Organic modified silicone composition, cured product thereof, die bond material, and optoelectronic device.

Abstract

The present invention provides an organically modified silicone composition that yields a cured product with excellent hardness and die shear strength. Furthermore, it provides a die-bonding material made from this composition, and an optoelectronic device obtained by die-bonding an optoelectronic semiconductor element with this die-bonding material. [Solution] (A) A reaction product of an organic compound having a cyclic unsaturated group and a siloxane having an acrylic oxy group and a SiH group, (B) an organic peroxide, (C) an organohydrogenpolysiloxane derivative represented by the following general formula (3), TIFF2026106849000045.tif54150 (D) an organically modified silicone composition characterized by containing a platinum group metal catalyst.

Description

Technical Field

[0001] The present invention relates to an organically modified silicone composition having a polycyclic hydrocarbon skeleton, a cured product thereof, a die bond material, and an optical semiconductor device.

Background Art

[0002] In the prior art, optical semiconductor elements such as light emitting diodes (LEDs) have excellent characteristics such as low power consumption, and are therefore applied to optical semiconductor devices for outdoor lighting applications and automotive applications. The optical semiconductor elements in the optical semiconductor devices are adhered and fixed to the housing using a die bond material.

[0003] Since the die bond material needs to hold the element in the wire bonding process after the die bond process, a high-strength material is generally used because strength is required. In addition, with the miniaturization of LED chips in recent years, the die bond material is required to exhibit high adhesiveness even in a small area.

[0004] In Patent Document 1, a die bond material exhibiting excellent die shear strength using an addition-curable organic hybrid silicone composition has been proposed. However, on the LED package, there may be components (sulfur compounds, nitrogen compounds, phosphorus compounds, etc.) that act as catalyst poisons for the addition-curing catalyst. In such a case, the curing reaction may be inhibited, and the hardness and adhesiveness may decrease.

[0005] On the other hand, peroxide curing using (meth)acrylic groups is also commonly used as a curing mechanism, but in peroxide curing, radicals are consumed by oxygen, inhibiting the surface curing reaction. In contrast, it has been proposed to use a heat-curable silicone composition that provides a cured product resistant to both reaction inhibition to hydrosilylation (addition) curing and oxygen inhibition to peroxide curing by combining peroxide thermal curing of (meth)acrylic groups with the addition reaction between SiH groups and unsaturated groups (Patent Document 2). However, compared to those exhibiting high die-shear strength, such die-bonding materials using a combination of peroxide curing and addition curing, exhibit insufficient adhesive strength at room temperature and high temperatures. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2020-136281 [Patent Document 2] Japanese Patent Publication No. 2018-076415 [Overview of the project] [Problems that the invention aims to solve]

[0007] This invention has been made in view of the above background, and aims to provide an organically modified silicone composition that gives a cured product with excellent hardness and die shear strength. Furthermore, it aims to provide a die bond material made from this composition, and an optoelectronic device obtained by die bonding an optoelectronic semiconductor element with this die bond material. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention provides: Organically modified silicone composition, (A) Addition product of an organic compound represented by the following general formula (1) and an organosilicon compound represented by the following general formula (2), X(-Z1 -R 1 ) n (1) (In the formula, X is an n-valent organic group containing a cyclic structure and not containing a silicon atom, and R 1 are, independently of each other, an allyl group or a norbornenylmethyl group, provided that one or more of R 1 are norbornenylmethyl groups, Z 1 is a single bond, -O- or -C(=O)O-, and n is a number from 2 to 4.)

Chemical formula

Chemical formula

[0009] The organically modified silicone composition of the present invention is excellent in curability, has high die shear strength, and is a cured product excellent in the adhesive strength between a light semiconductor element such as an LED element and a substrate, a die bond material, and can be applied to a light semiconductor element.

[0010] Furthermore, it is preferable that the organic compound represented by the general formula (1) is one or more of the organic compounds represented by the following general formulas (4), (5), and (6). [ka] (In the formula, R 1 R is an allyl group or a norborneylmethyl group, 2 These are, independently of each other, a hydrogen atom, an allyloxycarbonyl group, or a norbornenylmethyloxycarbonyl group. [ka] (In the formula, R 1 R is an allyl group or a norborneylmethyl group, 3 (This is a hydrogen atom, an allyl group, or a norbornenylmethyl group.) [ka] (In the formula, R 1 (This is either an allyl group or a norbornenylmethyl group.)

