Adhesive resin composition and electronic apparatus

Abstract

To provide an adhesive resin composition with an enhanced performance balance of adhesion and a low elastic modulus in an ultra-low temperature region, and also to provide an electronic apparatus.SOLUTION: An adhesive resin composition includes an urethane (meth)acrylate polymer, an inorganic filler and a coupling agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an adhesive resin composition and an electronic device.

Background Art

[0002] In recent years, attention has been increasing on flexible devices such as wearable devices. In flexible devices, for example, materials that can cope with bending and stretching are required. Here, since electronic components mounted on a flexible substrate cannot be made stretchable, a low-elastic adhesive resin composition is required to mount these electronic components on the flexible substrate.

[0003] As a technology related to a low-elastic adhesive resin composition, for example, the technology described in Patent Document 1 can be mentioned. Patent Document 1 aims to provide a resin composition that is low-elastic and curable at low temperature and has a long pot life, a conductive adhesive containing the resin composition, a cured product of the resin composition, and a semiconductor device containing the cured product of the conductive adhesive or the resin composition, and includes (A) a radically polymerizable curable resin, (B) a radical polymerization initiator, and (C) a radical polymerization inhibitor, wherein the component (C) contains (C1) a nitrosoamine compound, the component (A) contains (A1) a urethane acrylate oligomer, and the component (A1) has a mass average molecular weight of 1,600 or more and 20,000 or less.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention provides an adhesive resin composition and an electronic device with improved performance balance of adhesion and low elastic modulus in the ultra-low temperature region.

Means for Solving the Problems

[0006] The inventors of the present invention have conducted intensive studies to achieve the above problems. As a result, they have found that by using a urethane (meth) acrylate polymer, an inorganic filler, and a coupling agent in combination, the performance balance of adhesion and low elastic modulus in the ultra-low temperature region can be improved, and thus the present invention has been completed.

[0007] According to the present invention, the following adhesive resin composition and electronic device are provided.

[0008] [1] An adhesive resin composition containing a urethane (meth) acrylate polymer, an inorganic filler, and a coupling agent. [2] The adhesive resin composition according to the above [1], wherein the glass transition temperature (Tg) of the urethane (meth) acrylate polymer measured by the dynamic viscoelasticity measurement method is -40°C or lower. [3] The adhesive resin composition according to the above [1] or [2], wherein the mass average molecular weight of the urethane (meth) acrylate polymer measured by the GPC measurement method is 5000 or more and 200000 or less. [4] The adhesive resin composition according to any one of the above [1] to [3], wherein the content of the urethane (meth) acrylate polymer is 50% by mass or more and 99% by mass or less when the total amount of the adhesive resin composition is 100% by mass. [5] The adhesive resin composition according to any one of the above [1] to [4], further containing a nitrogen atom-containing compound. [6] The adhesive resin composition according to the above [5], wherein the nitrogen atom-containing compound contains one or more selected from the group consisting of dicyandiamide and dicyandiamide derivatives. [7] The content of the nitrogen atom-containing compound is 0.01 part by mass or more and 5.0 parts by mass or less when the total amount of the resin components contained in the adhesive resin composition is 100 parts by mass. The adhesive resin composition according to [5] or [6] above. [8] The content of the inorganic filler is 0.1% by mass or more and 10.0% by mass or less when the total amount of the adhesive resin composition is 100% by mass. The adhesive resin composition according to any one of [1] to [7] above. [9] The coupling agent contains one or more selected from the group consisting of epoxy silane, sulfide silane, and organo silane. The adhesive resin composition according to any one of [1] to [8] above.

[10] The content of the coupling agent is 0.01 part by mass or more and 3.0 parts by mass or less when the total amount of the resin components contained in the adhesive resin composition is 100 parts by mass. The adhesive resin composition according to any one of [1] to [9] above.

[11] The adhesive resin composition according to any one of [1] to

[10] above, further containing silicone oil.

[12] The content of the silicone oil is 1.0% by mass or more and 15.0% by mass or less when the total amount of the adhesive resin composition is 100% by mass. The adhesive resin composition according to

[11] above.

[13] (Meth)acrylic resin is further contained. The adhesive resin composition according to any one of [1] to

[12] above.

[14] The content of the (meth)acrylic resin is 1.0% by mass or more and 30.0% by mass or less when the total amount of the adhesive resin composition is 100% by mass. The adhesive resin composition according to

[13] above.

[15] The adhesive resin composition according to any one of [1] to

[14] above, further containing peroxide.

[16] The adhesive resin composition according to the above

[15] , wherein when the total amount of the resin components contained in the above peroxide is 100 parts by mass, the content of the peroxide is 0.1 part by mass or more and 10.0 parts by mass or less.

[17] The adhesive resin composition according to any one of the above [1] to

[16] , wherein when the total amount of the above adhesive resin composition is 100% by mass, the content of the epoxy resin is less than 1.0% by mass.

[18] The adhesive resin composition according to any one of the above [1] to

[17] , which has a peak in the range of -100 °C or higher and -30 °C or lower in the dynamic viscoelasticity curve obtained by the following (Method 1). (Method 1) On a glass substrate, two tapes are pasted in parallel with a 6 mm interval. The above adhesive resin composition is applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate together is heat-treated at 175 °C for 90 minutes to obtain a cured product of the above adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring device, tanδ is measured under the conditions of an initial temperature of -100 °C, a heating rate of 5 °C / min, a frequency of 10 Hz, and a measurement mode of tension. After the measurement, tanδ is plotted on the vertical axis and temperature (°C) is plotted on the horizontal axis to create a dynamic viscoelasticity curve. In the range of -100 °C or higher and -30 °C or lower of the above dynamic viscoelasticity curve, the presence or absence of a peak is confirmed when the point where tanδ is 0.1 or more and tanδ shows the maximum value in the above range is taken as the peak top.

[19] The adhesive resin composition according to any one of the above [1] to

[18] , wherein the maximum value of tanδ in the range of -100 °C or higher and -30 °C or lower obtained by the following (Method 2) is 0.1 or more and 2.5 or less. (Method 2) On a glass substrate, two tapes are pasted in parallel with a 6-mm gap therebetween. The adhesive resin composition is applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate with the composition is heat-treated at 175 °C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring device, tanδ is measured under the conditions of an initial temperature of -100 °C, a heating rate of 5 °C / min, a frequency of 10 Hz, and a measurement mode of tension. After the measurement, the maximum value of tanδ in the region of -100 °C or higher and -30 °C or lower is read.

