Polymerizable paste composition, high thermal conductivity material

Abstract

To provide a pasty polymerizable composition that exhibits excellent conductivity and heat radiation and has improved adhesion to a semiconductor element or a substrate.SOLUTION: The inventive pasty polymerizable composition contains (A) a compound represented by general formula (a) and (B) silver-containing particles. (In the general formula (a), R1, R2, R3 and R4 independently represent a hydrogen atom, or a substituted or unsubstituted, C1-12 organic group optionally having a heteroatom, where at least one of R1, R2, R3 and R4 is the organic group; and n is 0, 1 or 2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to Polymerizable pace T-group a composition and a high thermal conductivity material.

Background Art

[0002] A technique for manufacturing a semiconductor device using a thermosetting resin composition containing metal particles is known with the intention of enhancing the heat dissipation property of the semiconductor device. By including metal particles having a higher thermal conductivity than the resin in the thermosetting resin composition, the thermal conductivity of the cured product can be increased.

[0003] As a specific example of application to a semiconductor device, a technique for adhering / joining a semiconductor element and a substrate (supporting member) using a thermosetting resin composition containing metal particles is known as in Patent Documents 1 and 2 below.

[0004] Patent Document 1 discloses a thermosetting resin composition for semiconductor adhesion containing a (meth)acrylate compound having a predetermined structure, a radical initiator, silver fine particles, silver powder, and a solvent, and a semiconductor device in which a semiconductor element and a base material are joined with the composition. It is described in the document that the connection reliability against a temperature cycle after mounting can be improved (paragraph 0011).

[0005] Patent Document 2 discloses a resin paste composition containing an imide acrylate compound, a radical initiator, a filler, and a liquid rubber component, and a semiconductor device in which a semiconductor element and a base material are joined with the composition. It is described in the document that generation of chip cracks and chip warpage can be suppressed by reducing the stress of the resin paste composition (paragraph 0003).

[0006] Patent Document 3 discloses a resist paste obtained by dispersing conductive particles such as silver in a cyclic olefin resin. It is described in the document that a multilayer wiring board includes a resistor composed of the resist paste.

Prior Art Documents

Patent Document

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] The inventor has studied a semiconductor device in which a semiconductor element and a base material such as a copper lead frame are connected through an adhesive layer formed by sintering a paste T-group with respect to the conductivity, heat dissipation, and adhesion to the semiconductor element and the base material of this paste. As a result, the compositions described in Patent Documents 1 and 2 had room for improvement in these characteristics. T-group

[0009] T-group The present invention has been made in view of the above problems, and provides a paste having excellent conductivity and heat dissipation and improved adhesion to a semiconductor element and a base material.

Means for Solving the Problems

[0010] Polymerizable T-group The inventors have found that by sintering a paste containing a predetermined cyclic olefin monomer and silver - containing particles, it has excellent conductivity and heat dissipation and improved adhesion to a semiconductor element and a base material, and completed the present invention.

[0011] That is, the present invention can be shown as follows. Polymerizable According to the present invention, T-group (A) a compound represented by the following general formula (a), and And, (B) silver - containing particles, and including Polymerizable Pace T-group Composition And, The proportion of silver-containing particles (B) in the entire polymerizable paste composition is 50 to 98% by mass. is provided. [Chemical formula] (In general formula (a), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 12 carbon atoms which may have a substituted or unsubstituted heteroatom, and at least one of R 1 , R 2 , R 3 and R 4 is the organic group, and n is 0, 1 or 2.)

[0012] According to the present invention, the above-mentioned Polymerizable pace T-group A high thermal conductivity material obtained by sintering the composition a high thermal conductivity material comprising a linked structure of silver-containing particles (B) formed by heat treatment. is provided.

[0013] According to the present invention, A resin having a repeating structural unit represented by the following general formula (a1) including , The aforementioned A high thermal conductivity material is provided. [Chemical formula] (In general formula (a1), R 1 , R 2 , R 3 , R 4 , n has the same meaning as general formula (a). * is a bond.)

[0014] According to the present invention, a substrate, a semiconductor element mounted on the substrate via an adhesive layer, and the adhesive layer is formed by sintering the above-mentioned Polymerizable pace T-group A semiconductor device formed by sintering the composition is provided. [Effects of the Invention]

[0015] According to the present invention, excellent conductivity and heat dissipation are achieved, and adhesion to semiconductor elements and substrates is improved. Polymerizable pace T-group We can provide finished products. [Brief explanation of the drawing]

[0016] [Figure 1] This is a schematic cross-sectional view showing an example of a semiconductor device. [Figure 2] This is a schematic cross-sectional view showing an example of a semiconductor device. [Figure 3] (a) is a scanning electron microscope image of a cross-section (after polishing) of a sample used for die shear strength testing with the polymerizable paste composition of Example 5, and (b) is a magnified view of the portion of the sintered body of the composition that is in contact with the substrate. [Figure 4] (a) is a scanning electron microscope image of a cross-section (after polishing) of a sample used for die shear strength testing with the polymerizable paste composition of Comparative Example 1, and (b) is a magnified view of the portion of the sintered body of the composition that is in contact with the substrate. [Figure 5] This is a scanning electron microscope image of the cross-section (after polishing) of the heat-treated body obtained from the polymerizable paste composition of Example 5. [Figure 6] This is a scanning electron microscope image of the cross-section (after polishing) of the heat-treated body obtained from the polymerizable paste composition of Example 11. [Figure 7] This is a scanning electron microscope image of the cross-section (after polishing) of a heat-treated body obtained from the polymerizable paste composition of Example 12. [Figure 8] This is a scanning electron microscope image of the cross-section (after polishing) of the heat-treated body obtained from the polymerizable paste composition of Example 14. [Figure 9] This is a scanning electron microscope image of the cross-section (after polishing) of the heat-treated body obtained from the polymerizable paste composition of Example 17. [Figure 10] This is a scanning electron microscope image of the cross-section (after polishing) of a heat-treated body obtained from the polymerizable paste composition of Comparative Example 1. [Modes for carrying out the invention]

[0017] Embodiments of the present invention will be described below with reference to the drawings. In all drawings, similar components are denoted by the same reference numerals, and their descriptions are omitted as appropriate. Unless otherwise specified, "~" indicates a range from "greater than or equal to" to "less than or equal to".