[0011] If the organic compound represented by the general formula (1) is the specific compound mentioned above, it is preferable because it can yield a cured product with particularly excellent die shear strength.

[0012] Furthermore, in the organosilicon compound represented by the general formula (2), the above R 4 and the above R 5 is a methyl group, and the above Z 2 It is preferable that the group is a trimethylene group and that m is 1.

[0013] If the organic compound represented by the general formula (2) is the specific compound mentioned above, it is particularly preferable because it exhibits excellent curability.

[0014] Furthermore, it is preferable that component (B) is one or more selected from peroxyesters and diacyl peroxides.

[0015] If component (B) is the specific compound mentioned above, it is particularly preferable because it exhibits excellent curability.

[0016] Furthermore, in the organohydrogenpolysiloxane derivative represented by the general formula (3), Z 3 However, it is preferable that it be a divalent hydrocarbon group represented by the following formula (7). [ka] (In the equation, lines with a wavy line represent connections.)

[0017] If component (C) is the specific compound described above, it is preferable because it improves compatibility with component (A), enhances transparency, and suppresses the separation of each component when the die bond material is applied to a substrate such as an LED substrate by a die bonder.

[0018] Furthermore, the organically modified silicone composition of the present invention preferably contains (E) a filler.

[0019] The inclusion of component (E) is preferable because it can provide a cured product with particularly excellent hardness and strength.

[0020] Furthermore, the present invention provides a die bond material comprising the organically modified silicone composition described above.

[0021] The die bond material of the present invention provides a cured product with excellent curability, high die shear strength, and superior adhesion between optical semiconductor elements such as LED elements and substrates, as well as an optical semiconductor device.

[0022] Furthermore, the present invention provides a cured product which is obtained by curing the organic modified silicone composition.

[0023] The cured product of the present invention has high strength and excellent adhesion between the optical semiconductor element and the substrate at high temperatures.

[0024] Furthermore, the present invention provides an optical semiconductor device comprising the cured material.

[0025] The optical semiconductor device of the present invention is highly reliable because it is equipped with a cured material that has high strength and excellent adhesive strength at high temperatures. [Effects of the Invention]

[0026] As described above, the organic modified silicone composition of the present invention is an organic modified silicone composition having a polycyclic hydrocarbon skeleton, and by using a combination of curing with peroxide of (meth)acrylic groups and an addition reaction between hydrosilyl (Si-H) groups and unsaturated groups, it has resistance to addition curing inhibition and oxygen inhibition, thus providing a cured product with excellent curability and excellent adhesion between optical semiconductor elements such as LED elements and substrates at high temperatures. Therefore, the cured product obtained from such an organic modified silicone resin composition is particularly useful as a die bonding material used for die bonding of small LED elements and the like, and an optical semiconductor device can be provided by die bonding an optical semiconductor element with the above cured product. [Modes for carrying out the invention]

[0027] As described above, there was a need for a die bond material that exhibits excellent curing properties and provides a cured product with superior adhesion between optical semiconductor elements such as LED elements and substrates at high temperatures.

[0028] As a result of diligent research into the above-mentioned problems, the inventors of the present invention have found that an organically modified silicone composition containing components (A) to (D) described later can solve the above-mentioned problems, and have completed the present invention.

[0029] In other words, the present invention is Organically modified silicone composition, (A) Addition product of an organic compound represented by the following general formula (1) and an organosilicon compound represented by the following general formula (2), X(-Z 1 -R 1 ) n (1) (In the formula, X is an n-valent organic group that contains a cyclic structure and does not contain a silicon atom, R 1 These are independently an allyl group or a norborneylmethyl group, however, R 1 One or more of these are norborneylmethyl groups, Z 1 (where n is a single bond, -O-, or -C(=O)O-, and n is a number between 2 and 4.) [ka] (In the formula, R 4 R is a hydrogen atom or a methyl group, 5 These are monovalent hydrocarbon groups having 1 to 12 carbon atoms that do not have aliphatic unsaturated bonds, and Z 2 (where m is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have an ether bond, and m is a number from 0 to 8) (B) organic peroxide, (C) Organohydrogenpolysiloxane derivatives represented by the following general formula (3), [ka] (In the formula, Z 3 (Each is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may contain silicon atoms, independently of each other; r is independently 0 or 1; and s is an integer from 0 to 5.) and (D) platinum group metal catalysts, This is an organically modified silicone composition characterized by containing [a specific ingredient].

