JP7167441B2 - Resin composition, molding, laminate and adhesive - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition having excellent heat resistance and flexibility, and a laminate and an adhesive using the same.

With the miniaturization and high integration of electronic components, heat generation and resulting malfunctions have become a problem. Therefore, in order to operate the electronic parts normally, there is a demand for a member that achieves both high heat dissipation and heat resistance. In particular, adhesives and adhesive sheets having thermal conductivity and heat resistance are especially useful for miniaturizing electronic components, and thus are desired to be developed.
As a composition having high thermal conductivity, a composition obtained by blending a resin composition such as an epoxy resin with an inorganic filler having high thermal conductivity is disclosed. In order to achieve high thermal conductivity, it is necessary to add a large amount of highly thermally conductive filler. There was a problem that the handleability deteriorated and cracks occurred during handling. In response to this problem, Patent Document 1 discloses a heat dissipation sheet containing an epoxy resin having an alkylene ether structure with 2 to 6 carbon atoms and a highly thermally conductive inorganic filler. However, although the composition has improved handleability, the glass transition temperature is lowered, and there are problems with heat resistance and reliability.

JP 2012-69425 A

An object of the present invention is to provide a resin composition that is excellent in thermal conductivity and handleability and also has high heat resistance, a molded article obtained by molding the resin composition, a laminate containing the composition, and an adhesive. That's what it is.

As a result of intensive studies by the present inventors, a polycyclic aromatic epoxy resin (A1) and a non-aromatic epoxy resin (A1) having an aliphatic hydrocarbon structure with 6 or more carbon atoms and no aromatic ring structure ( The present inventors have found that the above problems can be solved by providing a resin composition characterized by containing A2) and a thermally conductive filler (B).

Further, in the resin composition, the non-aromatic epoxy resin (A2) is
Oxygen atoms derived from epoxy groups (number of moles) / Oxygen atoms other than those derived from epoxy groups (number of moles) ≥ 1
It provides a resin composition that is an aliphatic epoxy resin (A2-1).

Further, the present invention provides a resin composition wherein the aliphatic epoxy resin (A2-1) is a polyfunctional aliphatic epoxy resin (A2-2) characterized by containing 3 or more epoxy groups.

The present invention also provides a resin composition wherein the polycyclic aromatic epoxy resin (A1) is a polyfunctional polycyclic aromatic epoxy resin (A1-2) characterized by containing 3 or more epoxy groups. be.

Further, the present invention provides a resin composition in which the thermally conductive filler (B) has a thermal conductivity of 10 W/mK or higher.

Further, the present invention provides a molded article obtained by molding the resin composition, and a laminate obtained by laminating a substrate and the molded article.

Further, the present invention provides an adhesive characterized by containing the resin composition.

The present invention also provides an electronic member and a thermally conductive member comprising the molded article of the present invention.

The resin composition of the present invention comprises a polycyclic aromatic epoxy resin (A1) and a non-aromatic epoxy resin (A2) having an aliphatic hydrocarbon structure with 6 or more carbon atoms and no aromatic ring structure. By containing, it is possible to achieve both high heat resistance and handleability. In addition, since the thermally conductive filler (B) can be highly filled, the resin composition of the present invention can be suitably used as a thermally conductive material, and the molded article and laminate using the thermally conductive material are Since it has high thermal conductivity and is easy to handle, it can be suitably used as a thermally conductive member. In particular, it can be suitably used as an electronic member that is becoming more and more miniaturized.

The present invention provides a polycyclic aromatic epoxy resin (A1) and a non-aromatic epoxy resin (A2) having an aliphatic hydrocarbon structure with 6 or more carbon atoms and no aromatic ring structure and thermal conductivity. A resin composition containing a filler (B) is disclosed.

<Polycyclic aromatic epoxy resin (A1)>
The polycyclic aromatic epoxy resin (A1) of the present invention is an epoxy resin characterized by having a plurality of aromatic rings and an epoxy group. Having a plurality of aromatic rings includes the case where the single rings form a direct bond or form a condensed ring, and the case where the above aromatic rings are further bonded directly or via a linking group.
Since the polycyclic aromatic epoxy resin (A1) has a plurality of aromatic rings, a rigid structure is introduced into the epoxy resin, thereby improving the heat resistance of the entire resin composition. The polycyclic aromatic epoxy resin (A1) may be used alone or in combination.

A monocyclic aromatic ring in the present invention includes a benzene ring.
The condensed aromatic ring includes naphthalene ring, anthracene ring, phenanthrene ring, naphthacene ring, pentacene ring, pyrene ring, chrysene ring, triphenylene ring and the like.