[20] The adhesive resin composition according to any one of [1] to

[19] above, having a half-width of 10 or more and 100 or less by the following (Method 3). (Method 3) On a glass substrate, two tapes are pasted in parallel with a 6-mm gap therebetween. The adhesive resin composition is applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate with the composition is heat-treated at 175 °C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring device, tanδ is measured under the conditions of an initial temperature of -100 °C, a heating rate of 5 °C / min, a frequency of 10 Hz, and a measurement mode of tension. Then, the maximum value of tanδ in the region of -100 °C or higher and -30 °C or lower is read and taken as the peak top. Then, at the peak including the peak top, the temperature at which tanδ becomes half of the maximum value is T L (low-temperature side) and T H (high-temperature side), and the half-width is calculated by the following formula (1). Half-width (°C) = T H - T L (1)

[21] The adhesive resin composition according to any one of [1] to

[20] above, having a value of loss elastic modulus E'' at -40 °C of 1.0×10 -4 MPa or more and 1.0×10 5 MPa or less by the following (Method 4). (Method 4) On a glass substrate, two tapes are adhered in parallel with a 6-mm gap therebetween. The adhesive resin composition is applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate with the composition is heat-treated at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring device, the loss elastic modulus E'' is measured under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension, and the loss elastic modulus E'' at -40°C is read.

[22] The value of the storage elastic modulus E' at 25°C by the following (Method 5) is 1.0×10 -2 MPa or more and 1.0×10 5 MPa or less, and the adhesive resin composition according to any one of the above [1] to

[21] . (Method 5) On a glass substrate, two tapes are adhered in parallel with a 6-mm gap therebetween. The adhesive resin composition is applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate with the composition is heat-treated at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring device, the storage elastic modulus E' is measured under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension, and the storage elastic modulus E' at 25°C is read.

[23] The adhesive resin composition according to any one of the above [1] to

[22] , wherein the die shear strength by the following (Method 6) is 50 N or more. (Method 6) 2.5 mg of the adhesive resin composition is applied to the central portion of the upper surface of a gold-plated plate having a length of 10 mm × width of 10 mm × thickness of 1 mm so as to have a thickness of 20 μm. Then, a gold-plated silicon chip having a length of 5.0 mm × width of 5.0 mm × thickness of 350 μm is placed on the adhesive resin composition such that the central portion of the surface of the gold-plated plate and the central portion of the surface of the gold-plated silicon chip overlap in the vertical direction. And 0.05 kgf / cm is applied from a direction perpendicular to the surface of the gold-plated silicon chip 2A laminate is obtained by applying pressure. Thereafter, the laminate is heat-treated at 175 °C for 90 minutes to obtain a test piece. For the above test piece, using a universal bond tester, with a shear jig moving speed of 20 mm / min, the jig is pressed against the side surface of the gold-plated silicon chip at a point 50 μm away from the upper surface of the gold-plated board in a direction perpendicular to the upper surface of the gold-plated board, and the die shear strength at 25 °C is measured.

[24] An electronic device comprising a cured product of the adhesive resin composition according to any one of [1] to

[23] above.

[25] A base material, An adhesive layer on the above base material, An electronic component on the above adhesive layer, and comprising, The above adhesive layer contains a cured product of the above adhesive resin composition, and the electronic device according to

[24] above.

[26] The above electronic component includes a sensor, and the electronic device according to

[25] above.

[27] The electronic device according to any one of

[24] to

[26] above, which is a flexible device.

Advantages of the Invention

[0009] According to the present invention, it is possible to provide an adhesive resin composition and an electronic device in which the balance of performance between adhesion and low elastic modulus in the ultra-low temperature region is improved.

Brief Description of the Drawings

[0010]

Figure 1

Modes for Carrying Out the Invention

[0011] Hereinafter, the present embodiment will be described in detail. In this specification, the descriptions of "(meth)acrylic resin" and "(meth)acrylate polymer" respectively mean "at least one of acrylic resin and methacrylic resin" and "at least one of acrylate polymer and methacrylate polymer".

[0012] <Adhesive resin composition> First, the adhesive resin composition of this embodiment will be described.

[0013] The adhesive resin composition of this embodiment contains a urethane (meth)acrylate polymer, an inorganic filler, and a coupling agent. By having the above configuration, the adhesive resin composition of this embodiment can provide an adhesive resin composition and an electronic device with improved performance balance of adhesion and low elastic modulus in the ultra-low temperature region.

[0014] Hereinafter, each component contained in the adhesive resin composition of this embodiment will be described.

[0015] (Urethane (meth)acrylate polymer) The urethane (meth)acrylate polymer of this embodiment is, for example, a polymer having a urethane bond and a (meth)acryloyl group. More specifically, a urethane prepolymer having isocyanate groups (NCO groups) at both molecular ends is modified with a (meth)acrylate having active hydrogen, and (meth)acryloyl groups are introduced at both ends of the urethane prepolymer, and the like can be mentioned.

[0016] From the viewpoint of further reducing the elastic modulus in the ultra-low temperature region, the glass transition temperature (Tg) by the dynamic viscoelasticity measurement method of the urethane (meth)acrylate polymer of this embodiment is preferably -40°C or lower, more preferably -45°C or lower, still more preferably -50°C or lower, still more preferably -55°C or lower, still more preferably -60°C or lower. The lower limit value of the glass transition temperature is not particularly limited, but may be, for example, -200°C or higher, -150°C or higher, -100°C or higher, -75°C or higher.

[0017] An example of the dynamic viscoelasticity measurement method for measuring the glass transition temperature (Tg) of the urethane (meth) acrylate polymer of this embodiment is specifically the following method. Dissolve 1 part by mass of diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide (manufactured by BASF Japan Ltd., trade name Lucirin TPO-L) as a photopolymerization initiator in 100 parts by mass of the urethane (meth) acrylate polymer. Apply the obtained solution onto a glass substrate (50 mm × 50 mm) so that the thickness of the cured film becomes 200 μm, and expose the coating film with an exposure apparatus incorporating an ultra-high pressure mercury lamp at 4 J / cm 2 Expose to produce a cured film. For the cured film, using a dynamic viscoelasticity measuring device (DMA7100, manufactured by Hitachi High-Technologies Corporation), measure tanδ under the conditions of initial temperature: -100 °C, heating rate: 5 °C / min, frequency: 10 Hz, and measurement mode: tension. After the measurement, plot tanδ on the vertical axis and temperature (°C) on the horizontal axis to create a dynamic viscoelasticity curve. Take the maximum value of tanδ in the region of -100 °C or higher and -30 °C or lower at this time as the peak top, and read the peak including the above peak top. Read the temperature of the above peak top as the glass transition temperature (Tg).

[0018] From the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature region, the mass average molecular weight of the urethane (meth) acrylate polymer of this embodiment is preferably 5000 or more, more preferably 10000 or more, still more preferably 15000 or more, still more preferably 20000 or more, still more preferably 23000 or more, still more preferably 25000 or more, and preferably 200000 or less, more preferably 150000 or less, still more preferably 100000 or less, still more preferably 50000 or less, still more preferably 30000 or less, as measured by the GPC measurement method.

[0019] An example of the GPC measurement method (gel permeation chromatography method) for measuring the mass average molecular weight of the urethane (meth) acrylate polymer of the present embodiment is specifically to measure the mass average molecular weight of the urethane (meth) acrylate polymer based on the following <GPC measurement conditions> and convert it using the calibration curve of standard polystyrene. <GPC measurement conditions> Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.) Column: Gelpack GL-R420, Gelpack L-R430, Gelpack GL-R440 (manufactured by Hitachi Chemical Co., Ltd.) Eluent: Tetrahydrofuran Measurement temperature: 40 °C Flow rate: 2.05 mL / min Detector: L-3300 (RI detector, manufactured by Hitachi, Ltd.)