[0030] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0031] <(A) component> Component (A) in the organic modified silicone composition of the present invention is an addition product of an organic compound represented by the following general formula (1) and an organosilicon compound represented by the following general formula (2). X(-Z 1 -R 1 ) n (1) (In the formula, X is an n-valent organic group that contains a cyclic structure and does not contain a silicon atom, R 1 These are independently an allyl group or a norborneylmethyl group, however, R 1 One or more of these are norborneylmethyl groups, Z 1 (where n is a single bond, -O-, or -C(=O)O-, and n is a number between 2 and 4.) [ka] (In the formula, R 4 R is a hydrogen atom or a methyl group, 5 These are monovalent hydrocarbon groups having 1 to 12 carbon atoms that do not have aliphatic unsaturated bonds, and Z 2 (where m is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have an ether bond, and m is a number from 0 to 8)

[0032] In the above general formula (1), the organic group containing a cyclic structure of X and not containing a silicon atom may have a heterocyclic structure containing nitrogen atoms, sulfur atoms, oxygen atoms, etc., and may also contain carbonyl bonds, amide bonds, urethane bonds, urea bonds, etc. Specific examples of such structures include benzene rings, isocyanuryl rings, and isopropylidenediphenol structures.

[0033] R 1 The norborneylmethyl group is generally known to have structural isomers as shown in the following formula, and in the present invention, either the cis configuration (exo type) or the trans configuration (endo type) may be used. [ka]

[0034] The above R 1 One or more of these are norborneylmethyl groups, R 1 It is preferable that more than 50% of the total number of norborneylmethyl groups are norborneylmethyl groups.

[0035] The organic compound represented by the general formula (1) is preferably one or more of the organic compounds represented by the following general formulas (4), (5), and (6). [ka] (In the formula, R 1 R is an allyl group or a norborneylmethyl group, 2 These are, independently of each other, a hydrogen atom, an allyloxycarbonyl group, or a norbornenylmethyloxycarbonyl group. [ka] (In the formula, R 1 R is an allyl group or a norborneylmethyl group, 3 (This is a hydrogen atom, an allyl group, or a norbornenylmethyl group.) [ka] (In the formula, R 1 (This is either an allyl group or a norbornenylmethyl group.)

[0036] The organic compound represented by the general formula (1) can be produced, for example, by a Diels-Alder addition reaction between an organic compound having two or more allyl groups in one molecule, represented by the general formula (8) below, and cyclopentadiene. X(-Z 1 -R 6 ) n (8) (In the formula, X is an n-valent organic group that contains a cyclic structure and does not contain a silicon atom, R 6 It is an allyl group, and Z 1 (where n is a single bond, -O-, or -C(=O)O-, and n is a number between 2 and 4.)

[0037] Specific examples of compounds represented by the above general formula (8) include diallyl phthalate, triallyl trimellitate, tetraallyl pyromellitate, diallyl isocyanurate, triallyl isocyanurate, and 2,2-bis[4-(2-propenyloxy)phenyl]propane (bisphenol A diallyl ether).

[0038] The above-mentioned cyclopentadiene can generally be easily obtained by thermally decomposing dicyclopentadiene, a dimer that is generally stable at room temperature, at around 160°C.

[0039] Furthermore, since cyclopentadiene obtained by thermal decomposition undergoes a relatively rapid auto-Diels-Alder addition reaction at room temperature to revert to the dimer dicyclopentadiene, it is necessary to store it at a low temperature until it is mixed with a vinyl group-containing siloxane compound for reaction to suppress the auto-Diels-Alder addition reaction. For this reason, when supplying cyclopentadiene, it is preferable to mix the compound represented by the above general formula (8) with dicyclopentadiene, heat the mixture, and react the cyclopentadiene produced in the reaction vessel by the thermal decomposition of dicyclopentadiene with the compound represented by the above general formula (8).