Although the linking group is not particularly limited, for example, oxygen, sulfur, a divalent or higher valent atom such as nitrogen, a substituted or unsubstituted hydrocarbon group, a carbonyl group (-CO- group), an ester group (-COO- group) , amide group (-CONH- group), imino group (-C=N- group), azo group (-N=N- group), sulfide group (-S- group), sulfone group (-SO ₃ - group) , and a linking group formed by combining these.
As for the bond between the aromatic rings, a direct bond or a substituted or unsubstituted hydrocarbon group having 1 carbon atoms as a linking group is preferable because the heat resistance is further improved.

In the polycyclic aromatic epoxy resin (A1) of the present invention, the epoxy group may be directly bonded to the aromatic ring, or may be bonded via the linking group as described above.

Specific examples of structures having multiple aromatic rings include the following structures.

Moreover, the polycyclic aromatic epoxy resin (A1) of the present invention may have a plurality of structures having a plurality of aromatic rings.

The polycyclic aromatic epoxy resin (A1) of the present invention preferably has two or more epoxy groups. Particularly preferred is a polyfunctional polycyclic aromatic epoxy resin (A1-2) characterized by containing 3 or more epoxy groups. The polyfunctional polycyclic aromatic epoxy resin (A1-2) is preferable because the reactivity of the resin composition is improved and the network in the cured product is dense, thereby improving the heat resistance. The non-aromatic epoxy resin (A2) may be used alone or in combination.

Preferred structures of the polycyclic aromatic epoxy resin (A1) of the present invention are as follows.

<Non-aromatic epoxy resin (A2) having an aliphatic hydrocarbon structure having 6 or more carbon atoms and no aromatic ring structure>
The epoxy resin (A) of the present invention is a non-aromatic epoxy resin (A2) having an aliphatic hydrocarbon structure with 6 or more carbon atoms and no aromatic ring structure (hereinafter referred to as a non-aromatic epoxy resin ( A2)) is included.
Since the non-aromatic epoxy resin (A2) of the present invention has an aliphatic hydrocarbon structure with 6 or more carbon atoms, the flexibility of the composition is improved and the handleability is improved.

Non-aromatic epoxy resins (A2) having an aliphatic hydrocarbon structure with 6 or more carbon atoms and no aromatic ring structure include, for example, 1,6-hexanediol diglycidyl ether, neopentyl glycol glycidyl Ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, hydrogenated bisphenol A diglycidyl ether, C10-C18 alcohol glycidyl ether, 3,4-epoxycyclohexymethyl-3',4'- Epoxy cyclohexane carboxylate, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether and the like.

The non-aromatic epoxy resin (A2) of the present invention is an aliphatic epoxy resin (A2-1) (hereinafter referred to as Aliphatic epoxy resin (A2-1)) is preferred. This is because the oxygen atoms other than those derived from epoxy groups (for example, derived from structures such as ethers, esters, and amides) are small, so that the decomposition resistance due to heat and moisture is improved. Moreover, since it has an aliphatic hydrocarbon structure with 6 or more carbon atoms, the flexibility of the resin is improved and the handleability is improved. The aliphatic epoxy resin (A2-1) of the present invention is preferable because it can achieve both. Examples of the aliphatic epoxy resin (A2-1) of the present invention include 1,6-hexanediol diglycidyl ether, neopentyl glycol glycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, C10-C18 alcohol glycidyl ether, 3,4-epoxycyclohexymethyl-3',4'-epoxycyclohexanecarboxylate, cyclohexanedimethanol diglycidyl ether and the like can be mentioned.

Further, the aliphatic epoxy resin (A2-1) of the present invention is preferably a polyfunctional aliphatic epoxy resin (A2-2) characterized by having 3 or more epoxy groups. This is because, in the case of the polyfunctional aliphatic epoxy resin (A2-2), the reactivity of the resin composition is improved, and the network in the cured product is dense, so that the heat resistance is improved.
Examples of this are trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether.

The non-aromatic epoxy resin (A2) of the present invention preferably has a ratio of the theoretical epoxy equivalent to the measured epoxy equivalent of 1.00 to 1.30. This is because if it is within 1.30, it is close to the theoretical structure, a dense crosslinked structure can be formed, and residual chlorine is small.

<Contents of polycyclic aromatic epoxy resin (A1) and non-aromatic epoxy resin (A2)>
The content ratio of the polycyclic aromatic epoxy resin (A1) and the non-aromatic epoxy resin (A2) of the present invention is polycyclic aromatic epoxy resin (A1): non-aromatic epoxy resin (A2) = 50: 50-90:10 is preferred. This range is preferable because both heat resistance and flexibility can be achieved. Especially preferred is A1:A2=70:30 to 90:10.