[0020] From the viewpoint of further reducing the elastic modulus in the ultra-low temperature region, the content of the urethane (meth) acrylate polymer in the adhesive resin composition of the present embodiment, when the total amount of the adhesive resin composition is 100% by mass, is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, still more preferably 65% by mass or more, still more preferably 70% by mass or more, and from the viewpoint of further improving the adhesion, it is preferably 99% by mass or less, more preferably 97% by mass or less, still more preferably 95% by mass or less, still more preferably 93% by mass or less, still more preferably 91% by mass or less, still more preferably 90% by mass or less.

[0021] Specific examples of such urethane (meth) acrylate polymers include CN9004 (manufactured by Sartomer) and UN-6207 (manufactured by Negami Kogyo Co., Ltd.). The urethane (meth) acrylate polymer may be used alone or in combination of two or more.

[0022] (Inorganic filler) The adhesive resin composition of the present embodiment contains an inorganic filler from the viewpoint of improving the performance balance of fluidity, adhesion, and low elastic modulus in the ultra-low temperature region. Examples of the inorganic filler of the present embodiment include fused silica such as fused crushed silica and fused spherical silica, crystalline silica, alumina, kaolin, talc, clay, mica, rock wool, wollastonite, glass powder, glass flakes, glass beads, glass fibers, silicon carbide, silicon nitride, aluminum nitride, carbon black, graphite, titanium dioxide, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, and the like. Among these, from the viewpoint of improving the performance balance of fluidity, adhesion, and low elastic modulus in the ultra-low temperature region, silica such as fused crushed silica, fused spherical silica, and crystalline silica is preferable, and fused spherical silica is more preferable. Further, among these, calcium carbonate and wollastonite are preferable from the viewpoint of cost. The inorganic filler may be used alone or in combination of two or more kinds.

[0023] The average particle diameter D of the inorganic filler of the present embodiment 50 is preferably 0.001 μm or more, more preferably 0.003 μm or more, still more preferably 0.005 μm or more, still more preferably 0.008 μm or more, still more preferably 0.01 μm or more, and preferably 75 μm or less, more preferably 50 μm or less, still more preferably 25 μm or less, still more preferably 10 μm or less, still more preferably 5 μm or less, still more preferably 1 μm or less, still more preferably 0.1 μm or less, still more preferably 0.05 μm or less, still more preferably 0.03 μm or less, still more preferably 0.02 μm or less from the viewpoint of improving the performance balance of fluidity, adhesion, and low elastic modulus in the ultra-low temperature region. The average particle diameter D 50 can be measured, for example, by a laser diffraction type measuring device RODOS SR type (HELOS&RODOS manufactured by SYMPATEC).

[0024] From the viewpoint of improving the performance balance of fluidity, adhesion, and low elastic modulus in the ultra-low temperature region, when the total amount of the adhesive resin composition is 100% by mass, the content of the inorganic filler in the adhesive resin composition of the present embodiment is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, still more preferably 1.2% by mass or more, still more preferably 1.4% by mass or more, still more preferably 1.6% by mass or more, still more preferably 1.8% by mass or more, still more preferably 2.0% by mass or more, still more preferably 2.2% by mass or more, still more preferably 2.4% by mass or more, and preferably 10.0% by mass or less, more preferably 9.0% by mass or less, still more preferably 8.0% by mass or less, still more preferably 7.0% by mass or less, still more preferably 6.0% by mass or less, still more preferably 5.0% by mass or less, still more preferably 4.0% by mass or less, still more preferably 3.0% by mass or less.

[0025] (Coupling agent) The adhesive resin composition of the present embodiment contains a coupling agent from the viewpoint of improving the mechanical strength, adhesion, and performance balance of low elastic modulus in the ultra-low temperature region of the cured product of the adhesive resin composition. As the coupling agent of the present embodiment, known coupling agents can be used. From the viewpoint of improving the mechanical strength, adhesion, and performance balance of low elastic modulus in the ultra-low temperature region of the cured product of the adhesive resin composition, it preferably contains one or more selected from the group consisting of epoxy silane, sulfide silane, and organosilane.

[0026] Examples of epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like. Examples of sulfide silane include bis(3-(triethoxysilyl)propyl)disulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide, and the like. Examples of the organosilane include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,Trifunctional silanes such as (4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropyl succinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acephenanthrylyltrimethoxysilane; bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane, di(1-naphthyl)diethoxysilane; monofunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, etc. are included., Among these, from the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature region, it preferably contains sulfide silane, and more preferably contains bis(3-(triethoxysilyl)propyl)tetrasulfide. The coupling agent may be used alone or in combination of two or more kinds.,

[0027] From the viewpoint of improving the balance of performance such as fluidity, adhesion, and low elastic modulus in the ultra-low temperature region, when the total amount of the resin components contained in the adhesive resin composition is 100 parts by mass, the content of the coupling agent in the adhesive resin composition of this embodiment is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.1 part by mass or more, still more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, and preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, still more preferably 2.0 parts by mass or less, still more preferably 1.5 parts by mass or less.

[0028] Here, the "resin component" in this specification refers to monomers and polymers excluding fillers such as inorganic fillers; additives such as low stress agents, coupling agents, nitrogen atom-containing compounds and peroxides to be described later; solvents; etc. Specific resin components in this embodiment include, for example, urethane (meth)acrylate polymers, silicone oils, (meth)acrylic resins, and epoxy resins.

[0029] In addition to the above components, the adhesive resin composition of this embodiment may further contain the following components.

[0030] (Nitrogen atom-containing compound) From the viewpoint of further improving the curability, mechanical strength of the cured product of the adhesive resin composition, adhesion, and balance of performance of low elastic modulus in the ultra-low temperature region, the adhesive resin composition of this embodiment preferably further contains a nitrogen atom-containing compound.

[0031] Examples of the nitrogen atom-containing compound of this embodiment include primary amine compounds, secondary amine compounds, tertiary amine compounds, amide compounds, imine compounds, and nitrile compounds. Examples of the primary amine compound include phenethylamine, toluidine, catecholamine, and 2,4,6-trimethylaniline. Examples of the secondary amine compound include dibenzylamine, 2-nitrodiphenylamine, and 4-(2-octylamino)diphenylamine. Examples of the tertiary amine compound include 1,8-bis(dimethylamino)naphthalene, N,N-dibenzyl-2-aminoethanol, and N-benzyl-N-methylethanolamine. Examples of the amide compound include dicyandiamide, dicyandiamide derivatives, N-cyclohexyl-p-toluenesulfonamide, 4-acetamido-1-benzylpiperidine, and N-hydroxy-3-[1-(phenylthio)methyl-1H-1,2,3-triazol-4-yl]benzamide. Examples of the imine compound include diphenylmethanimine, 2,3-bis(2,6-diisopropylphenylimino)butane, and N,N'-(ethane-1,2-diylidene)bis(2,4,6-trimethylaniline). Examples of the nitrile compound include 3-indoleacetonitrile, 4-[(4-chloro-2-pyrimidinyl)amino]benzonitrile, and 4-bromo-2,2-diphenylbutyronitrile. Among these, from the viewpoint of improving the balance of adhesion and low elastic modulus performance in the ultra-low temperature region, it preferably contains one or more selected from the group consisting of dicyandiamide and dicyandiamide derivatives.