[0040] The reaction temperature is preferably 100 to 250°C, and more preferably 120 to 200°C, from the standpoint of suppressing the reverse reaction of the Diels-Alder addition reaction (the elimination of cyclopentadiene from the norbornel group) and promoting the thermal decomposition of dicyclopentadiene (the release of cyclopentadiene).

[0041] The reaction time is not particularly limited, but in either case of reacting the compound represented by the general formula (8) with cyclopentadiene or dicyclopentadiene, the reaction is preferably carried out for 0.5 to 50 hours, and more preferably for 1 to 24 hours.

[0042] In the above reaction, a solvent may be used, and various solvents such as aromatic hydrocarbons like toluene, xylene, mesitylene, and decalin, aliphatic hydrocarbons like decane, undecane, dodecane, and liquid paraffin, ethers, and alcohols can be used.

[0043] The above solvents may be used individually or as a mixture of two or more. It is preferable that the boiling point of the solvent be at least 20°C away from the boiling point of the target substance, as this facilitates separation during purification.

[0044] After the above reaction is complete, preferably 1 to 10 5 Under reduced pressure conditions of approximately Pa, unreacted raw materials (and possibly the reaction solvent) can be removed from the reaction mixture by general distillation, followed by the removal of the target norbornenyl group-containing compound. This allows for the obtaining of a purified, high-purity norbornenyl group-containing compound (however, as mentioned above, this will result in an isomer mixture). It should be noted that if the norbornenyl group-containing compound is exposed to excessively high temperatures, some of it may undergo the reverse reaction of the Diels-Alder addition reaction, decomposing into reaction raw materials (cyclopentadiene and allyl group-containing compounds). These compounds may then be mixed into the fraction of the target product, reducing its purity. Therefore, it is desirable to maintain the highest possible pressure during distillation and keep the system temperature during distillation as low as possible, around 0-250°C. Furthermore, measures can be taken to reduce the thermal history of the target product and mitigate the effects of heat during distillation by using special equipment such as thin-film distillation apparatus.

[0045] In the organosilicon compound represented by the above general formula (2), the above R 5Specific examples of monovalent hydrocarbon groups with 1 to 12 carbon atoms that do not have an aliphatic unsaturated bond include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, cyclopentyl, and cyclohexyl; aryl groups with 6 to 12 carbon atoms such as phenyl and naphthyl; alkylaryl groups with 7 to 12 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, and hexylphenyl; and aralkyl groups with 7 to 12 carbon atoms such as benzyl and phenethyl.

[0046] Among these, the above R 5 Preferably, the alkyl group has 1 to 8 carbon atoms, and a methyl group is more preferred.

[0047] The above Z 2 Examples of divalent hydrocarbon groups having 1 to 10 carbon atoms that may have an ether bond include linear, branched, or cyclic alkylene groups such as methylene, ethylene, propylene, trimethylene, pentamethylene, hexamethylene, cyclohexylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; arylene groups such as phenylene; aralkylene groups such as phenylenemethylene and methylenephenylenemethylene; and alkyleneoxyalkylene groups such as ethyleneoxyethylene, ethyleneoxypropylene, ethyleneoxybutylene, and propyleneoxypropylene.

[0048] Among these, the above Z 2 Preferably, an alkylene group having 1 to 8 carbon atoms is preferred, and a trimethylene group is more preferred.

[0049] The above value of m is a number between 0 and 8, preferably 0 or 1, and more preferably 1.

[0050] Specific examples of organosilicon compounds represented by the above general formula (2) include those represented by the following formula. [ka]

[0051] In the organosilicon compound represented by the general formula (2) above, R 4 and R 5 The group is a methyl group, Z 2 It is preferable that the group is a trimethylene group and m is 1.