<Other epoxy resins>
The resin composition of the present invention may contain epoxy resins other than the polycyclic aromatic epoxy resin (A1) and the non-aromatic epoxy resin (A2).
Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, bisphenol A, bisphenol F, Tri- or more functional epoxy compounds having a structure of bisphenol S, solid bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene- Examples include phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resins, biphenyl-modified novolak type epoxy resins, and the like.

<Phenoxy resin>
The resin composition of the present invention may further contain a phenoxy resin, which is a high molecular weight epoxy resin. A phenoxy resin is a resin obtained by reacting a bisphenol compound and epihalohydrin in the presence of a strong alkali. and bisphenol S-modified phenoxy resin.
When a phenoxy resin is blended in the resin composition of the present invention, the epoxy equivalent of the phenoxy resin is 1,000 g/eq or more and 100,000 g/eq or less, the compatibility with the epoxy resin is improved, and the surface is smooth. It is preferable because a compact molded article, particularly a sheet-like molded article can be obtained. The epoxy equivalent of the phenoxy resin is more preferably 2,000 to 50,000 g/equivalent, still more preferably 3,000 to 20,000 g/equivalent.

The total amount of the polycyclic aromatic epoxy resin (A1) and the non-aromatic epoxy resin (A2) is preferably 60% or more in the total amount of the epoxy resin and the phenoxy resin of the present invention. This is because when the content is 60% or more, the heat resistance and flexibility of the resin composition are not impaired. Especially preferably, it is 70% or more.

<Thermal conductive filler (B)>
The resin composition of the present invention contains a thermally conductive filler (B). As the thermally conductive filler (B), known and commonly used fillers may be used, such as gold, platinum, silver, copper, nickel, palladium, iron, aluminum, stainless steel, graphite (graphite), silicon oxide, silicon nitride. , aluminum nitride, boron nitride, aluminum borate, aluminum oxide, magnesium oxide, diamond, PBO (polyparaphenylenebenzoxazole), and the like. The shape of the thermally conductive filler (B) is not particularly limited. do not have. Spherical or polyhedral particles are preferable because they can be highly filled in the resin composition.

When the thermally conductive filler (B) is particulate, the 50% cumulative particle size is preferably 500 μm to 5 nm, more preferably 100 μm to 100 nm.
A plurality of fillers (B) having different filler particle sizes may be blended. For example, it is preferable to blend three components of a small particle size, a medium particle size, and a large particle size, because both high thermal conductivity and high filling can be achieved. As the filler with a particle size of three components, a filler (B1) having a 50% cumulative particle size of 100 to 10 μm, a 50% cumulative particle size of 30 to 1 μm and 1 with respect to the 50% cumulative particle size of the filler (B1) / Filler (B2) that is 10 or more and 1/2 or less, a filler ( B3) is preferably blended. The blending ratio is 50 to 80% for filler (B1), 10 to 40% for filler (B2), and 10 for filler (B3), with the total volume of fillers (B1), (B2) and (B3) being 100%. ~40% is preferred. Further, the filler (B1) preferably has a 90% cumulative particle size of 1/2 or less of the dry thickness after coating or molding. (For those not mentioned above, the cumulative particle size is based on volume-based measurement.)

As the thermally conductive filler (B) of the present invention, it is particularly preferable to use a filler having a thermal conductivity of 10 W/mK or more, because high thermal conductivity can be imparted to the resin composition. Specifically, aluminum oxide (alumina), aluminum nitride, boron nitride, silicon nitride, and magnesium oxide are preferable in terms of ensuring thermal conductivity and insulation. It is more preferable because the filling property is improved.

In order to impart high thermal conductivity to the resulting molded article, the thermally conductive filler (B) preferably accounts for 60 to 95% by volume of the entire resin composition. Particularly preferred is 70 to 95% by volume, particularly preferred is 75 to 95% by volume.

<Other compounds>
The resin composition of the present invention may contain a compound other than the polycyclic aromatic epoxy resin (A1), the non-aromatic epoxy resin (A2) and the thermally conductive filler (B).

<Curing agent>
Since the resin composition of the present invention contains an epoxy resin, it preferably contains a curing agent. The curing agent may be any known and commonly used curing agent for epoxy resins, and examples thereof include amine curing agents, amide curing agents, acid anhydride curing agents, and phenol curing agents.

Specifically, amine curing agents include diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylether, diaminodiphenylsulfone, orthophenylenediamine, metaphenylenediamine, paraphenylenediamine, metaxylenediamine, paraxylenediamine, diethyltoluenediamine, and diethylenetriamine. , triethylenetetramine, isophoronediamine, imidazole compounds, BF3-amine complexes, guanidine derivatives, guanamine derivatives and the like.

Examples of amide-based curing agents include dicyandiamide and polyamide resins synthesized from dimers of linolenic acid and ethylenediamine.
Acid anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hydrophthalic anhydride and the like.