[0032] From the viewpoint of improving the balance of adhesion and low elastic modulus performance in the ultra-low temperature region, when the total amount of the resin components contained in the adhesive resin composition is 100 parts by mass, the content of the nitrogen atom-containing compound in the adhesive resin composition of the present embodiment is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.1 part by mass or more, still more preferably 0.5 part by mass or more, still more preferably 1.0 part by mass or more, still more preferably 1.5 part by mass or more, and is preferably 5.0 parts by mass or less, more preferably 4.5 parts by mass or less, still more preferably 4.0 parts by mass or less, still more preferably 3.5 parts by mass or less, still more preferably 3.0 parts by mass or less, still more preferably 2.5 parts by mass or less, still more preferably 2.0 parts by mass or less.

[0033] (Silicone oil) From the viewpoint of improving the performance balance of fluidity, adhesion, and low elastic modulus in the ultra-low temperature region, the adhesive resin composition of this embodiment preferably further contains silicone oil.

[0034] From the viewpoint of improving the performance balance of fluidity, adhesion, and low elastic modulus in the ultra-low temperature region, the mass average molecular weight of the silicone oil of this embodiment measured by the GPC measurement method is preferably 1000 or more, more preferably 5000 or more, and preferably 50000 or less, more preferably 25000 or less.

[0035] An example of the GPC measurement method (gel permeation chromatography method) for measuring the mass average molecular weight of the silicone oil of this embodiment is specifically to measure the mass average molecular weight of the silicone oil based on the following <GPC measurement conditions> and convert it using the calibration curve of standard polystyrene. <GPC measurement conditions> Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.) Column: Gelpack GL-R420, Gelpack L-R430, Gelpack GL-R440 (manufactured by Hitachi Chemical Co., Ltd.) Eluent: Tetrahydrofuran Measurement temperature: 40 °C Flow rate: 2.05 mL / min Detector: L-3300 (RI detector, manufactured by Hitachi, Ltd.)

[0036] Specific examples of the silicone oil of this embodiment include organopolysiloxane. Here, as the organopolysiloxane, a modified silicone oil having a functional group such as an epoxy group, an amino group, a methoxy group, a phenyl group, a carboxyl group, a polyether group, a hydroxyl group, an alkyl group, a vinyl group, or a mercapto group introduced into its structure may be used. As the functional group introduced into the structure of the organopolysiloxane, for example, a carboxyl group, an epoxy group, or a polyether group is preferable.

[0037] From the perspective of compatibility with urethane (meth)acrylate polymers and the like, the silicone oil of this embodiment preferably has polyethylene oxide or butyl glycidyl ether introduced into its side chain.

[0038] From the perspective of further reducing the elastic modulus in the ultra-low temperature region, the glass transition temperature (Tg) of the silicone oil of this embodiment by the dynamic viscoelasticity measurement method is preferably -40°C or lower, more preferably -45°C or lower, still more preferably -50°C or lower, and even more preferably -55°C or lower. The lower limit value of the glass transition temperature is not particularly limited, and for example, it may be -200°C or higher, -150°C or higher, -100°C or higher, or -75°C or higher.

[0039] Examples of commercially available products of the silicone oil of this embodiment include FZ-3730, BY-750, etc. manufactured by Toray Dow Corning Co., Ltd., and X22-2445, etc. manufactured by Shin-Etsu Silicone Co., Ltd. One or more of the above commercially available products can be used in combination.

[0040] From the perspective of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature region, when the total amount of the adhesive resin composition is 100% by mass, the content of the silicone oil in the adhesive resin composition of this embodiment is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, still more preferably 3.0% by mass or more, even more preferably 4.0% by mass or more, even more preferably 5.0% by mass or more, even more preferably 6.0% by mass or more, even more preferably 7.0% by mass or more, and even more preferably 8.0% by mass or more, and is preferably 15.0% by mass or less, more preferably 14.0% by mass or less, still more preferably 13.0% by mass or less, even more preferably 12.0% by mass or less, even more preferably 11.0% by mass or less, even more preferably 10.0% by mass or less, and even more preferably 9.0% by mass or less.

[0041] ((Meth)acrylic resin) From the viewpoint of further improving the balance of adhesion and low elastic modulus performance in the ultra-low temperature region, the adhesive resin composition of the present embodiment preferably further contains a (meth)acrylic resin. Here, the (meth)acrylic resin of the present embodiment does not contain the above-mentioned urethane (meth)acrylate polymer.

[0042] Examples of the (meth)acrylic resin of the present embodiment include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-propyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, chloro-2-hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol mono(meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, and isobornyl (meth)acrylate. Among these, one or a combination of two or more can be used. Among these, from the viewpoint of improving the balance of adhesion and low elastic modulus performance in the ultra-low temperature region, it preferably contains isodecyl (meth)acrylate.

[0043] From the viewpoint of further reducing the elastic modulus in the ultra-low temperature region, the glass transition temperature (Tg) of the (meth)acrylic resin of the present embodiment by the dynamic viscoelasticity measurement method is preferably -40°C or lower, more preferably -45°C or lower, still more preferably -50°C or lower, and even more preferably -55°C or lower. The lower limit value of the glass transition temperature is not particularly limited, and for example, it may be -200°C or higher, -150°C or higher, -100°C or higher, -75°C or higher, or -65°C or higher.

[0044] From the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature region, when the total amount of the adhesive resin composition of this embodiment is 100% by mass, the content of the (meth)acrylic resin in the adhesive resin composition of this embodiment is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, still more preferably 5.0% by mass or more, still more preferably 8.0% by mass or more, still more preferably 10.0% by mass or more, still more preferably 12.0% by mass or more, still more preferably 15.0% by mass or more, still more preferably 16.0% by mass or more, and is preferably 30.0% by mass or less, more preferably 28.0% by mass or less, still more preferably 26.0% by mass or less, still more preferably 24.0% by mass or less.

[0045] (Low stress agent) From the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature region, the adhesive resin composition of this embodiment preferably further contains a low stress agent. Here, the low stress agent of this embodiment does not contain the above-mentioned silicone oil.

[0046] Examples of the low stress agent of this embodiment include silicone compounds such as silicone rubber; polybutadiene compounds such as polybutadiene maleic anhydride adduct and modified polybutadiene; acrylic acid-based polymers such as acrylonitrile-butadiene copolymer compounds, and allyl ester resins. Among these, one or a combination of two or more can be used. Among these, from the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature region, it preferably contains a polybutadiene compound. Examples of commercially available products of the low stress agent of this embodiment include RICOBOND 1731 manufactured by Cray Valley. Among the above commercially available products, one or a combination of two or more can be used.

