(4) An LED member using the epoxy resin composition of (1).

(5) An electronic circuit using the epoxy resin composition according to (1).

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] First, the epoxy resin composition of the present invention is characterized by containing a fluorine-substituted adamantanediol represented by the general formula (1) as a curing agent.

The fluorine-substituted adamantanediol represented by the above general formula (1) is a force obtained by fluorinating 1,3-adamantanediol, and n is 14 in the general formula (1). Fluoroadamantanediol is the most common. [0011] As the epoxy resin, known ones can be applied. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and cresol novolac type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate Nitrogen-containing heterocyclic epoxy resin such as hydantoin epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin, glycidyl ether type epoxy resin, bisphenol S type epoxy resin, low water absorption cured type Mainly used are biphenyl type epoxy resins, dicyclo ring type epoxy resins, naphthalene type epoxy resins and the like. These may be used alone or in combination of two or more.

These epoxy resins are selected according to the intended use because of their transparency, light resistance, heat resistance, and mechanical strength.

[0012] The epoxy resin may be solid or liquid at room temperature, but it is generally preferred that the epoxy resin used has an average epoxy equivalent of 90 to 1000. In addition, when it is solid, it has a softening point. A temperature of 160 ° C. or lower is preferable. If the epoxy equivalent is less than 90, the cured product of the epoxy resin composition may become brittle. If the epoxy equivalent exceeds 1000, the cured product may have a low glass transition temperature (Tg).

[0013] As the curing agent used in the epoxy resin composition of the present invention, the fluorine-substituted adamantanediol represented by the general formula (1) may be used alone, but other hardeners may be used depending on the purpose. An acid anhydride curing agent, a phenol curing agent, an amine curing agent, or the like may be used in combination as the agent.

Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, anhydrous Examples include glutaric acid, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

Examples of the phenolic curing agent include phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, and triazine-modified phenol novolak resin.

Examples of amine curing agents include dicyandiamide, m-phenylenediamine, 4, 4 And aromatic diamines such as diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and m-xylylenediamine.

Among these curing agents that may be used in combination, acid anhydride curing agents and phenol curing agents are preferred from the viewpoint of the physical properties of the cured resin.

[0014] The blending ratio of the epoxy resin and the curing agent is such that the active group capable of reacting with the epoxy group in the curing agent (such as an acid anhydride group or a hydroxyl group) is 0 with respect to 1 equivalent of the epoxy group in the epoxy resin. It is preferable that the ratio is 5 to 1.5 equivalents, more preferably 0.7 to 1.2 equivalents. By setting the blending ratio of the epoxy resin and the curing agent within the above range, the curing rate of the epoxy resin composition is not slowed, and the glass transition temperature of the cured product is not lowered. It is preferable because there is no decrease.

[0015] The epoxy resin composition of the present invention is conventionally used as necessary, for example, a curing accelerator, a deterioration preventing agent, a modifier, a silane coupling agent, a defoaming agent, an inorganic Various known additives such as powders, leveling agents, mold release agents, dyes and pigments may be appropriately blended.

Examples of the curing accelerator include, but are not limited to, for example, 1,8 diazabicyclo (5,4,0) undecene 7, triethylenediamine, trie 2,4,6 dimethylaminomethylphenol. Tertiary amines such as 2-ethyl 4-methylimidazole, imidazoles such as 2-methinoreimidazole, triphenylphosphine, tetraphenylphosphonium tetraphenolevoleate, tetra-n-butinorephosphonium o, o Examples include phosphorus compounds such as tinole phosphorodithioate, quaternary ammonium salts, organometallic salts, and derivatives thereof. These may be used alone or in combination. Among these curing accelerators, tertiary amines, imidazoles, and phosphorus compounds are preferably used.

The content of the curing accelerator is preferably 0.01 to 8.0% by mass, more preferably 0.0 :! to 3.0% by mass with respect to the epoxy resin. By setting the content of the curing accelerator within the above range, a sufficient curing accelerating effect can be obtained, and no discoloration is observed in the obtained cured product.