Phenolic curing agents include bisphenol A, bisphenol F, bisphenol S, resorcinol, catechol, hydroquinone, fluorene bisphenol, 4,4′-biphenol, 4,4′,4″-trihydroxytriphenylmethane, naphthalenediol, 1 , 1,2,2-tetrakis(4-hydroxyphenyl)ethane, calixarene, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resins), polyhydric phenol novolak resins synthesized from polyhydric hydroxy compounds represented by resorcinol novolac resins and formaldehyde, naphthol aralkyl resins, trimethylolmethane resins, tetraphenylolethane resins, naphthol novolac resins, naphthol-phenol cocondensation Novolac resin, naphthol-cresol cocondensed novolak resin, biphenyl-modified phenolic resin (polyhydric phenol compound with phenolic nucleus linked with bismethylene group), biphenyl-modified naphthol resin (polyhydric naphthol compound with phenolic nucleus linked with bismethylene group) , aminotriazine-modified phenol resins (polyhydric phenol compounds in which the phenol nucleus is linked with melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring-modified novolac resins (polyhydric phenol compounds in which the phenol nucleus and alkoxy group-containing aromatic rings are linked with formaldehyde) compound) and other polyhydric phenol compounds.
These curing agents may be used alone or in combination of two or more.

Among curing agents, amine-based or amide-based curing agents are preferable because they improve the adhesiveness of the thermally conductive adhesive or the thermally conductive adhesive sheet.
When long-term storage stability is required, it is preferable to select a latent curing agent. Specific examples of latent curing agents include dicyandiamide, imidazoles, hydrazides, boron trifluoride-amine complexes, amine imides, polyamine salts, modified products thereof, and microcapsule types thereof.

<Curing accelerator>
A curing accelerator may be added to the resin composition of the present invention. Various compounds that promote the curing reaction of epoxy resins can be used as curing accelerators, and examples thereof include phosphorus compounds, tertiary amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, and amine complex salts. Among these, imidazole compounds, phosphorus compounds, and tertiary amine compounds are preferably used. .

<Other resins>
The resin composition of the present invention may contain other resins than the epoxy resin as long as the effects of the present invention are not impaired. Other resins include thermosetting resins and thermoplastic resins.

Thermosetting resins are resins that have the property of being able to become substantially insoluble and infusible when cured by means of heat, radiation, catalysts, or the like. Specific examples thereof include phenol resins, urea resins, melamine resins, benzoguanamine resins, alkyd resins, unsaturated polyester resins, vinyl ester resins, diallyl terephthalate resins, silicone resins, urethane resins, furan resins, ketone resins, xylene resins, heat curable polyimide resin and the like. These thermosetting resins can be used singly or in combination of two or more.

A thermoplastic resin is a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resins, polysulfone resins, polyphenylene sulfide resins, polyetherimide resins, polyethersulfone resins, polyarylate resins, thermoplastic polyimide resins, polyamideimide resins, polyetheretherketone resins, polyketone resins, liquid crystal polyester resins, fluororesins, synth otakutic polystyrene resins, cyclic polyolefin resins, and the like. These thermoplastic resins can be used singly or in combination of two or more.

<Solvent>
The resin composition of the present invention may contain a solvent depending on the intended use. Examples of solvents include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate usage amount thereof may be appropriately selected depending on the application.

<Other compounds>
The resin composition of the present invention contains reactive compounds, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, coupling agents, stabilizers, flow agents, as long as the effects of the present invention are not impaired. Adjustment agents, dyes, leveling agents, rheology control agents, UV absorbers, antioxidants, plasticizers, etc. may be blended.

<Molded body>
The molded article of the present invention is a molded article obtained by molding the above resin composition. As the molding method, a known and commonly used method may be used, and the molding method may be appropriately selected depending on the type of resin or application. There are no restrictions on the shape of the molded body, and it may be plate-shaped, sheet-shaped, or film-shaped, and may have a three-dimensional shape. It may be molded so as to exist between substrates. The resin composition of the present invention is suitable for producing a sheet because it has high handleability even when highly filled with a filler.
As a molding method, for example, if a plate-like or sheet-like product is to be manufactured, extrusion molding is generally used, but flat pressing is also possible. In addition, it is possible to use profile extrusion molding, blow molding, compression molding, vacuum molding, injection molding, and the like. If a film-like product is to be produced, a solution casting method can be used in addition to the melt extrusion method. When using a melt molding method, inflation film molding, cast molding, extrusion lamination molding, calender molding, and sheet molding can be used. , fiber molding, blow molding, injection molding, rotational molding, coating molding, and the like. Moreover, in the case of a resin that is cured by an active energy ray, a molding can be produced using various curing methods using an active energy ray.