[0047] From the viewpoint of improving the balance of adhesion and low elastic modulus performance in the ultra-low temperature region, when the total amount of the resin components contained in the adhesive resin composition is 100 parts by mass, the content of the low stress agent in the adhesive resin composition of the present embodiment is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.1 part by mass or more, still more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, still more preferably 0.7 part by mass or more, still more preferably 1.0 part by mass or more, and preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, still more preferably 2.0 parts by mass or less, still more preferably 1.5 parts by mass or less, still more preferably 1.0 part by mass or less.

[0048] (Peroxide) From the viewpoint of improving the balance of adhesion and low elastic modulus performance in the ultra-low temperature region, the adhesive resin composition of the present embodiment preferably further contains a peroxide.

[0049] Examples of the peroxide of the present embodiment include octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, oxalic acid peroxide, 1,1-di(tert-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl peroxy 2-ethylhexanoate, t-hexyl peroxy 2-ethylhexanoate, t-butyl peroxy 2-ethylhexanoate, m-toluoyl peroxide, benzoyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, dilauroyl peroxide, t-butyl perbenzoate, parachlorobenzoyl peroxide, cyclohexanone peroxide, and the like. Among these, one or a combination of two or more can be used. Among these, from the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature region, it preferably contains one or two selected from the group consisting of 1,1-di(tert-butylperoxy)cyclohexane and dilauroyl peroxide.

[0050] From the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature region, when the total amount of the resin components contained in the adhesive resin composition is 100 parts by mass, the content of the peroxide in the adhesive resin composition of the present embodiment is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, still more preferably 0.7 part by mass or more, still more preferably 1.0 part by mass or more, and preferably 10.0 parts by mass or less, more preferably 9.0 parts by mass or less, still more preferably 8.0 parts by mass or less, still more preferably 7.0 parts by mass or less, still more preferably 6.0 parts by mass or less.

[0051] (Other components) In addition to the other components described above, colorants such as carbon black, red iron oxide, and titanium oxide; ion scavengers; natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax, higher fatty acids such as stearic acid and zinc stearate, and their metal salts or release agents such as paraffin may be appropriately blended.

[0052] From the viewpoint of being able to improve the performance balance of adhesion and low elastic modulus in the ultra-low temperature region, when the total amount of the adhesive resin composition is 100% by mass, the content of the epoxy resin in the adhesive resin composition of the present embodiment is preferably less than 1.0% by mass, more preferably less than 0.5% by mass, still more preferably less than 0.1% by mass, still more preferably less than the detection limit.

[0053] Examples of such epoxy resins include known epoxy resins. Specific examples of epoxy resins include novolak-type epoxy resins such as phenol novolak-type epoxy resins and cresol novolak-type epoxy resins, bisphenol-type epoxy resins such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins, aromatic glycidylamine-type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diamino diphenylmethane-type glycidylamine, and aminophenol-type glycidylamine, hydroquinone-type epoxy resins, biphenyl-type epoxy resins, stilbene-type epoxy resins, trisphenol methane-type epoxy resins, trisphenol propane-type epoxy resins, alkyl-modified trisphenol methane-type epoxy resins, triazine nucleus-containing epoxy resins, dicyclopentadiene-modified phenol-type epoxy resins, naphthol-type epoxy resins, naphthalene-type epoxy resins, phenol aralkyl-type epoxy resins having a phenylene and / or biphenylene skeleton, naphthol aralkyl-type epoxy resins having a phenylene and / or biphenylene skeleton, and other aromatic epoxy resins such as aralkyl-type epoxy resins, and alicyclic epoxies such as vinyl cyclohexene dioxide, dicyclopentadiene dioxide, and aliphatic epoxy resins such as Alicyclic diepoxy - adipate.

[0054] From the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature region, the content of the monomer component in the adhesive resin composition of this embodiment is preferably less than 1.0% by mass, more preferably less than 0.5% by mass, still more preferably less than 0.1% by mass, and even more preferably less than the detection limit when the total amount of the adhesive resin composition is 100% by mass.

[0055] Here, the "monomer component" in this specification refers to the raw material components (that is, the raw material components or compounds used for polymerization) used as raw materials such as the urethane (meth)acrylate polymer of this embodiment.

[0056] The adhesive resin composition of the present embodiment preferably has a peak in the range of -100°C or higher and -30°C or lower, more preferably in the range of -90°C or higher and -30°C or lower, still more preferably in the range of -80°C or higher and -30°C or lower, still more preferably in the range of -70°C or higher and -30°C or lower, still more preferably in the range of -60°C or higher and -30°C or lower, still more preferably in the range of -60°C or higher and -40°C or lower, and still more preferably in the range of -60°C or higher and -50°C or lower in the dynamic viscoelasticity curve obtained by the following (Method 1) from the viewpoint of improving the balance of adhesion and low elastic modulus performance in the ultra-low temperature region.

[0057] (Method 1) On a glass substrate, two tapes are pasted in parallel with a 6-mm gap. The adhesive resin composition is applied between the two tapes with a length of 20 mm, a width of 6 mm, and a thickness of 0.5 mm, and the glass substrate is heat-treated at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring device, tanδ is measured under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension. After the measurement, tanδ is plotted on the vertical axis and temperature (°C) is plotted on the horizontal axis to create a dynamic viscoelasticity curve. In the region of 100°C or higher and -30°C or lower of the dynamic viscoelasticity curve, the presence or absence of a peak is confirmed when the point where tanδ is 0.1 or higher and tanδ shows the maximum value in the region is taken as the peak top.

[0058] As the dynamic viscoelasticity measuring device, for example, DMA7100 (manufactured by Hitachi High-Tech Science Corporation) can be used.

[0059] The adhesive resin composition of the present embodiment, according to the following (Method 2), the maximum value of tanδ in the range of -100°C or higher and -30°C or lower is preferably 0.1 or higher, more preferably 0.2 or higher, still more preferably 0.3 or higher, still more preferably 0.4 or higher, from the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature range, and is preferably 2.5 or lower, more preferably 2.0 or lower, still more preferably 1.5 or lower, still more preferably 1.0 or lower, still more preferably 0.9 or lower, still more preferably 0.8 or lower.

[0060] (Method 2) On a glass substrate, two tapes are pasted in parallel with a 6-mm gap. The adhesive resin composition is applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate is heat-treated at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, tanδ is measured using a dynamic viscoelasticity measuring device under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension. After the measurement, the maximum value of tanδ in the range of -100°C or higher and -30°C or lower is read.

[0061] The adhesive resin composition of the present embodiment, according to the following (Method 3), the half-value width is preferably 10 or higher, more preferably 13 or higher, still more preferably 15 or higher, still more preferably 17 or higher, still more preferably 20 or higher, from the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature range, and is preferably 100 or lower, more preferably 90 or lower, still more preferably 80 or lower, still more preferably 70 or lower, still more preferably 60 or lower, still more preferably 55 or lower.