[0052] The addition reaction product of component (A) above is R in the organic compound represented by the general formula (1) above. 1 It is produced by an addition reaction between an aliphatic unsaturated bond contained in the allyl group or norbornenylmethyl group and a hydrogen atom (Si-H) bonded to a silicon atom contained in the organosilicon compound represented by the general formula (2) above.

[0053] The above component (A) can be synthesized by known methods. For example, it can be synthesized by adding 1 mole of the above general formula (2) to 1 mole of the above general formula (1) in the presence of a hydrosilylation catalyst, preferably in an amount of more than 1 mole and 10 moles or less, and more preferably more than 1 mole and 5 moles or less of the above general formula (2).

[0054] In this case, known catalysts can be used for the hydrosilylation reaction. Specific examples include platinum-based catalysts such as platinum-supported carbon powder, platinum black, platinum-dic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetate; as well as platinum group metal catalysts such as palladium-based catalysts and rhodium-based catalysts. Furthermore, the addition reaction conditions and the use of solvents are not particularly limited and may be as known.

[0055] Among the terminal structures of component (A) above, the R in the organic compound represented by the general formula (1) above 1The addition reaction rate of the organosilicon compound represented by the above general formula (2) relative to the total number of is preferably 50% or more, and particularly preferably 100%.

[0056] Specific examples of the above component (A) include those represented by the following formula.

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] The above component (A) may be used alone or in combination of two or more types.

[0062] <(B) component> Component (B) in the organically modified silicone composition of the present invention is an organic peroxide, which is added to cure the organically modified silicone composition of the present invention by a crosslinking reaction after heat treatment, and is appropriately selected depending on the desired connection temperature, connection time, pot life, etc.

[0063] The organic peroxide of component (B) described above preferably has a 10-hour half-life temperature of 40°C or higher and a 1-minute half-life temperature of 200°C or lower, and more preferably has a 10-hour half-life temperature of 60°C or higher and a 1-minute half-life temperature of 180°C or lower, from the viewpoint of achieving both high reactivity and a long pot life.

[0064] The organic peroxide of component (B) above is preferably one or more selected from peroxyesters and diacyl peroxides.

[0065] Examples of the above-mentioned diacyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxytoluene, and benzoyl peroxide. These can be used individually or in combination of two or more.

[0066] Examples of the above peroxyesters include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanonate, and t-butyl peroxy-2 Examples include ethylhexanoate, t-butyl peroxyisobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-toluylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, t-butylperoxyacetate, and bis(t-butylperoxy)hexahydroterephthalate. These can be used individually or in combination of two or more.

[0067] Other organic peroxides include dialkyl peroxides, peroxydicarbonates, peroxyketals, hydroperoxides, and silyl peroxides. These organic peroxides can also be used in combination with organic peroxides containing one or more selected from the above-mentioned diacyl peroxides and peroxyesters.

[0068] Examples of the above-mentioned dialkyl peroxides include α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and t-butylcumyl peroxide.

[0069] Examples of the above-mentioned peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, bis(2-ethylhexylperoxy)dicarbonate, dimethoxybutyl peroxydicarbonate, and bis(3-methyl-3-methoxybutylperoxy)dicarbonate.

[0070] Examples of the above-mentioned peroxyketals include 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-(t-butylperoxy)cyclododecane, and 2,2-bis(t-butylperoxy)decane.

[0071] Examples of the above-mentioned hydroperoxides include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

[0072] Examples of the silyl peroxides mentioned above include t-butyltrimethylsilyl peroxide, bis(t-butyl)dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis(t-butyl)divinylsilyl peroxide, tris(t-butyl)vinylsilyl peroxide, t-butyltrialylsilyl peroxide, bis(t-butyl)diallylsilyl peroxide, and tris(t-butyl)allylsilyl peroxide.

[0073] The above component (B) may be used individually or in combination of two or more types.

[0074] The amount of component (B) added may be any amount effective for curing the organic modified silicone composition of the present invention, but preferably it is 0.1 to 30 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (A). Within this range of amounts, the curing reaction by heating can be more effectively promoted.