Also, if the resin composition is liquid, it can be molded by coating. Examples of the coating method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, a doctor blade method, a curtain coating method, a slit coating method, a screen printing method, an inkjet method, and the like. .

<Adhesive>
Since the resin composition of the present invention has excellent adhesiveness, it can be used as an adhesive. The form of the adhesive is not particularly limited, and may be a liquid or paste adhesive, or a solid adhesive. Since the resin composition of the present invention contains the thermally conductive filler (B), it can be suitably used as a thermally conductive adhesive.
In the case of a liquid or paste adhesive, it may be a one-liquid adhesive or a two-liquid adhesive with a separate curing agent. The method of use is not particularly limited, but it is sufficient to inject a liquid or paste resin composition into the interface of the bonding surfaces, bond them together, and cure them.
In the case of a solid adhesive, a powdered, chip-shaped, or sheet-shaped adhesive may be placed on the interface of the bonding surface, melted by heat, and cured. In particular, the resin composition of the present invention is very suitable for use as an adhesive sheet because of its excellent flexibility. In particular, even when the thermally conductive filler (B) is highly filled, it can be suitably used as a thermally conductive adhesive sheet because it can achieve both heat resistance and flexibility (handleability).

<Laminate>
A laminate can be obtained by laminating the molded article of the present invention on a substrate. The laminate may have two layers or three layers or more.
The material of the base material is not particularly limited, and may be appropriately selected according to the application. I don't mind. Also, the shape of the substrate is not particularly limited, and may be any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape having a curvature over its entire surface or part thereof. Moreover, there are no restrictions on the hardness, thickness, etc. of the base material.
The molded article may be formed by direct coating or molding on the base material, or may be formed by stacking already molded articles. In the case of direct coating, the coating method is not particularly limited, and includes a spray method, spin coating method, dipping method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, A screen printing method, an inkjet method, and the like can be mentioned. Direct molding includes in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding, and the like.
When laminating the molded resin composition, an uncured or semi-cured composition layer may be laminated and then cured, or a cured product layer obtained by completely curing the composition may be laminated on the substrate. good too.
Further, the cured product of the present invention may be laminated by applying a precursor that can be a base material and curing it, and the precursor that can be a base material or the composition of the present invention is uncured or semi-cured. It may be cured after being adhered in the state of . Precursors that can serve as base materials are not particularly limited, and various curable resin compositions and the like can be mentioned.
Moreover, you may produce a laminated body by using the resin composition of this invention as an adhesive agent.

The resin composition of the present invention comprises a polycyclic aromatic epoxy resin (A1) and a non-aromatic epoxy resin (A2) having an aliphatic hydrocarbon structure with 6 or more carbon atoms and no aromatic ring structure. By containing, it is possible to achieve both high heat resistance and handleability. In addition, by using the thermally conductive filler (B1), the resin composition of the present invention can be suitably used as a thermally conductive material, and the molded article and laminate using the thermally conductive material are thermally conductive. It can be suitably used as a heat-conducting member because it is highly flexible and easy to handle. In particular, it can be suitably used as an electronic member that is becoming more and more miniaturized.

The present invention will be described in more detail below based on examples, but the description does not limit the present invention. In the examples, unless otherwise specified, the values are in terms of mass.

(Method for measuring epoxy equivalent)
An epoxy resin sample (1 ± 0.3 millimole equivalent) was dissolved in 20 ml of methyl ethyl ketone, 5 ml of a 20 mass% acetic acid solution of cetyltrimethylammonium bromide (CTMAB) was added, 4 to 6 drops of crystal violet indicator (acetic acid solution) were added, and a stirrer was added. It was titrated with a 0.1 mol/l perchloric acid-acetic acid solution (0.1 mol/l HClO4) while stirring at . One drop of 0.1 mol/l perchloric acid-acetic acid solution was added, and the color changed from bluish purple to blue. In addition, the temperature of the perchloric acid-acetic acid solution was recorded because the volume expansion coefficient of the solvent needs to be corrected according to the temperature. At the same time, a blank test was performed without using a sample, and the titration amount was measured in the same manner.