[0018] < Polymerizable pace T-group Products > This embodiment Polymerizable pace T-group The finished product is (A) Compounds represented by general formula (a), (B) Silver-containing particles and Includes.

[0019] [Compound (A)] Compound (A) is represented by the following general formula (a).

[0020] [ka]

[0021] In general formula (a), R 1 , R 2 , R 3 and R 4 Each of these is an organic group having 1 to 12 carbon atoms, which may independently contain a hydrogen atom or a substituted or unsubstituted heteroatom.

[0022] R 1 , R 2 , R 3 and R 4 At least one of them is the aforementioned organic group, R 1 , R 2 , R 3 and R 4 Any one of the above, or R 1 (or R 2 ) and R 3 (or R 4 Preferably, the two of ) are the aforementioned organic groups, R1 , R 2 , R 3 and R 4 It is more preferable that one of them is the aforementioned organic group. Compound (A) may contain one or more compounds selected from those represented by general formula (a).

[0023] In this embodiment, the Δ value of the Hansen solubility parameter between compound (A) and silver-containing particles (B) is large, and the affinity between (A) and (B) is low, resulting in high affinity between (B) particles themselves. This makes it easier for silver-containing particles (B) to form a bonded structure, which is expected to improve thermal conductivity and electrical conductivity, as well as adhesion to semiconductor devices and substrates.

[0024] As organic groups having 1 to 12 carbon atoms, any known organic groups can be selected as long as they can exhibit the effects of the present invention. Examples include C1-C12 alkyl groups, C1-C12 alkenyl groups, C1-C12 alkynyl groups, C1-C12 aralkyl groups, C1-C12 alkalyl groups, C3-C12 cycloalkyl groups, or C1-C12 alkoxy groups.

[0025] Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Examples of alkenyl groups include vinyl groups, allyl groups, butynyl groups, and cyclohexenyl groups. Examples of alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, and 2-butynyl group. Examples of aralkyl groups include benzyl groups and phenethyl groups. Examples of alkalyl groups include tolyl groups and xylyl groups. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0026] Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, neopentyloxy, and n-hexyloxy groups.

[0027] Examples of C1-C12 organic groups having heteroatoms include the aforementioned C1-C12 organic groups that have at least one of the following types of bonds in their structure: ether bond, ester bond, carbonate bond, amide bond, urethane bond, and thiourethane bond.

[0028] From the viewpoint of the effects of the present invention, the organic group having 1 to 12 carbon atoms and a heteroatom is preferably a group having at least one selected from an ether bond, an ester bond, or a carbonate bond, and more preferably a group having at least one selected from an ether bond and an ester bond.

[0029] Furthermore, the substituents of the C1-C12 organic group, which may have a substituted heteroatom, can be selected from at least one of the following: a hydroxyl group, an amino group, a carboxyl group, and a mercapto group. From the viewpoint of the effects of the present invention, the substituent is preferably a hydroxyl group, an amino group, or a carboxyl group, and more preferably a hydroxyl group. The substituent is preferably located at the terminal end. n is 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0030] Examples of organic groups with 1 to 12 carbon atoms that have substituted or unsubstituted heteroatoms include the following groups:

[0031] [ka]

[0032] In the formula, X 1 X is a single bond or an alkylene group having 1 to 12 carbon atoms. 2X represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl alcohol group having 1 to 12 carbon atoms, an alkyl carboxyl group having 1 to 12 carbon atoms, or an alkylamino group having 1 to 12 carbon atoms, and the total number of carbon atoms in each of the groups represented by the above formula is 1 to 12. Multiple X present in the same group 1 The elements may be the same or different. * indicates a link.

[0033] In this embodiment, preferred C1-C12 organic groups, which may have substituted or unsubstituted heteroatoms, are C1-C12 alkyl groups, C1-C12 alkyl groups substituted with a hydroxyl group, an amino group, or a carboxyl group, or groups represented by the following general formula.

[0034] [ka]

[0035] In the formula, X 1 X is a single bond or an alkylene group having 1 to 12 carbon atoms. 2 X represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl alcohol group having 1 to 12 carbon atoms, an alkyl carboxyl group having 1 to 12 carbon atoms, or an alkylamino group having 1 to 12 carbon atoms, and the total number of carbon atoms in each group is 1 to 12. Multiple X groups present within the same group. 1 The elements may be the same or different. * indicates a link. In this embodiment, among the C1-C12 organic groups which may have substituted or unsubstituted heteroatoms, alkyl groups with hydroxyl groups substituted with C1-C12 are more preferred.

[0036] Polymerizable pace T-group From the viewpoint of the effects of the present invention, the proportion of compound (A) in the whole product is 1 to 30% by mass, preferably 2 to 20% by mass, and more preferably 5 to 15% by mass.

[0037] [Silver-containing particles (B)] Silver-containing particles (B) can undergo sintering through appropriate heat treatment, forming a particle linkage structure (sintered structure).

[0038] especially, Polymerizable pace T-group The presence of silver-containing particles in the finished product, particularly silver particles with relatively small particle size and relatively large specific surface area, facilitates the formation of a sintering structure even during heat treatment at relatively low temperatures (around 180°C). Preferred particle size will be discussed later.