[0075] <(C) component> In the organically modified silicone composition of the present invention, component (C) is an organohydrogenpolysiloxane derivative represented by the following general formula (3), having a hydrogen atom bonded to a silicon atom (i.e., a Si-H group), and acts as a crosslinking agent that reacts with the addition-reactive aliphatic unsaturated bond contained in component (A) through a hydrosilylation reaction.

[0076] [ka] (In the formula, Z 3 (Each is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may contain silicon atoms, independently of each other; r is independently 0 or 1; and s is an integer from 0 to 5.)

[0077] The above Z 3Examples of divalent hydrocarbon groups that may contain silicon atoms include linear, branched, or cyclic alkylene groups such as methylene, ethylene, propylene, trimethylene, pentamethylene, hexamethylene, cyclohexylene, heptamethylene, octamethylene, nonamethylene, and decamethylene groups; arylene groups such as phenylene groups; aralkylene groups such as phenylenemethylene and methylenephenylenemethylene groups; divalent hydrocarbon groups represented by the following formula (7); and divalent groups represented by the following formula (9).

[0078] [ka] (In the equation, lines with a wavy line represent connections.)

[0079] [ka] (In the formula, R 7 Each of these is independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, preferably a methyl group or a phenyl group. (The wavy lines indicate bonding.)

[0080] The above Z 3 In particular, a divalent hydrocarbon group represented by the above formula (7) is preferred. In this case, compatibility with component (A) is increased, transparency is improved, and separation of each component can be suppressed when the die bond material is applied to the LED substrate by a die bonder.

[0081] The above s is an integer between 0 and 5, preferably 0 or 1, and more preferably 0.

[0082] Specific examples of the above-mentioned component (C) include, for example, organohydrogenpolysiloxane derivatives represented by the following structural formula. [ka]

[0083] Such organosilicon compounds can be obtained, for example, by a hydrosilylation reaction of 2,4,6,8-tetramethyltetracyclosiloxane with vinylnorbornene or diphenyldivinylsilane.

[0084] The above component (C) may be used alone or in combination of two or more types.

[0085] The amount of component (C) blended is preferably such that the number of hydrogen atoms bonded to silicon atoms in component (C) is 0.1 to 3.0 times the total number of aliphatic unsaturated bonds in component (A), and more preferably 0.2 to 2.0 times. Within this range, crosslinking proceeds sufficiently, and a cured product with excellent surface hardness and hardness can be obtained.

[0086] <(D) component> The platinum group metal catalyst of component (D) in the organic modified silicone composition of the present invention is not particularly limited as long as it is a component that promotes the addition reaction between the aliphatic unsaturated bond in component (A) and the hydrogen atom bonded to the silicon atom in component (C). Specific examples include platinum group metals such as platinum, palladium, and rhodium; platinum-based compounds such as chloroplatinic acid, alcohol-modified chloroplatinic acid, and coordination compounds of chloroplatinic acid with olefins, vinylsiloxanes, or acetylene compounds; and platinum group metal compounds such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium. However, platinum-based compounds are preferred, and coordination compounds of chloroplatinic acid and vinylsiloxanes are particularly preferred.

[0087] The above component (D) may be used alone or in combination of two or more types.

[0088] The amount of component (D) described above should be an effective amount as a catalyst, but it is preferably in the range of 1 to 500 ppm, and more preferably in the range of 1 to 100 ppm, when calculated by mass of platinum group metal elements relative to the total amount of components (A) and (C). When this range is satisfied, the reaction rate of the addition reaction becomes appropriate, and a cured product with high strength can be obtained.

[0089] <(E) component> The organically modified silicone composition of the present invention may include a filler as component (E). Specifically, inorganic fillers such as fumed silica, crystalline silica, hollow fillers, silsesquioxane, and nanoalumina, and fillers obtained by surface hydrophobizing these fillers with organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low molecular weight siloxane compounds; silicone rubber powder, silicone resin powder, etc. can be used.

[0090] It is preferable to use a filler that can impart thixotropy to the above-mentioned filler, as imparting thixotropy allows for the production of a cured product with excellent workability and die shear strength. Particularly preferable is a filler with a BET specific surface area of ​​100 to 300 m². 2 This is fumed silica in units of / g. The BET specific surface area is measured using Macsorb® HM Model-1201, manufactured by Mountec Co., Ltd., in accordance with JIS Z 8830:2013.