Epoxy equivalent (g/eq.) = (1000 x W)/[(Vs-Vb) x 0.1 x [F20/{1 + 0.011 (t-20)}]...(1)

W: Epoxy resin sample amount (g)
Vs: Appropriate amount (ml) of 0.1 mol/l HClO4 required for this test
Vb: Appropriate amount (ml) of 0.1 mol/l HClO4 required for blank test
F20: Potency of 0.1 mol/l HClO4 at 20°C t: Liquid temperature of 0.1 mol/l HClO4 during titration (°C)

<Synthesis Example 1> Epoxy resin (EP-1)
Synthesis of 2,2',7,7'-tetraglycidyloxy-1,1'-binaphthalene In a flask equipped with a thermometer, a stirrer and a reflux condenser, while purging with nitrogen gas, iron (III) chloride hexahydrate was added. 278 g (1.0 mol) of the hydrolyzate and 2660 mL of water were charged, and the inside of the reaction vessel was replaced with nitrogen while stirring. was added and stirred at 40° C. for 30 minutes. A mixed solution of 278 g (1.0 mol) of iron (III) chloride hexahydrate, 1328 mL of water and 188 mL of isopropyl alcohol was added, and the mixture was heated to 40° C. and further stirred for 1 hour. 1000 mL of ethyl acetate was added to the reaction solution and stirred. After the organic layer was separated from the reaction solution using a separatory funnel, the aqueous layer was further extracted with ethyl acetate. The combined organic layer was washed with saturated brine. After distilling off the solvent to about 400 mL under vacuum, the solution was transferred to a SUS container equipped with a thermometer, a stirrer, and a Dean-Stark trap, and after adding 10 L of toluene, ethyl acetate and water were replaced with toluene. After cooling the toluene solution to room temperature, the insoluble matter was filtered off. The filtrate is heated to a temperature above the boiling point and concentrated by distilling toluene to about 1000 mL to obtain crystals of [1,1′-binaphthalene]-2,2′,7,7′-tetraol. Precipitated. After filtering the precipitate and solvent by hot filtration at a temperature of 80 ° C. or higher, drying at 110 ° C. for 5 hours, [1,1'-binaphthalene]-2,2',7,7 as phenol compound 1 A yield of 106 g (68% yield) of '-tetraol was obtained.
Next, 79.5 g (0.25 mol) of the above phenol compound 1 and 462 g (5.0 mol) of epichlorohydrin were placed in a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer while purging with nitrogen gas. , and 126 g of n-butanol were charged and dissolved. After raising the temperature to 40° C., 100 g (1.20 mol) of a 48% aqueous sodium hydroxide solution was added over 8 hours, then the temperature was further raised to 50° C. and the reaction was allowed to proceed for 1 hour. After completion of the reaction, 150 g of water was added and left to stand, and then the lower layer was discarded. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. 230 g of methyl isobutyl ketone was added and dissolved in the crude epoxy resin thus obtained. Further, 100 g of a 10% by weight sodium hydroxide aqueous solution was added to this solution and reacted at 80° C. for 2 hours, followed by repeated washing with water until the pH of the washing liquid became neutral. The system is then dehydrated, and after microfiltration, the solvent is distilled off under reduced pressure to obtain 2,2',7,7'-tetraglycidyloxy-1,1'- as an epoxy resin (EP-1). 135 g of binaphthalene were obtained. The obtained epoxy resin (EP-1) had a softening point of 61° C. (B&R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150° C.) of 1.1 dPa s, and an epoxy equivalent of 144 g/ was equivalent.

<Synthesis Example 2> 114 g of bisphenol A and 191.6 g of bisphenol A type epoxy resin (EPCLON-850S manufactured by DIC Corporation) (epoxy equivalent: 188 ), 130.9 g of cyclohexanone (nonvolatile content: 70%) was charged, the inside of the system was replaced with nitrogen, nitrogen was slowly flowed, and the temperature was raised to 80 ° C. while stirring, and 120 mg of 2E4MZ (manufactured by Shikoku Kogyo Kasei Co., Ltd.) (400 ppm relative to the theoretical resin solid content) was added, and the temperature was further raised to 150°C. Then, the mixture was stirred at 150° C. for 20 hours, and adjusted by adding MEK and cyclohexanone so that the non-volatile content (N.V.) was 30% (MEK:cyclohexanone=1:1). The obtained phenoxy resin solution had a viscosity of 5200 mPa·s and an epoxy equivalent weight of non-volatile matter of 12500 g/equivalent.

<Synthesis Example 3> Alumina 1
300 parts by mass of aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., average particle size 45 μm) and 75 parts by mass of molybdenum oxide (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed in a mortar. The resulting mixture was fired in a ceramic electric furnace at 1100° C. for 10 hours. After the temperature was lowered, the crucible was taken out, and the contents were washed with 10% aqueous ammonia and ion-exchanged water, and then dried at 150°C for 2 hours to obtain 190 parts by mass of blue powder. A polyhedron having a 50% cumulative particle size of 5 μm, a 90% cumulative particle size of 7 μm, and a density of 3.95, with a crystal plane other than the [001] plane as the main crystal plane, and a crystal plane with a larger area than the [001] plane. It was confirmed that the particles were shaped alumina (aluminum oxide) particles.