[0039] The shape of the silver-containing particles (B) is not particularly limited. A preferred shape is spherical, but non-spherical shapes such as ellipsoidal, flattened, plate-like, needle-like, flaky, aggregated, and polyhedral shapes are also acceptable. The silver-containing particles (B) may contain at least one of these shapes.

[0040] In this embodiment, it is preferable to include two or more types of silver-containing particles selected from spherical, flaky, aggregated, and polyhedral shapes, more preferably spherical silver-containing particles b1 and one or more types of silver-containing particles b2 selected from flaky, aggregated, and polyhedral shapes, and particularly preferable to include spherical silver-containing particles b1 and flaky silver-containing particles b2-1. This further improves the contact rate between the silver-containing particles, Polymerizable pace T-group After sintering the finished product, a network is easily formed, further improving thermal and electrical conductivity.

[0041] By including silver-containing particles (B) and silver-containing particles b2, Polymerizable pace T-group This method can suppress resin cracking in molded products obtained from the material, and can also suppress increases in the coefficient of thermal expansion. In this embodiment, "spherical" is not limited to a perfect sphere, but also includes shapes with slight irregularities on the surface. The degree of circularity is, for example, 0.90 or higher, preferably 0.92 or higher, and more preferably 0.94 or higher.

[0042] The silver-containing particles (B) may have their surface treated with a carboxylic acid, a saturated fatty acid having 4 to 30 carbon atoms, a monovalent unsaturated fatty acid having 4 to 30 carbon atoms, a long-chain alkyl nitrile, etc.

[0043] The silver-containing particles (B) may be (i) particles consisting substantially of silver only, or (ii) particles consisting of silver and components other than silver. Alternatively, (i) and (ii) may be used in combination as the metal-containing particles.

[0044] In this embodiment, the silver-containing particles (B) are particularly preferably silver-coated resin particles in which the surface of the resin particles is coated with silver. This results in a cured product with superior thermal conductivity and superior storage modulus. Polymerizable pace T-group The finished product can be prepared.

[0045] Silver-coated resin particles, having a silver surface and a resin core, are thought to have good thermal conductivity and be softer than particles made solely of silver. Therefore, using silver-coated resin particles makes it easier to design materials with appropriate thermal conductivity and storage modulus.

[0046] Typically, increasing the amount of silver-containing particles is considered to improve thermal conductivity. However, since metals are generally "hard," too much silver-containing particle can result in an excessively high elastic modulus after sintering. By having some or all of the silver-containing particles be silver-coated resin particles, it is possible to obtain a cured product with the desired thermal conductivity and storage modulus. Polymerizable pace T-group The finished product can be easily designed. In the case of silver-coated resin particles, it is sufficient for the silver layer to cover at least a portion of the surface of the resin particle. Of course, the entire surface of the resin particle may also be covered with silver.

[0047] Specifically, in silver-coated resin particles, the silver layer covers preferably 50% or more, more preferably 75% or more, and even more preferably 90% or more of the surface of the resin particles. Particularly preferably, in silver-coated resin particles, the silver layer covers substantially the entire surface of the resin particles. From another perspective, it is preferable that when silver-coated resin particles are cut at a certain cross-section, a silver layer is observed around the entire perimeter of that cross-section.

[0048] From another perspective, the mass ratio of resin to silver in the silver-coated resin particles is, for example, 90 / 10 to 10 / 90, preferably 80 / 20 to 20 / 80, and more preferably 70 / 30 to 30 / 70.

[0049] Examples of "resins" in silver-coated resin particles include silicone resin, (meth)acrylic resin, phenolic resin, polystyrene resin, melamine resin, polyamide resin, and polytetrafluoroethylene resin. Of course, other resins may also be used. Furthermore, only one type of resin may be used, or two or more types of resins may be used in combination. From the viewpoint of elastic properties and heat resistance, silicone resin or (meth)acrylic resin is preferred as the resin.

[0050] The silicone resin may also consist of particles composed of organopolysiloxanes obtained by polymerizing organochlorosilanes such as methylchlorosilane, trimethyltrichlorosilane, and dimethyldichlorosilane. Alternatively, the silicone resin may have a basic framework consisting of organopolysiloxanes further cross-linked in three dimensions.

[0051] (Meth)acrylic resin can be a resin obtained by polymerizing a monomer containing a (meth)acrylic acid ester as the main component (50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more). Examples of (meth)acrylic acid esters include at least one compound selected from the group consisting of 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, chloro-2-hydroxyethyl (meth)acrylate, diethylene glycol mono (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isovonol (meth)acrylate. Furthermore, the monomer component of the acrylic resin may contain small amounts of other monomers. Examples of such other monomer components include styrene monomers. For silver-coated (meth)acrylic resins, please also refer to the description in Japanese Patent Publication No. 2017-126463.

[0052] Various functional groups may be introduced into silicone resins or (meth)acrylic resins. The functional groups that can be introduced are not particularly limited. Examples include epoxy groups, amino groups, methoxy groups, phenyl groups, carboxyl groups, hydroxyl groups, alkyl groups, vinyl groups, mercapto groups, and the like.

[0053] The resin particle portion of the silver-coated resin particles may contain various additive components, such as low-stress modifiers. Examples of low-stress modifiers include butadiene styrene rubber, butadiene acrylonitrile rubber, polyurethane rubber, polyisoprene rubber, acrylic rubber, fluororubber, liquid organopolysiloxane, and liquid synthetic rubbers such as liquid polybutadiene. In particular, when the resin particle portion contains silicone resin, the inclusion of a low-stress modifier can improve the elastic properties of the silver-coated resin particles.