[0062] (Method 3) On a glass substrate, two tapes are adhered in parallel with a 6-mm gap therebetween. The adhesive resin composition is applied between the two tapes in a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate together with the composition is heat-treated at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring device, tanδ is measured under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension. Next, the maximum value of tanδ in the region of -100°C or higher and -30°C or lower is read and taken as the peak top. Then, in the peak including the peak top, the temperature at which tanδ becomes half of the maximum value is defined as T L (low temperature side) and T H (high temperature side), and the half-width is calculated by the following formula (1). Half-width (°C) = T H - T L (1)

[0063] Here, the half-width in the present embodiment means the temperature width (i.e., the full half-width) of the peak at the position where the value of tanδ becomes half (1 / 2) of the maximum value (peak top) in the peak of the loss tangent tanδ.

[0064] The adhesive resin composition of the present embodiment preferably has a value of the loss modulus E'' at -40°C according to the following (Method 4) of 1.0×10 -4 MPa or more, more preferably 1.0×10 -3 MPa or more, still more preferably 1.0×10 -2 MPa or more, still more preferably 1.0×10 -1 MPa or more, still more preferably 1.0×10 0 MPa or more, still more preferably 3.0×10 0 MPa or more, and preferably 1.0×10 5 MPa or less, more preferably 1.0×10 4 MPa or less, still more preferably 1.0×10 3 MPa or less, still more preferably 1.0×10 2MPa or less, more preferably 1.0×10 1 MPa or less.

[0065] (Method 4) On a glass substrate, two tapes are pasted in parallel with a 6-mm gap therebetween. The adhesive resin composition is applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the whole glass substrate is heat-treated at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring device, the loss elastic modulus E’’ is measured under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension, and the loss elastic modulus E’’ at -40°C is read.

[0066] The adhesive resin composition of the present embodiment preferably has a value of the storage elastic modulus E’ at 25°C according to the following (Method 5) of 1.0×10 -2 MPa or more, more preferably 2.0×10 -2 MPa or more, still more preferably 3.0×10 -2 MPa or more, still more preferably 4.0×10 -2 MPa or more, and preferably 1.0×10 5 MPa or less, more preferably 1.0×10 4 MPa or less, still more preferably 1.0×10 3 MPa or less, still more preferably 1.0×10 2 MPa or less, still more preferably 1.0×10 1 MPa or less, still more preferably 1.0×10 0 MPa or less, still more preferably 5.0×10 -1 MPa or less.

[0067] (Method 5) On a glass substrate, two tapes are pasted in parallel with a 6-mm gap therebetween. The adhesive resin composition is applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate together with the composition is heat-treated at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring apparatus, the storage elastic modulus E’ is measured under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension, and the storage elastic modulus E’ at 25°C is read out.

[0068] The adhesive resin composition of the present embodiment preferably has a die shear strength according to the following (Method 6) of 50 N or more, more preferably 51 N or more, still more preferably 52 N or more, still more preferably 53 N or more, still more preferably 54 N or more, from the viewpoint of improving the performance balance of adhesion and low elastic modulus in the ultra-low temperature region. The lower limit value of the die shear strength is not particularly limited, and the higher the better. For example, it may be 1000 N or less, 500 N or less, 300 N or less, or 150 N or less.

[0069] (Method 6) 2.5 mg of the adhesive resin composition is applied to the central portion of the upper surface of a gold-plated plate having a length of 10 mm × width of 10 mm × thickness of 1 mm and is applied so as to have a thickness of 20 μm. Next, a gold-plated silicon chip having a length of 5.0 mm × width of 5.0 mm × thickness of 350 μm is placed on the adhesive resin composition such that the central portion of the surface of the gold-plated plate and the central portion of the surface of the gold-plated silicon chip overlap in the vertical direction. Then, a pressure of 0.05 kgf / cm 2 is applied in the direction perpendicular to the surface of the gold-plated silicon chip to obtain a laminate. Thereafter, the laminate is heat-treated at 175°C for 90 minutes to obtain a test piece. For the test piece, using a universal bond tester, at a shear jig moving speed of 20 mm / min, the die shear strength at 25°C is measured by pressing a jig against the side surface of the gold-plated silicon chip at a point 50 μm away from the upper surface of the gold-plated plate in the direction perpendicular thereto.

[0070] <Method for manufacturing an adhesive resin composition> The method for manufacturing the adhesive resin composition of the present embodiment is not particularly limited. For example, after preliminarily mixing the above-described respective components, kneading is performed using a three-roll mill, and further vacuum degassing is performed to obtain a paste-like adhesive resin composition. At this time, the long-term workability of the adhesive resin composition can be improved by appropriately adjusting the preparation conditions, such as performing the preliminary mixing under reduced pressure.

[0071] The viscosity of the adhesive resin composition of the present embodiment can be adjusted according to the application. The viscosity of the adhesive resin composition can be controlled by adjusting the types of the respective components used and their blending amounts and the like.

[0072] <Electronic device> The electronic device of the present embodiment preferably includes a cured product of the above-described adhesive resin composition. Thereby, peeling of electronic components is suppressed by the adhesive resin composition in which the balance of adhesion and low elastic modulus performance in the ultra-low temperature region is improved, and an electronic device with improved reliability is obtained. Examples of the electronic device of the present embodiment include elements, devices, final products, and other general electrical-related devices to which the technologies of electronics are applied, such as semiconductor chips, semiconductor elements, printed wiring boards, flexible devices, electric circuits, display devices such as television receivers and monitors, information communication terminals, light-emitting diodes, physical batteries, and chemical batteries. Among these, the electronic device of the present embodiment is preferably a flexible device.

[0073] An example of the electronic device of the present embodiment will be specifically described with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of the electronic device of the present embodiment. The electronic device 100 of the present embodiment preferably includes a base material 30, an adhesive layer 10 on the base material 30, and an electronic component 20 on the adhesive layer 10, and the adhesive layer 10 includes a cured product of the adhesive resin composition of the present embodiment. Thereby, the reliability of the electronic device 100 can be improved.

[0074] Examples of the base material 30 in the electronic device 100 of the present embodiment include known members used as the base material of the wiring board of the electronic device. For example, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, and cured products of resin compositions including silicone rubber, fluororubber, nitrile rubber, acrylic rubber, styrene rubber, chloroprene rubber, ethylene propylene rubber, urethane rubber, etc. can be mentioned. The base material 30 includes, in addition to the unprocessed base material, for example, a base material on which a semiconductor element or a display element is formed on the surface. Also, a printed wiring board or the like may be used. In order to improve the adhesiveness, the surface of the base material 30 may be treated with an adhesion aid such as a silane coupling agent.

[0075] From the viewpoint of obtaining an electronic device with improved reliability, the thickness of the adhesive layer 10 in the electronic device 100 of the present embodiment is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, and still more preferably 15 μm or more, and is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and still more preferably 25 μm or less.

[0076] Examples of the electronic component 20 in the electronic device 100 of the present embodiment include known members used as members of the electronic device. For example, semiconductor elements such as integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and solid-state imaging devices, capacitors, coils, and sensors can be mentioned. Among these, the electronic component 20 of the present embodiment preferably includes a sensor.