<Example 1> Resin composition 1
60 parts by mass of the epoxy resin (EP-1) obtained in Synthesis Example 1, 10 parts by mass of trimethylolpropane triglycidyl ether (manufactured by Nagase ChemteX Corporation, EX321L), and the phenoxy resin obtained in Synthesis Example 2 100 parts by mass of the solution (NV30%), a total of 1267 parts by mass of the three types of alumina listed in Table 1, and 6.73 parts of the silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM4803). Kneaded with a type kneading device, 2P4MHZ-PW (imidazole-based curing agent, manufactured by Shikoku Kasei Co., Ltd.) 1.3 parts by mass, AH-154 (dicyandiamide, manufactured by Ajinomoto Fine Techno Co., Ltd.) 1.7 parts by mass, and , 140 parts by mass of methyl ethyl ketone (MEK) are blended and kneaded in a rotation-revolution type kneading device at room temperature for 5 minutes under a reduced pressure of 0.1 MPa by degassing using a decompressor to obtain a resin composition. Got item 1.

Next, the resin composition 1 was applied to the surface of a release film in which one side of a polyethylene terephthalate film having a thickness of 75 μm was subjected to release treatment with a silicone compound, using a rod-shaped metal applicator, to a thickness of 120 μm after drying. It was coated so as to be

Next, the coated product is dried at 50 ° C. for 10 minutes, dried at 70 ° C. for 10 minutes, and further dried at 100 ° C. for 20 minutes to form a sheet having a thickness of 120 μm on the release film Laminate got

(Method for measuring glass transition temperature)
A sheet obtained by removing the release film from the laminate was molded with a hot press at a temperature of 180° C. and a pressure of 5 MPa for 15 minutes, and then cured at 200° C. for 2 hours to prepare a cured product sample.
The dynamic viscoelasticity of this cured product sample was measured from 0 to 300° C. using a solid viscoelasticity measuring device DMA (RSA III manufactured by Rheometrics Co., Ltd.) at a frequency of 1 Hz and a heating rate of 3° C./min. The temperature at which the loss tangent (tan δ), which is the ratio of the storage elastic modulus E′ and the loss elastic modulus E″, shows a maximum and the main chain changes from a glassy state to a rubbery state was taken as the glass transition temperature.

(Method for measuring sheet flexibility)
The laminate was cut to 10 mm x 100 mm, the sheet was turned outward, wrapped around a cylinder with a diameter of 5 mm or 20 mm and folded 180 degrees. The presence or absence of cracks in the folded sheet was visually evaluated according to the following criteria.
⊚: No cracks were found in the 5 mm cylinder. ◯: There were cracks in the 5 mm cylinder, but no cracks were found in the 20 mm cylinder.
×: Cracks were observed in a cylinder of 20 mm.

(Method for measuring thermal conductivity of sheet)
A sheet obtained by removing the release film from the laminate was molded with a hot press at a temperature of 180° C. and a pressure of 5 MPa for 15 minutes, and then cured at 200° C. for 2 hours to prepare a cured product sample.
The resulting cured product was cut into 10 mm squares as test samples, and the thermal conductivity at 25° C. was measured using a thermal conductivity measuring device (Xe flash type LFA467, manufactured by NETZSCH).

<Examples and Comparative Examples>
In the same manner as in Example 1, a resin composition and a sheet were prepared at the compounding ratios shown in Tables 1-1 and 1-2 below, and sheet flexibility, glass transition temperature, and thermal conductivity were measured.

The materials used in this example are as follows.
Polycyclic aromatic epoxy resin (A1):
-HP-4700 naphthalene type epoxy resin DIC Corporation non-aromatic epoxy resin having an aliphatic hydrocarbon structure with 6 or more carbon atoms and no aromatic ring structure (A2):
・EX-321L Trimethylolpropane triglycidiether low chlorine product manufactured by Nagase ChemteX Corporation ・EX-216L Cyclohexanedimethanol diglycidyl ether low chlorine product manufactured by Nagase ChemteX Corporation ・EX-321 Trimethylolpropane triglycidyl ether Nagase ChemteX Co., Ltd. SR-16HL Hexanediol diglycidyl ether Low chlorine product Sakamoto Chemical Industry Co., Ltd.
・SR-16 Hexanediol diglycidyl ether Sakamoto Yakuhin Kogyo Co., Ltd.
・EX-830 polyethylene glycol diglycidyl ether manufactured by Nagase ChemteX Co., Ltd. Other epoxy resins:
・ Epiclon 850S bisphenol A type epoxy resin manufactured by DIC Corporation ・ mp-CGE mp-cresyl glycidyl ether Sakamoto Yakuhin Kogyo Co., Ltd.
Thermally conductive filler (B):
・DAW45 (55 μm sieve processing) aluminum oxide 50% cumulative particle size 33 μm, 90% cumulative particle size 50 μm, density 3.90, manufactured by Denki Kagaku Kogyo Co., Ltd. ・AA-04 aluminum oxide 50% cumulative particle size 0.3 μm, 90% cumulative particle size 1 μm, density 3.95, manufactured by Sumitomo Chemical Co., Ltd. Others:
・Imidazole curing agent 2P4MHZ-PW manufactured by Shikoku Kasei Co., Ltd. ・Dicyandiamide curing agent AH-154 manufactured by Ajinomoto Fine Techno Co., Ltd. ・Silane coupling agent KBM-4803 manufactured by Shin-Etsu Chemical Co., Ltd.