[0054] The shape of the resin particles in the silver-coated resin particles is not particularly limited. Preferably, a combination of spherical and other non-spherical shapes, such as flattened, plate-shaped, or needle-shaped, is preferred.

[0055] The specific gravity of the silver-coated resin particles is not particularly limited, but the lower limit is, for example, 2 or more, preferably 2.5 or more, and more preferably 3 or more. The upper limit of the specific gravity is, for example, 10 or less, preferably 9 or less, and more preferably 8 or less. An appropriate specific gravity is preferable in terms of the dispersibility of the silver-coated resin particles themselves and the uniformity when silver-coated resin particles are used in combination with other silver-containing particles.

[0056] When using silver-coated resin particles, the proportion of silver-coated resin particles in the total silver-containing particles (B) is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and even more preferably 5 to 40% by mass. By appropriately adjusting this proportion, it is possible to further improve heat dissipation while suppressing the decrease in adhesive strength due to heat cycling.

[0057] Incidentally, if the proportion of silver-coated resin particles in the total silver-containing particles (B) is not 100% by mass, then the silver-containing particles other than the silver-coated resin particles are, for example, particles that consist substantially of only silver.

[0058] Median diameter D of silver-containing particle (B) 50 This is, for example, 0.01 to 50 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 10 μm. 50By setting this to an appropriate value, it is easier to balance thermal conductivity, sinterability, and resistance to heat cycling. Also, D 50 Setting this to an appropriate value can sometimes improve the workability of application / adhesion. The particle size distribution of silver-containing particles (horizontal axis: particle size, vertical axis: frequency) may be unimodal or multimodal.

[0059] From the viewpoint of the effects of the present invention, it is preferable that the silver-containing particles (B) include spherical silver-containing particles b1 and flaky silver-containing particles b2-1. It is more preferable that these silver-containing particles consist substantially of only silver.

[0060] Median diameter D of spherical silver-containing particle b1 50 The particle size is, for example, 0.1 to 20 μm, preferably 0.5 to 10 μm, and more preferably 0.5 to 5.0 μm. The specific surface area of ​​the spherical silver-containing particles b1 is, for example, 0.1 to 2.5 m². 2 / g, preferably 0.5-2.3m 2 / g, more preferably 0.8~2.0m 2 It is / g. The tap density of spherical silver-containing particles b1 is, for example, 1.5 to 6.0 g / cm³. 3 Preferably 2.5 to 5.8 g / cm³ 3 More preferably 4.5 to 5.5 g / cm³ 3 That is the case. The circularity of the spherical silver-containing particles b1 is, for example, 0.90 or higher, preferably 0.92 or higher, and more preferably 0.94 or higher. By satisfying these characteristics, it achieves an excellent balance of thermal conductivity, sinterability, and resistance to heat cycling.

[0061] Median diameter D of flaky silver-containing particle b2-1 50 The particle size is, for example, 0.1 to 20 μm, preferably 1.0 to 15 μm, and more preferably 2.0 to 10 μm. The specific surface area of ​​the flaky silver-containing particles b2-1 is, for example, 0.1 to 2.5 m². 2 / g, preferably 0.2-2.0m 2 / g, more preferably 0.25~1.2m 2 It is / g. The tap density of the flaky silver-containing particles b2-1 is, for example, 1.5 to 6.0 g / cm³. 3 Preferably 2.5 to 5.9 g / cm³ 3 , more preferably 4.0 to 5.8 g / cm³ 3 That is the case. By satisfying these characteristics, it achieves an excellent balance of thermal conductivity, sinterability, and resistance to heat cycling.

[0062] In this embodiment, by combining spherical silver-containing particles b1 that satisfy at least one of the above characteristics with flake-shaped silver-containing particles b2-1 that satisfy at least one of the above characteristics, thermal conductivity and electrical conductivity are particularly improved.

[0063] The ratio of the content of spherical silver-containing particles b1 to the content of flaky silver-containing particles b2-1 (b1 / b2-1) is preferably 0.1 to 10, more preferably 0.3 to 5, and particularly preferably 0.5 to 3. This significantly improves the contact rate between the silver-containing particles. Polymerizable pace T-group After sintering, a network is easily formed in the finished product, resulting in particularly improved thermal and electrical conductivity.

[0064] Median diameter D of flaky silver-containing particle b2-1 50 Median diameter D of spherical silver-containing particle b1 50 The ratio (b1 / b2-1) is preferably 0.01 or more and 0.8 or less, more preferably 0.05 or more and 0.6 or less. As a result, spherical silver-containing particles efficiently fill the gaps between the flaky silver-containing particles, and the contact rate between the silver-containing particles is particularly improved, Polymerizable pace T-group After sintering, a network is easily formed in the finished product, resulting in particularly improved thermal and electrical conductivity.

[0065] The ratio of the tap density of spherical silver-containing particles b1 to the tap density of flaky silver-containing particles b2-1 (b1 / b2-1) is preferably 0.5 or more and 2.0 or less, more preferably 0.7 or more and 1.2 or less. As a result, the packing density of silver-containing particles is improved, and the contact rate between silver-containing particles is particularly improved, Polymerizable pace T-group After sintering, a network is easily formed in the finished product, resulting in particularly improved thermal and electrical conductivity.

[0066] Median diameter D of silver-coated resin particles 50 The thickness is, for example, 5.0 to 25 μm, preferably 7.0 to 20 μm, and more preferably 8.0 to 15 μm. This can further improve thermal conductivity.

[0067] Median diameter D of silver-containing particle (B) 50 This can be determined, for example, by performing particle image measurement using the FPIA(registered trademark)-3000 flow-type particle image analyzer manufactured by Sysmex Corporation. More specifically, the particle size of silver-containing particles (B) can be determined by measuring the volume-based median diameter using this instrument in a wet manner.