[0091] Alternatively, silica whose surface has been hydrophobized by reacting the silanol groups present on the surface with a surface modifier may be used. Examples of surface modifiers include alkylsilane compounds, with specific examples including dimethyldichlorosilane, hexamethyldisilazane, octylsilane, and dimethylsilicone oil.

[0092] Specific examples of the above-mentioned fumed silica include, for example, "Aerosil" (registered trademark) manufactured by Nippon Aerosil Co., Ltd. Examples of hydrophilic Aerosil (registered trademark) include "90", "130", "150", "200", and "300", while examples of hydrophobic Aerosil (registered trademark) include "R8200", "R972", "R972V", "R972CF", "R974", "R202", "R805", "R812", "R812S", "RY200", "RY200S", and "RX200". In addition, examples of "Rheoroseal" manufactured by Tokuyama Corporation include "DM-10", "DM-20", and "DM-30S".

[0093] The above component (E) may be used alone or in combination of two or more types.

[0094] The amount of component (E) is preferably 1 to 50 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of component (A). Within this range, it is possible to prevent transfer failure due to insufficient thixotropy and deterioration of workability due to increased viscosity when using the organically modified silicone composition of the present invention as a die bond material.

[0095] <(F) component> The organically modified silicone composition of the present invention may contain a reaction control agent as component (F) to adjust the curability. Examples of reaction control agents include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene compounds; hydroperoxy compounds; maleic acid derivatives; and known compounds that have a curing inhibitory effect on the platinum group metal catalyst of component (D) above, such as 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyne-3-ol, ethinylmethyldecylcarbinol, and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

[0096] The degree of curing inhibition by the above-mentioned reaction control agent varies depending on the chemical structure of the reaction control agent; therefore, when using a reaction control agent, it is desirable to adjust the amount to the optimal level for each reaction control agent. Preferably, the amount is 0.001 to 10 parts by mass per 100 parts by mass of component (A). If the amount is 0.001 parts by mass or more, sufficient long-term storage stability of the composition at room temperature can be obtained. If the amount is 10 parts by mass or less, the curing of the composition will not be inhibited.

[0097] <(G) component> The organic modified silicone resin composition of the present invention may contain an adhesion enhancer as component (G) to improve adhesive strength. As the adhesion enhancer for component (G), organosilicon compounds such as silanes and siloxanes containing functional groups that impart adhesion, non-silicone organic compounds, etc., can be used.

[0098] Specific examples of functional groups that impart adhesiveness include polymerizable groups having carbon-carbon unsaturated bonds bonded to silicon atoms (e.g., vinyl group, allyl group, γ-acryloxypropyl group, γ-methacryloxypropyl group, etc.), epoxy groups bonded to silicon atoms via carbon atoms (e.g., γ-glycidoxypropyl group, β-(3,4-epoxycyclohexyl)ethyl group, etc.), and alkoxysilyl groups (e.g., trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, etc.).

[0099] Examples of organosilicon compounds containing functional groups that impart adhesive properties include silane coupling agents, siloxanes having alkoxysilyl groups and organic functional groups, and compounds in which alkoxysilyl groups are introduced into organic compounds having reactive organic groups.

[0100] Examples of the non-silicone organic compounds mentioned above include organic acid allyl esters, organotitanium compounds, organozirconium compounds, and organoaluminum compounds.

[0101] When using the above-mentioned adhesion improver, it is preferable to add 1 to 20 parts by mass, particularly 3 to 10 parts by mass, per 100 parts by mass of component (A). These can be used individually or in combination of two or more.

[0102] Furthermore, to improve workability in die bonding (transfer method), the viscosity of the organically modified silicone composition of the present invention is preferably 5 to 100 Pa·s, and more preferably 20 to 50 Pa·s, at 25°C. The viscosity was measured using a B-type rotational viscometer at 25°C.

[0103] [Cured product] Furthermore, the present invention provides a cured product which is obtained by curing the organically modified silicone composition of the present invention.

[0104] The organically modified silicone composition of the present invention can be cured under known conditions, for example, at 100 to 160°C for 10 minutes to 5 hours.