[0077] (Method for manufacturing an electronic device) An example of the method for manufacturing the electronic device 100 according to the present embodiment will be described. First, the adhesive resin composition of the present embodiment is applied onto the substrate 30, and then the electronic component 20 is placed thereon. That is, the substrate 30, the adhesive resin composition of the present embodiment, and the electronic component 20 are laminated in this order. The method for applying the adhesive resin composition of the present embodiment is not limited, but specifically, dispensing, printing method, inkjet method, etc. can be used. Next, the whole including the adhesive resin composition of the present embodiment is heat-treated to cure the adhesive resin composition of the present embodiment. Thereby, the substrate 30 and the electronic component 20 are adhered via the adhesive layer 10, and the electronic device 100 is obtained.

[0078] As described above, the embodiments of the present invention have been described, but these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope capable of achieving the object of the present invention are included in the present invention.

Example

[0079] The embodiments of the present invention will be described in detail based on examples and comparative examples. The present invention is not limited to the examples.

[0080] <Examples, Comparative Examples> (Preparation of Adhesive Resin Composition) For each of the examples and comparative examples, the adhesive resin composition was prepared as follows. First, each component was uniformly mixed according to the formulation (parts by mass) shown in Table 1 to obtain a varnish. Next, the varnish obtained according to the formulation shown in Table 1 and the inorganic filler were mixed to obtain the adhesive resin compositions of each example and each comparative example, respectively. Details of each component in Table 1 are as follows.

[0081] (Epoxy Resin) Epoxy Resin 1: Siloxane skeleton epoxy resin (TSL-9906-2, manufactured by Momentive Performance Materials Japan LLC)

[0082] (Urethane (meth)acrylate polymer) Urethane (meth)acrylate polymer 1: Urethane (meth)acrylate polymer (CN9004, manufactured by Sartomer Co., Ltd., glass transition temperature (Tg): -74°C) Urethane (meth)acrylate polymer 2: Urethane (meth)acrylate polymer (UN-6207, manufactured by Negami Kogyo Co., Ltd., glass transition temperature (Tg): -59°C)

[0083] (Silicone oil) Silicone oil 1: Modified silicone oil (X22-2445, manufactured by Shin-Etsu Silicone Co., Ltd., glass transition temperature (Tg): -60°C)

[0084] (Acrylic resin) Acrylic resin 1: Isodecyl acrylate (SR395NS, manufactured by ARKEMA Co., Ltd., glass transition temperature (Tg): -60°C)

[0085] (Low stress agent) Low stress agent 1: Modified polybutadiene (RICOBOND1731, manufactured by Cray Valley Co., Ltd.)

[0086] (Coupling agent) Coupling agent 1: Bis(3-(triethoxysilyl)propyl)tetrasulfide (Kabras 4, manufactured by Osaka Soda Co., Ltd.)

[0087] (Nitrogen atom-containing compound) Nitrogen atom-containing compound 1: Dicyandiamide derivative (EH-3636AS, manufactured by ADEKA Co., Ltd.)

[0088] (Peroxide) Peroxide 1: 1,1-Di(tert-butylperoxy)cyclohexane (Perhexa (registered trademark) CS, manufactured by NOF Corporation) Peroxide 2: Dilauroyl peroxide (Luperox LP, manufactured by Arkema Kifuku Co., Ltd.)

[0089] (Inorganic filler) Inorganic filler 1: Fumed silica (AEROSIL (registered trademark) R-805, manufactured by Nippon Aerosil Co., Ltd., D 50 : 0.012 μm)

[0090] (Physical property evaluation) The physical properties of the adhesive resin compositions obtained in each example were evaluated by the following methods.

[0091] (tanδ, glass transition temperature (Tg), half-width) On a glass substrate, two tapes were pasted in parallel with a 6-mm interval. The adhesive resin compositions of each example and each comparative example were applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate was heat-treated at 175 °C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product was removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring device (DMA7100, manufactured by Hitachi High-Technologies Corporation), tanδ was measured under the conditions of initial temperature: -100 °C, heating rate: 5 °C / min, frequency: 10 Hz, and measurement mode: tension. After the measurement, tanδ was plotted on the vertical axis and temperature (°C) was plotted on the horizontal axis to create a dynamic viscoelasticity curve. The maximum value of tanδ in the region of -100 °C or higher and -30 °C or lower at this time was taken as the peak top, and the peak including the peak top was read. The temperature of the peak top was read as the glass transition temperature (Tg). The measurement results are shown in Table 1. Next, in the peak including the peak top, the temperature at which tanδ becomes half of the maximum value was defined as T L (low-temperature side) and T H (high-temperature side), and the half-width was calculated by the following formula (1). The measurement results are shown in Table 1. Half-width (°C) = T H - T L (1)

[0092] (Loss elastic modulus E'', storage elastic modulus E') Two tapes were adhered in parallel on a glass substrate with a 6-mm gap therebetween. An adhesive resin composition of each example and each comparative example was applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate with the composition was heat-treated at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product was removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring apparatus (DMA7100, manufactured by Hitachi High-Technologies Corporation), the loss elastic modulus E'' and the storage elastic modulus E' were measured under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension, and the loss elastic modulus E'' at -40°C and the storage elastic modulus E' at 25°C were read. The measurement results are shown in Table 1.

[0093] (Die shear strength) 2.5 mg of the adhesive resin composition of each example and each comparative example was applied to the central portion of the upper surface of a gold-plated plate with a length of 10 mm × width of 10 mm × thickness of 1 mm and was coated so as to have a thickness of 20 μm. Next, a gold-plated silicon chip with a length of 5.0 mm × width of 5.0 mm × thickness of 350 μm was placed on the adhesive resin composition such that the central portion of the surface of the gold-plated plate and the central portion of the surface of the gold-plated silicon chip overlapped in the vertical direction. Then, a pressure of 0.05 kgf / cm 2 was applied in the direction perpendicular to the surface of the gold-plated silicon chip to obtain a laminate. Thereafter, the laminate was heat-treated at 175°C for 90 minutes to obtain a test piece. For the test piece, using a universal bond tester (Dage4000PLUS, manufactured by Nordson Advanced Technology Co., Ltd.), at a shear jig moving speed of 20 mm / min, the jig was pressed against the side surface of the gold-plated silicon chip at a point 50 μm away in the direction perpendicular to the upper surface of the test laminate to measure the die shear strength at 25°C. The measurement results are shown in Table 1.

[0094]

Table 1

[0095] In each example, the balance of performance in terms of adhesion and low elastic modulus in the ultra-low temperature region was improved for each comparative example.

Explanation of Signs

[0096] 10 Adhesive layer 20 Electronic component 30 Substrate 100 Electronic device

Claims

1. A urethane (meth) acrylate polymer, an inorganic filler, and a coupling agent, comprising an adhesive resin composition.

2. The adhesive resin composition according to claim 1, wherein the glass transition temperature (Tg) of the urethane (meth) acrylate polymer by dynamic viscoelasticity measurement method is -40 ° C or lower.

3. The adhesive resin composition according to claim 1 or 2, wherein the mass average molecular weight of the urethane (meth) acrylate polymer by GPC measurement method is 5,000 or more and 200,000 or less.

4. The adhesive resin composition according to claim 1 or 2, wherein the content of the urethane (meth) acrylate polymer is 50% by mass or more and 99% by mass or less when the total amount of the adhesive resin composition is 100% by mass.