[0068] Polymerizable pace T-group The proportion of silver-containing particles (B) in the overall product is, for example, 1 to 98% by mass, preferably 30 to 95% by mass, and more preferably 50 to 90% by mass. A proportion of metal-containing particles of 1% by mass or more makes it easier to improve thermal conductivity. A proportion of silver-containing particles (B) of 98% by mass or less improves the workability of coating / adhesion.

[0069] Of the silver-containing particles (B), those consisting substantially of only silver can be obtained from companies such as DOWA High-Tech Co., Ltd. and Fukuda Metal Foil & Powder Industry Co., Ltd. Silver-coated resin particles can be obtained from companies such as Mitsubishi Materials Corporation, Sekisui Chemical Co., Ltd. and Sanno Co., Ltd.

[0070] [Silane coupling agent (C)] This embodiment Polymerizable pace T-group The product may further contain a silane coupling agent (C). This can further improve the adhesive strength.

[0071] Examples of silane coupling agents (C) include well-known silane coupling agents, specifically vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane;

[0072] Epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; Styrylsilanes such as p-styryltrimethoxysilane; Norbornene silanes such as norbornenetrimethoxysilane, norbornenemethyltrimethoxysilane, norbornenemethyltriethoxysilane, and norbornenemethyltrimethoxysilane; Methacrylsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; Acrylic silanes such as 3-(trimethoxysilyl)propyl methacrylate and 3-acryloxypropyltrimethoxysilane; Aminosilanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and N-phenyl-γ-aminopropyltrimethoxysilane; Isocyanurate silane; Alkylsilane; Ureidosilanes such as 3-ureidopropyltrialkoxysilane; Mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; Examples include isocyanate silanes such as 3-isocyanatetopropyltriethoxysilane. When using silane coupling agents, one type may be used alone, or two or more types may be used in combination. The silane coupling agent (C) preferably contains a norbornene-based silane coupling agent.

[0073] This embodiment Polymerizable pace T-group If the product contains a silane coupling agent (C), the amount is, for example, 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, when the amount of cyclic olefin compound (A) is 100 parts by mass.

[0074] [Polymerization catalyst (D)] This embodiment Polymerizable pace T-group The product may further contain a polymerization catalyst (D). Examples of polymerization catalysts (D) include ring-opening metathesis polymerization catalysts, which can be used to obtain cyclic polyolefins by ring-opening polymerization of cyclic olefin compounds (A).

[0075] Known catalysts can be used for ring-opening metathesis polymerization. Specifically, complexes formed by bonding multiple ions, atoms, polyatomic ions, and / or compounds to a transition metal atom can be used as catalysts for ring-opening metathesis polymerization. Atoms from groups 5, 6, and 8 (long-period periodic table, hereinafter the same) can be used as transition metal atoms. While the atoms of each group are not particularly limited, preferred group 5 atoms are tantalum, preferred group 6 atoms are molybdenum and tungsten, and preferred group 8 atoms are ruthenium and osmium. The ring-opening metathesis polymerization catalyst is preferably a complex of ruthenium and osmium from group 8, and more preferably a ruthenium carbene complex.

[0076] This embodiment Polymerizable pace T-group If the product contains a polymerization catalyst (D), its amount is, for example, 0.0001 to 0.01 parts by mass, when the amount of cyclic olefin compound (A) is 100 parts by mass.

[0077] (solvent) This embodiment Polymerizable pace T-group The product may further contain a solvent. Depending on the solvent, for example, Polymerizable pace T-group This method can improve the fluidity of the product and the workability when forming an adhesive layer on a substrate. The solvent is typically an organic solvent.

[0078] Organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl methoxybutanol, α-terpineol, β-terpineol, hexylene glycol, benzyl alcohol, 2-phenylethyl alcohol, isopalmityl alcohol, isostearyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, butylpropylene triglyceride, glycerin, ethylene glycol, cyclohexanol, cyclohexanemethanol, and other alcohols; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5,5-trimethyl-2-cyclohexen-1-one), and diisobutyl ketone (2,6-dimethyl-4-heptanone); Ethyl acetate, butyl acetate, diethyl phthalate, dibutyl phthalate, acetoxyethane, methyl butyrate, methyl hexanoate, methyl octanoate, methyl decanoate, methyl cellosolve acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 1,2-diacetoxyethane, tributyl phosphate, tricresyl phosphate, tripentyl phosphate, propyl carbonate, and other esters; Ethers such as tetrahydrofuran, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether, 1,2-bis(2-diethoxy)ethane, 1,2-bis(2-methoxyethoxy)ethane, and tripropylene glycol mono-n-butyl ether; Ester ethers such as 2-(2-butoxyethoxy)ethane acetate; Ether alcohols such as 2-(2-methoxyethoxy)ethanol; Hydrocarbons such as toluene, xylene, n-paraffin, isoparaffin, dodecylbenzene, turpentine oil, kerosene, and diesel fuel; Nitriles such as acetonitrile or propionitrile; Amides such as acetamide and N,N-dimethylformamide; Lactones such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone Examples include low molecular weight volatile silicone oils and volatile organic modified silicone oils. When using solvents, one type of solvent may be used, or two or more solvents may be used in combination.

[0079] When using a solvent, the amount is not particularly limited. The amount used should be adjusted as appropriate based on the desired fluidity, etc. As an example, the solvent is: Polymerizable pace T-group It is used in quantities such that the non-volatile component concentration of the resulting product is 50-90% by mass.

[0080] (Other ingredients)

[0081] This embodiment Polymerizable pace T-group The resulting product may contain, to the extent that it does not impair the effects of the present invention, other components such as epoxy resin, curing agent, polyolefin such as polystyrene elastomer and polyethylene, low modulus of elasticity materials such as acrylic resin elastomer and polyurethane elastomer, dispersion stabilizers such as nanosilica, and defoaming agents.