The resin composition of the present invention comprises a polycyclic aromatic epoxy resin (A1) and a non-aromatic epoxy resin (A2) having an aliphatic hydrocarbon structure with 6 or more carbon atoms and no aromatic ring structure. By containing, it is possible to achieve both high heat resistance and handleability. In addition, since the thermally conductive filler (B) can be highly filled, the resin composition of the present invention can be suitably used as a thermally conductive material, and a molded article and laminate using the thermally conductive material. has high thermal conductivity and is easy to handle, it can be suitably used as a thermally conductive member. In particular, it can be suitably used as an electronic member that is becoming more and more miniaturized.

Claims (15)

A polycyclic aromatic epoxy resin (A1);
a non-aromatic epoxy resin (A2) having an aliphatic hydrocarbon structure with 6 or more carbon atoms and no aromatic ring structure;
a phenoxy resin having an epoxy equivalent of 2,000 to 50,000 g/equivalent;
The thermally conductive filler (B) contains three components of large particle size (B1), medium particle size (B2), and small particle size (B3),
The polycyclic aromatic epoxy resin (A1) is one or more polycyclic aromatic epoxy resins selected from the group consisting of the following structural formulas (1) to (3),

The non-aromatic epoxy resin (A2) includes 1,6-hexanediol diglycidyl ether , trimethylolpropane triglycidyl ether , hydrogenated bisphenol A diglycidyl ether, C10-C18 alcohol glycidyl ether, 3,4-epoxycyclohexane one or more non-aromatic epoxy resins selected from the group consisting of dimethyl-3′,4′-epoxycyclohexanecarboxylate and cyclohexanedimethanol diglycidyl ether ;
The phenoxy resin is a phenoxy resin having an epoxy equivalent of 2,000 to 50,000 g/equivalent obtained by reacting a bisphenol compound with epihalohydrin,
The three components of the thermally conductive filler (B) are a filler (B1) with a 50% cumulative particle size of 100 to 10 μm, and a 50% cumulative particle size of 30 to 1 μm and a 50% cumulative particle size of the filler (B1). On the other hand, the filler (B2) is 1/10 or more and 1/2 or less, the 50% cumulative particle diameter is 5 μm to 100 nm, and the 50% cumulative particle diameter of the filler (B2) is 1/100 or more and 1/2 or less. A resin composition characterized by being a certain filler (B3). The non-aromatic epoxy resin (A2) is
Oxygen atoms derived from epoxy groups (number of moles) / Oxygen atoms other than those derived from epoxy groups (number of moles) ≥ 1
is an aliphatic epoxy resin (A2-1),
The resin composition according to claim 1. 3. The resin composition according to claim 2, wherein the aliphatic epoxy resin (A2-1) is a polyfunctional aliphatic epoxy resin (A2-2) containing 3 or more epoxy groups. The content ratio of the polycyclic aromatic epoxy resin (A1) and the non-aromatic epoxy resin (A2) is polycyclic aromatic epoxy resin (A1): non-aromatic epoxy resin (A2) = 50: 50 ~ The resin composition according to any one of claims 1 to 3, which is 90:10. The resin composition according to any one of claims 1 to 4, wherein the thermally conductive filler (B) has a thermal conductivity of 10 W/mK or more. The thermally conductive filler (B) is one selected from the group consisting of aluminum oxide (alumina), aluminum nitride, boron nitride, silicon nitride, and magnesium oxide, according to any one of claims 1 to 5. Resin composition. The resin composition according to any one of claims 1 to 6, wherein the thermally conductive filler (B) is spherical or polyhedral. The resin composition according to any one of claims 1 to 7, wherein the thermally conductive filler (B) accounts for 70 to 95% by volume of the entire resin composition. The resin composition according to any one of claims 1 to 8 , further comprising an amine-based or amide-based latent curing agent.
A molded article obtained by molding the resin composition according to any one of claims 1 to 9. A laminate obtained by laminating a substrate and the molded article according to claim 10 . An adhesive comprising the resin composition according to any one of claims 1 to 9. 13. The adhesive according to claim 12, which is an adhesive sheet. An electronic member comprising the molded article according to claim 10 . A thermally conductive member comprising the molded article according to claim 10 .