5. The adhesive resin composition according to claim 1 or 2, further comprising a nitrogen atom-containing compound.

6. The adhesive resin composition according to claim 5, wherein the nitrogen atom-containing compound contains one or more selected from the group consisting of dicyandiamide and dicyandiamide derivatives.

7. The adhesive resin composition according to claim 5, wherein the content of the nitrogen atom-containing compound is 0.01 part by mass or more and 5.0 parts by mass or less when the total amount of the resin components contained in the adhesive resin composition is 100 parts by mass.

8. The adhesive resin composition according to claim 1 or 2, wherein the content of the inorganic filler is 0.1% by mass or more and 10.0% by mass or less when the total amount of the adhesive resin composition is 100% by mass.

9. The adhesive resin composition according to claim 1 or 2, wherein the coupling agent contains one or more selected from the group consisting of epoxy silane, sulfide silane and organo silane.

10. The adhesive resin composition according to claim 1 or 2, wherein the content of the coupling agent is 0.01 part by mass or more and 3.0 parts by mass or less when the total amount of the resin components contained in the adhesive resin composition is 100 parts by mass.

11. The adhesive resin composition according to claim 1 or 2, further comprising silicone oil.

12. The adhesive resin composition according to claim 11, wherein the content of the silicone oil is 1.0% by mass or more and 15.0% by mass or less when the total amount of the adhesive resin composition is 100% by mass.

13. The adhesive resin composition according to claim 1 or 2, further comprising a (meth) acrylic resin.

14. The adhesive resin composition according to claim 13, wherein the content of the (meth)acrylic resin is 1.0% by mass or more and 30.0% by mass or less when the total amount of the adhesive resin composition is 100% by mass.

15. The adhesive resin composition according to claim 1 or 2, further comprising a peroxide.

16. The adhesive resin composition according to claim 15, wherein the content of the peroxide is 0.1 part by mass or more and 10.0 parts by mass or less when the total amount of the resin components contained in the adhesive resin composition is 100 parts by mass.

17. The adhesive resin composition according to claim 1 or 2, wherein the content of the epoxy resin is less than 1.0% by mass when the total amount of the adhesive resin composition is 100% by mass.

18. The adhesive resin composition according to claim 1 or 2, which has a peak in the region of -100°C or higher and -30°C or lower in the dynamic viscoelasticity curve obtained by the following (Method 1). (Method 1) On a glass substrate, two tapes are pasted in parallel with a 6-mm interval. The adhesive resin composition is applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate is heat-treated at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. The cured product is removed from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring device, tanδ is measured under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension. After the measurement, tanδ is plotted on the vertical axis and temperature (°C) is plotted on the horizontal axis to create a dynamic viscoelasticity curve. In the region of -100°C or higher and -30°C or lower of the dynamic viscoelasticity curve, the presence or absence of a peak is confirmed when tanδ is 0.1 or more and the point where tanδ shows the maximum value in the above region is taken as the peak top.

19. The adhesive resin composition according to claim 1 or 2, wherein the maximum value of tanδ in the region of -100°C or higher and -30°C or lower obtained by the following (Method 2) is 0.1 or more and 2.5 or less. (Method 2) On a glass substrate, two tapes are pasted in parallel with a 6-mm interval. The adhesive resin composition is applied between the two tapes with a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and the glass substrate is heat-treated at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. Remove the cured product from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring apparatus, measure tan δ under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension. After the measurement, read the maximum value of tan δ in the region of -100°C or higher and -30°C or lower.

20. The adhesive resin composition according to claim 1 or 2, wherein the half-value width according to the following (Method 3) is 10 or more and 100 or less. (Method 3) On a glass substrate, stick two tapes in parallel with a 6-mm interval therebetween. Apply the adhesive resin composition between the two tapes in a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and heat-treat the whole glass substrate at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. Remove the cured product from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring apparatus, measure tan δ under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension. Then, read the maximum value of tan δ in the region of -100°C or higher and -30°C or lower, and use it as the peak top. Next, at the peak including the peak top, the temperature at which tan δ becomes half of the maximum value is defined as T Ｌ (low temperature side) and T Ｈ (high temperature side), and the half-value width is calculated by the following formula (1). Half-value width (°C) = T Ｈ - T Ｌ (1)

21. The value of the loss elastic modulus E'' at -40°C by the following (Method 4) is 1.0 × 10 －４ MPa or more and 1.0 × 10 ５ MPa or less, and the adhesive resin composition according to claim 1 or 2. (Method 4) On a glass substrate, stick two tapes in parallel with a 6-mm interval therebetween. Apply the adhesive resin composition between the two tapes in a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and heat-treat the whole glass substrate at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. Remove the cured product from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring apparatus, measure the loss elastic modulus E'' under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension, and read the loss elastic modulus E'' at -40°C.

22. The value of the storage elastic modulus E' at 25°C by the following (Method 5) is 1.0 × 10 －２ MPa or more and 1.0 × 10 ５ MPa or less, and the adhesive resin composition according to claim 1 or 2. (Method 5) On a glass substrate, stick two tapes in parallel with a 6-mm interval therebetween. Apply the adhesive resin composition between the two tapes in a length of 20 mm × width of 6 mm × thickness of 0.5 mm, and heat-treat the whole glass substrate at 175°C for 90 minutes to obtain a cured product of the adhesive resin composition. Remove the cured product from the glass substrate, and for the cured product, using a dynamic viscoelasticity measuring apparatus, measure the storage elastic modulus E' under the conditions of an initial temperature of -100°C, a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement mode of tension, and read the storage elastic modulus E' at 25°C.

23. The adhesive resin composition according to claim 1 or 2, wherein the die shear strength by the following (Method 6) is 50 N or more. (Method 6) Apply 2.5 mg of the adhesive resin composition to the central portion of the upper surface of a gold-plated plate having a length of 10 mm × a width of 10 mm × a thickness of 1 mm, and coat it so that the thickness becomes 20 μm. Next, place a gold-plated silicon chip having a length of 5.0 mm × a width of 5.0 mm × a thickness of 350 μm on the adhesive resin composition such that the central portion of the surface of the gold-plated plate and the central portion of the surface of the gold-plated silicon chip overlap in the vertical direction. Then, apply a pressure of 0.05 kgf / cm ２ from a direction perpendicular to the surface of the gold-plated silicon chip to obtain a laminate. Thereafter, heat-treat the laminate at 175 °C for 90 minutes to obtain a test piece. For the test piece, using a universal bond tester, the die shear strength at 25°C is measured by pressing a jig against the side surface of the gold-plated silicon chip at a point 50 μm away from the upper surface of the gold-plated plate in a direction perpendicular to the upper surface of the gold-plated plate at a shear jig moving speed of 20 mm / min.

24. An electronic device comprising a cured product of the adhesive resin composition according to claim 1 or 2.

25. A base material, An adhesive layer on the base material, An electronic component on the adhesive layer, and The electronic device according to claim 24, wherein the adhesive layer contains a cured product of the adhesive resin composition.

26. The electronic device according to claim 25, wherein the electronic component includes a sensor.

27. The electronic device according to claim 24, which is a flexible device.

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