[0082] (Properties of the composition) This embodiment Polymerizable pace T-group The product can be obtained by uniformly dispersing and mixing each component using conventionally known methods. Subsequently, defoaming treatment can be performed as needed.

[0083] This embodiment Polymerizable pace T-group The resulting product is preferably a paste at 20°C. That is, the product of this embodiment Polymerizable pace T-group The resulting product can preferably be applied to a substrate or the like in an adhesive state at 20°C. Polymerizable pace T-group The resulting product can preferably be used as an adhesive for semiconductor devices, etc. 。

[0084] <High thermal conductivity materials> This embodiment Polymerizable pace T-group A high thermal conductivity material can be obtained by sintering the resulting product. During the heat treatment in sintering, a cyclic olefin compound (A) undergoes ring-opening polymerization, yielding a high thermal conductivity material containing a resin having repeating structural units represented by the following general formula (a1), and a linked structure of silver-containing particles (B) formed by the heat treatment.

[0085] [ka]

[0086] In general formula (a1), R1 , R 2 , R 3 and R 4 This is equivalent to general formula (a). * represents a bond.

[0087] This embodiment Polymerizable pace T-group The resulting product exhibits a large Δ value of the Hansen solubility parameter between the cyclic olefin compound (A) and the silver-containing particles (B), indicating low compatibility between (A) and (B). This results in high affinity between (A) particles or between (B) particles. Consequently, heat treatment during sintering facilitates ring-opening polymerization between the cyclic olefin compounds (A) to form a cyclic polyolefin, while the silver-containing particles (B) form a linking structure. This composite structure is expected to exhibit excellent conductivity and heat dissipation. Furthermore, the linking structure formed between the silver-containing particles (B), as well as between the silver-containing particles (B) and metal substrates such as lead frames or plated chips used as substrates, is expected to improve adhesion to semiconductor devices and substrates.

[0088] Specifically, the temperature is raised from 30°C to 200°C over 30 to 120 minutes under a nitrogen atmosphere, followed by heat treatment at 100°C to 350°C for 60 to 180 minutes. This allows for the suitability of obtaining the resin having the repeating structural units represented by the general formula (a1), and also allows for the suitability of forming the linked structure of the silver-containing particles (B). By changing the shape of high thermal conductivity materials, they can be applied to various components in the automotive and electrical fields that require heat dissipation.

[0089] <Semiconductor device> This embodiment Polymerizable pace T-group Semiconductor devices can be manufactured using the material. For example, the material of this embodiment Polymerizable pace T-group By using the resulting product as an "adhesive" between a substrate and a semiconductor element, semiconductor devices can be manufactured.

[0090] In other words, the semiconductor device of this embodiment includes, for example, a substrate and the above-mentioned Polymerizable pace T-group The system comprises a semiconductor element mounted on a substrate via an adhesive layer obtained by sintering a molded product through heat treatment. The semiconductor device of this embodiment is less susceptible to deterioration of the adhesion of the adhesive layer even under heat cycling. In other words, the semiconductor device of this embodiment has high reliability.

[0091] Examples of semiconductor devices include ICs, LSIs, power semiconductor devices, and various other types of devices. Examples of substrates include various semiconductor wafers, lead frames, BGA substrates, mounted substrates, heat spreaders, and heat sinks. An example of a semiconductor device will be described below with reference to the drawings. Figure 1 is a cross-sectional view showing an example of a semiconductor device.

[0092] The semiconductor device 100 includes a substrate 30 and Polymerizable pace T-group The system comprises a semiconductor element 20 mounted on a substrate 30 via an adhesive layer 10 (die attach material), which is a heat-treated finished product.

[0093] The semiconductor element 20 and the substrate 30 are electrically connected, for example, via bonding wires 40. The semiconductor element 20 is also sealed, for example, with a sealing resin 50.

[0094] The thickness of the adhesive layer 10 is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 20 μm or more. Polymerizable pace T-group This improves the stress absorption capacity of the finished product and enhances its resistance to heat cycling. The thickness of the adhesive layer 10 is, for example, 100 μm or less, preferably 50 μm or less.

[0095] In Figure 1, the substrate 30 is, for example, a lead frame. In this case, the semiconductor element 20 is mounted on the die pad 32 or the substrate 30 via an adhesive layer 10. The semiconductor element 20 is also electrically connected to the outer lead 34 (substrate 30) via, for example, a bonding wire 40. The substrate 30, which is the lead frame, is made of, for example, a 42 alloy, a Cu frame, etc.

[0096] The substrate 30 may be an organic substrate or a ceramic substrate. Examples of organic substrates include those made of epoxy resin, cyanate resin, maleimide resin, etc. The surface of the substrate 30 may be coated with a metal such as silver or gold. This improves the adhesion between the adhesive layer 10 and the substrate 30. Figure 2 is a cross-sectional view showing an example of a semiconductor device 100 different from that in Figure 1.

[0097] In the semiconductor device 100 shown in Figure 2, the substrate 30 is, for example, an interposer. On the substrate 30, which is an interposer, a plurality of solder balls 52 are formed on the side opposite to the side on which the semiconductor element 20 is mounted. In this case, the semiconductor device 100 is connected to other wiring boards via the solder balls 52. An example of a semiconductor device manufacturing method will be described.

[0098] First, on the base material 30, Polymerizable pace T-group The material is coated, and then the semiconductor element 20 is placed on it. That is, the base material 30, Polymerizable pace T-group The finished product and semiconductor element 20 are stacked in this order. Polymerizable pace T-group The method of coating the finished product is not particularly limited. Specifically, examples include dispensing, printing, and inkjet methods.