[0017] Examples of the deterioration preventing agent include phenolic compounds, amine compounds, and organic sulfur. Conventionally known deterioration inhibitors such as yellow compounds and phosphorus compounds can be used.

Examples of phenolic compounds include Irganox 1010 (Irganoxl010, Ciba 'Specialty' Chemicals, Trademark), Inoreganox 1076 (Irganoxl076, Chinoku 'Specialty' Chemikanorez, Trademark), Inoreganox 1330 (Irganoxl330, Chino's Specialty 'Chemica Norez, Trademark), Inoreganox 3114 (Irganox 3114, Chinoku' Specialty 'Chemicals, Trademark), Inoreganox 3125 (Irganox3125, Chinoku' Specialty 'Chemicals, Trademark), Inoreganox 3790 (Irganox3790 , Chinoku 'Specialty' Chemicals, Inc., Trademark) BHT, Cyanox 1790 (Cyanoxl790, Cyanamide, Trademark), Sumilizer GA-8 0 (SumilizerGA_80, Sumitomo Chemical, Trademark) .

[0018] Examples of amine compounds include Irgastab FS042 (Tinoku 'Specialty' Chemicals, Trademark), GENOX EP (Crimpton, Trademark, Compound Name; Dialkyl_N_methylamino oxide), and hindered amines. ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-68, LA-77, LA-82, LA-87, LA-94, CSC from Asahi Denka Tinuvinl23, 144, 440, 662, Chimassorb2020, 119, 944, Hoechst Hostavin N30, Cytec Cyasorb UV-3346, UV-3526, GLC Uval 299, Clariant SanduvorPR-31 The ability to list

Examples of organic sulfur compounds include DSTP (Yoshitomi, Trademark), DLTP (Yoshitomi, Trademark), DLTOIB (Yoshitomi, Trademark), DMTP (Yoshitomi, Trademark), Seeno X412S (Cypro Kasei Co., Ltd., trademark), Cyanox 1212 (Cyanamide Co., Ltd., trademark) and other commercial products can be listed.

[0019] Examples of the modifying agent include conventionally known modifying agents such as glycols, silicones, and alcohols. Examples of the silane coupling agent include conventionally known silane coupling agents such as silane and titanate. Examples of the defoaming agent include known defoaming agents such as silicones. Examples of the inorganic powder include conventionally known inorganic powders such as glass powder and silica powder. In addition, the epoxy resin composition of the present invention may contain a solvent as necessary. As a solvent, when the epoxy resin is a powder, or as a diluent solvent for coating, toluene is used. Aromatic solvents such as xylene, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone can be used.

[0020] The epoxy resin composition of the present invention mixes the above-mentioned epoxy resin component and curing agent with various additives, and injects them into a mold (resin mold) to be molded, or a desired film or the like by coating. After making into a shape, it is cured by heating. The curing temperature is 50 to 200 ° C, preferably 100 to 150 ° C. Setting it to 50 ° C or higher does not cause poor curing. Setting it to 200 ° C or lower eliminates coloring and the like. The curing time varies depending on the epoxy resin used, the curing accelerator, and the curing temperature, but is preferably 0.5 to 6 hours.

In the epoxy resin composition of the present invention, the cured product has excellent characteristics such as optical characteristics, heat resistance, electrical characteristics and mechanical strength, and is used for optical waveguides, LED sealing resins and electronic circuits. It can be suitably used for various optical materials such as optical resins such as adhesives, reflective materials and optical communication devices.

The present invention also provides an optical material, an optical waveguide, an LED member, and an electronic circuit obtained using the above epoxy resin composition.

Example

[0022] Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[0023] Example 1

(Synthesis of epoxy resin)

1, 3 _Perfluoroadamantanediol 3. Og, hydrogenated bisphenol A type epoxy resin (manufactured by Shin Nippon Chemical Co., Ltd., epoxy equivalent 214) 3.6 g and 4-methylolene as an antioxidant 2, Mix 6-di-tert-butylphenol (0.015 g), cast on a Teflon sheet, heat cure at 80 ° C for 1 hour, and 130 ° C for 5 hours to form a transparent cured resin (film thickness 100 μm Sheet). The following evaluation was performed on the obtained sheet (sample).