[0099] Next, Polymerizable pace T-groupThe product is heat-cured. Heat curing is preferably carried out by pre-curing and post-curing. By heat curing, Polymerizable pace T-group The finished product is a heat-treated body (cured product). By heat curing (heat treatment), Polymerizable pace T-group Metal-containing particles in the material aggregate, and a structure is formed in the adhesive layer 10 in which the interfaces between multiple metal-containing particles disappear. As a result, the substrate 30 and the semiconductor element 20 are bonded together via the adhesive layer 10. Next, the semiconductor element 20 and the substrate 30 are electrically connected using bonding wires 40. Then, the semiconductor element 20 is sealed with sealing resin 50. In this way, a semiconductor device can be manufactured.

[0100] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., within the scope that can achieve the objectives of the present invention are included in the present invention. [Examples]

[0101] Embodiments of the present invention will be described in detail based on examples and comparative examples. The present invention is not limited to these examples. The components used in the examples are shown below.

[0102] (Compound represented by general formula (a) (polymerizable monomer)) • Monomer 1: A cyclic olefin compound represented by the following chemical formula (NBBu, manufactured by Promerus LLC). [ka]

[0103] • Monomer 2: A cyclic olefin compound represented by the following chemical formula (NBHex, manufactured by Promerus LLC). [ka]

[0104] • Monomer 3: A cyclic olefin compound represented by the following chemical formula (NBDec, manufactured by Promerus LLC). [ka]

[0105] • Monomer 4: A cyclic olefin compound represented by the following chemical formula (NBTON, manufactured by Promerus LLC). [ka]

[0106] • Monomer 5: A cyclic olefin compound represented by the following chemical formula (NBMeOH, manufactured by Promerus LLC). [ka]

[0107] • Monomer 6: A cyclic olefin compound represented by the following chemical formula (NBOAc, manufactured by Promerus LLC). [ka]

[0108] • Monomer 7: A cyclic olefin compound represented by the following chemical formula (NBEtOH, manufactured by Promerus LLC). [ka]

[0109] • Monomer 8: A cyclic olefin compound represented by the following chemical formula (NBEsEtOH, manufactured by Promerus LLC). [ka]

[0110] • Monomer 9: A cyclic olefin compound represented by the following chemical formula (NBDiMeOH, manufactured by Tokyo Chemical Industry Co., Ltd.) [ka]

[0111] • Monomer 10: A cyclic olefin compound represented by the following chemical formula (NBCOOH, manufactured by Tokyo Chemical Industry Co., Ltd.) [ka]

[0112] (thermosetting component) • Epoxy resin 1: Bisphenol F type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., RE303-L) • Acrylic monomer 1: Ethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester EG) (Hardening agent) • Hardener 1: Phenolic resin having a bisphenol F skeleton (solid at room temperature of 25°C, manufactured by DIC Corporation, DIC-BPF)

[0113] (Silver-containing particles) • Silver filler 1: DOWA Electronics Co., Ltd., AG-DSB-114, spherical, D 50 :0.7μm, specific surface area: 1.05m 2 / g, tap density 5.25g / cm³ 3 Circularity: 0.953 • Silver filler 2: Manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., HKD-12, flake-like, median diameter D 50 :7.6μm, specific surface area: 0.315m 2 / g, tap density: 5.5g / cm³ 3

[0114] (Polymerization catalyst) • Ring-opening metathesis polymerization catalyst 1: 1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, manufactured by Sigma-Aldrich.

[0115] (Polymerization initiator) • Radical polymerization initiator 1: Dicumyl peroxide (manufactured by Kayaku Akzo, Percadox BC)

[0116] (curing catalyst) Curing catalyst 1:2PZ-PW:2-phenylimidazole manufactured by Shikoku Chemicals Co., Ltd.

[0117] (solvent) Solvent 1: Tripropylene glycol mono-n-butyl ether (BFTG, manufactured by Nippon Emulsifier Co., Ltd., boiling point 274°C)

[0118] [Examples 1-17, Comparative Example 1] According to the proportions shown in Table 1, each raw material component was uniformly dispersed and kneaded using a three-roller system. After kneading, the mixture was degassed under reduced pressure at room temperature for 15 minutes. Polymerizable pace T-group It was completed.

[0119] (viscosity measurement) Polymerizable pace T-group Approximately 0.7 mL of the product was taken, and its viscosity at 25°C was measured using an E-type viscometer (Brookfield).

[0120] (Volume resistivity) Polymerizable pace T-group The material was applied to a glass plate and heated in a nitrogen atmosphere from 30°C to 200°C over 60 minutes, followed by heat treatment at 200°C for 120 minutes. This resulted in a thickness of 0.05 mm. Polymerizable pace T-group A heat-treated body was obtained. The resistance of the heat-treated body surface was measured using a DC four-electrode method with a milliohmmeter (HIOKI Corporation) and electrodes spaced 40 mm apart.

[0121] (Thermal conductivity) Polymerizable pace T-group The material was applied to a Teflon plate and heated in a nitrogen atmosphere from 30°C to 200°C over 60 minutes, followed by heat treatment at 200°C for 120 minutes. As a result, a 1 mm thick layer was produced. Polymerizable pace T-group A heat-treated finished product was obtained. Next, the thermal diffusion coefficient α in the thickness direction of the heat-treated body was measured using the xenon flash method with a xenon flash measuring instrument (TD-1 RTV, manufactured by ULVAC, Inc.). The measurement temperature was 25°C. Furthermore, the specific heat Cp was measured using differential scanning calorimetry (DSC). In addition, the density ρ was measured in accordance with JIS 6911. The thermal conductivity was calculated using the following formula. Thermal conductivity λ[W / (m*K)]=α[m 2 / sec]xCp[J / kg*K]xρ[g / cm 3 ]

[0122] (Storage modulus) Polymerizable pace T-group The heat-treated material was cut into strips approximately 0.1 mm × 10 mm × 4 mm in size to obtain evaluation strips. The storage modulus (E') at 25°C was measured using DMA (dynamic viscoelasticity measurement, tensile mode) under conditions of a heating rate of 5°C / min and a frequency of 10 Hz.

[0123] (Die share strength) obtained Polymerizable pace T-group The material was coated onto a Cu lead frame, and a 7mm square Si chip was mounted on top of it so that its thickness after heat treatment was approximately 50 μm. Under a nitrogen atmosphere, the temperature was increased from 30°C to 200°C over 60 minutes, followed by heat treatment at 200°C for 120 minutes. The resulting sample was stored in a constant temperature and humidity chamber at 60°C / 60%RH for 48 hours. After storage, the sample was placed on a hot plate at 260°C, and the die shear strength at 500 μm / sec was measured after 20 seconds.

[0124] The cross-sections of the samples obtained in Example 5 and Comparative Example 1 were polished using a CP polishing apparatus and observed using a scanning electron microscope. Figures 3 and 4 show scanning electron microscope images of Example 5 and Comparative Example 1. As shown in Figures 3(a) and 3(b), in Example 5, which uses the cyclic olefin compound according to the present invention, a sintered structure (connected structure) between the substrate (Cu lead frame) and the silver filler was confirmed. On the other hand, as shown in Figures 4(a) and 4(b), in Comparative Example 1, which uses a conventional material system such as epoxy resin, a sintered structure like that in Figure 3 was not confirmed. From this, it can be concluded that the die shear strength of the sample in Example 5 was improved by the sintering of the substrate and the silver filler.

[0125] (Cross-sectional SEM observation) Thickness of approximately 0.05 mm Polymerizable pace T-group The cross-sections of the heat-treated finished products were polished using a CP polishing device and observed using a scanning electron microscope. Figures 5-10 show scanning electron microscope images of Examples 5, 11, 12, 14, 17 and Comparative Example 1. As shown in Figures 5-10, Examples 5, 11, 12, 14, and 17 of the present invention Polymerizable pace T-group In the heat-treated finished product (high thermal conductivity material), a linkage structure of silver-containing particles formed by heat treatment was confirmed, but in Comparative Example 1, no such linkage structure was confirmed.

[0126] [Table 1]

[0127] As shown in Table 1, the examples Polymerizable pace T-group The resulting product demonstrated excellent conductivity and heat dissipation, as well as improved adhesion to semiconductor elements and substrates. In other words, it exhibited an excellent balance of these properties. [Explanation of symbols]

[0128] 100 Semiconductor Devices 10 Adhesive layer 20 Semiconductor elements 30 Base material 32 die pads 34 Outer lead 40 Bonding Wires 50 Sealing resin 52 Solder ball

Claims

1. (A) A compound represented by the following general formula (a), (B) Silver-containing particles and A polymerizable paste composition comprising, The polymerizable paste composition wherein the proportion of silver-containing particles (B) in the entire polymerizable paste composition is 50 to 98% by mass. 【Chemistry 1】 (In general formula (a), R １ , R ２ , R ３ and R ４ Each of these is an organic group having 1 to 12 carbon atoms, which may independently have a hydrogen atom or a substituted or unsubstituted heteroatom, and R １ , R ２ , R ３ and R ４ At least one of them is the aforementioned organic group, and n is 0, 1, or 2.

2. The polymerizable paste composition according to claim 1, wherein the organic group having 1 to 12 carbon atoms is an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an alkaryl group, a cycloalkyl group (having 3 to 10 carbon atoms), or an alkoxy group.

3. The polymerizable paste composition according to claim 1 or 2, wherein the organic group having 1 to 12 carbon atoms and a heteroatom comprises at least one selected from an ether bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, and a thiourethane bond.

4. The polymerizable paste composition according to any one of claims 1 to 3, wherein the substituent of the C1 to C12 organic group, which may have a substituted heteroatom, is at least one selected from a hydroxyl group, an amino group, a carboxyl group, and a mercapto group.

5. A polymerizable paste composition according to any one of claims 1 to 4, wherein the silver-containing particles (B) comprises two or more types selected from spherical, flaky, aggregated, and polyhedral silver-containing particles.

6. The silver-containing particles (B) consist of spherical silver-containing particles b1 and flaky silver-containing particles b2-1. The polymerizable paste composition according to any one of claims 1 to 5, wherein the content ratio (b1 / b2-1) of these silver-containing particles is 0.5 or more and 3 or less.

7. The polymerizable paste composition according to any one of claims 1 to 6, further comprising a norbornene-based silane coupling agent (C).

8. The polymerizable paste composition according to any one of claims 1 to 7, further comprising a polymerization catalyst (D).

9. A high thermal conductivity material obtained by sintering a polymerizable paste composition according to any one of claims 1 to 8, A highly thermally conductive material containing a linked structure of silver-containing particles (B) formed by heat treatment.

10. The high thermal conductivity material according to claim 9, comprising a resin having repeating structural units represented by the following general formula (a1). 【Chemistry 2】 (In the general formula (a1), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 12 carbon atoms which may have a substituted or unsubstituted heteroatom, and at least one of R １ , R ２ , R ３ and R ４ is the organic group, and n is 0, 1 or 2. * is a bond.)

11. Substrate and The system comprises a semiconductor element mounted on the substrate via an adhesive layer, The adhesive layer is obtained by sintering a polymerizable paste composition according to any one of claims 1 to 8, in a semiconductor device.

Images