[0024] (Measurement of glass transition temperature)

Using a differential scanning calorimeter (Seiko Electronics; DSC220), the sample was heated from 25 ° C to 350 ° C under a nitrogen stream (20 ml / min) at a heating rate of 10 ° C / min. Immediately cool to remove the thermal history of the sample, and JIS K7121 The glass transition temperature was measured according to the above. As a result, the glass transition temperature was 70 ° C.

[0025] (Evaluation of optical properties)

(1) Transparency

A test piece having a length of 40 mm and a width of 40 mm was cut out from the obtained sheet, and haze was measured on the test piece by a haze meter (manufactured by Suga Test Instruments Co., Ltd .; HGM-2DP type). As a result, the haze is 0.2. /. Met.

(2) Refractive index

A test piece having a length of 20 mm and a width of 10 mm was cut out from the obtained sheet, and the refractive index was measured with an Abbe refractometer (manufactured by Atago Co., Ltd.). As a result, the refractive index was 1.50.

[0026] (Evaluation of optical loss (stroke))

A transparent thin film layer having a thickness of 0.01 mm was formed on a 10.2 cm (4 inch) silicon substrate by thermosetting (film formation) under the same conditions as in Example 1. With respect to this thin film sample, light of a predetermined wavelength (830 nm, 1300 nm) was incident using a prism force bra, and the light was propagated in the thin film. At that time, the detector was scanned along the propagation light to detect the scattered light from the sample, and the light loss of the thin film propagation light was calculated from the attenuation of the intensity.

As a result, the optical loss when 830 nm light was incident was 1.0 dB / cm (TM direction), and the optical loss when 1300 nm light was incident was 1.3 dB / cm (TM direction).

[0027] (Dielectric constant evaluation)

Using a dielectric loss measuring device TR-10C manufactured by Ando Electric Co., Ltd., measurement was performed at 1 MHz 23 ° C in accordance with IEC60250. As a result, the dielectric constant was 3.4.

Industrial applicability

[0028] The epoxy resin composition containing the fluorine-substituted adamantanediol of the present invention as a curing agent, the cured product has excellent characteristics such as optical characteristics, heat resistance, electrical characteristics and mechanical strength, It can be suitably used for various optical materials such as optical waveguides, LED members, and display sealants.

That is, since the epoxy resin composition of the present invention has such excellent characteristics, it can be used for optical semiconductors (LEDs, etc.), flat panel displays (organic EL elements, etc.), electronic circuits, It can be suitably used for optical electronic members such as resin (sealing agent, adhesive) for circuit (optical waveguide), optical communication lens, and optical film. For this reason, the epoxy resin composition of the present invention is used as a semiconductor element / integrated circuit (IC, etc.), individual semiconductor (diode, transistor, thermistor, etc.), LED (LED lamp, chip LED, light receiving element, optical semiconductor lens). , Sensors (temperature sensors, optical sensors, magnetic sensors), passive components (high-frequency devices, resistors, capacitors, etc.), mechanical components (connectors, switches, relays, etc.), automotive components (circuit systems, control systems, sensors) , Lamp seals, etc.), adhesives (optical components, optical discs, pickup lenses), etc., and for surface coatings, optical films such as antireflection films and sealing films.

Claims

Claims [1] An epoxy resin composition comprising a fluorine-substituted adamantanediol represented by the general formula (1) as a curing agent.

[Chemical 1]

(Where n is an integer from:! To 14)

[2] An optical material comprising the epoxy resin composition according to claim 1.

[3] An optical waveguide comprising the epoxy resin composition according to claim 1.

[4] An LED member comprising the epoxy resin composition according to claim 1.

[5] An electronic circuit comprising the epoxy resin composition according to claim 1.