[0105] Preferably, the Shore D hardness of the cured product obtained by curing the organically modified silicone composition of the present invention is 60 or higher.

[0106] [Diebond material] Furthermore, the present invention provides a die bond material comprising the organically modified silicone composition of the present invention.

[0107] [Optical Semiconductor Equipment] Furthermore, the present invention provides an optoelectronic device in which an optoelectronic semiconductor element is die-bonded with a cured product of the organically modified silicone composition of the present invention.

[0108] One example of a method for die-bonding an optical semiconductor device using the cured product of the organically modified silicone composition of the present invention is to fill a syringe with the organically modified silicone composition of the present invention, apply it to a substrate such as a package to a thickness of 5 to 100 μm in a dry state using a dispenser, place an optical semiconductor device (e.g., a light-emitting diode) on the applied organically modified silicone composition, and then cure the organically modified silicone composition to die-bond the optical semiconductor device to the substrate. Alternatively, the organically modified silicone composition of the present invention may be placed on a squeegee dish, applied to a substrate to a thickness of 5 to 100 μm in a dry state by stamping while squeezing, place an optical semiconductor device on the applied organically modified silicone composition, and then cure the organically modified silicone composition to die-bond the optical semiconductor device to the substrate. The curing conditions for the organically modified silicone composition may be as described above. In this way, a highly reliable optical semiconductor device can be die-bonded with the cured product of the organically modified silicone resin composition of the present invention. [Examples]

[0109] The present invention will be specifically described below using synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited to these. The viscosity was measured at 25°C using a B-type rotational viscometer.

[0110] [Synthesis Example 1] 103.6 g (0.25 mol) of tetraallyl pyromellitic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., TRIAM-805) and 119.0 g (0.90 mol) of dicyclopentadiene were placed in a 500 mL four-necked flask equipped with a stirrer, condenser, and thermometer, and the mixture was reacted at 160 °C for 24 hours. After the reaction, the mixture was concentrated under reduced pressure at 130 °C and 1 kPa for 2 hours to obtain organic compound (1).

[0111] 1From the integral ratio of the peak derived from the allyl group of pyromellitic tetraallyl and the peak derived from the unsaturated bond of the norborneylmethyl group in the 1H-NMR spectrum, the obtained organic compound (1) is represented by the following formula: 1 The molar ratio was allyl group:norborneylmethyl group = 23:77. [ka]

[0112] 25 g of the obtained organic compound (1) and 25 g of toluene were placed in a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, which were prepared separately. While stirring at 70°C, 0.03 g of a toluene solution of the reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane (platinum concentration 0.5 mass%) was added, and 29.80 g of an organosilicon compound represented by CH2=C(CH3)COOC3H6(CH3)2SiO(CH3)2SiH was added dropwise. The reaction was then carried out by stirring at 95°C for 10 hours. After the reaction, the mixture was cooled to 25°C, filtered with activated carbon, and then concentrated under reduced pressure at 110°C and 1 kPa for 2 hours to obtain the addition reaction product (A-1).

[0113] The above addition reaction product (A-1) has a viscosity of 3000 mPa·s. 1 From the 1H-NMR spectrum and GPC (gel column chromatography), the molar ratio of R in the following equation was expressed as a:b = 23:77. [ka] (In the equation, lines with a wavy line represent connections.)

[0114] [Synthesis Example 2] 93.48 g (0.375 mol) of triallyl isocyanurate (manufactured by Shinryo Co., Ltd., TAIC) and 89.24 g (0.675 mol) of dicyclopentadiene were placed in a 500 mL four-necked flask equipped with a stirrer, condenser, and thermometer, and the mixture was reacted at 160 °C for 24 hours. After the reaction, the mixture was concentrated under reduced pressure at 130 °C and 1 kPa for 2 hours to obtain organic compound (2).

[0115] 1 From the integral ratio of the peaks derived from the allyl group of triallyl isocyanurate and the unsaturated bond of the norbornel group in the 1H-NMR spectrum, the obtained organic compound (2) is represented by the following formula: 1 The molar ratio was allyl group:norborneylmethyl group = 50:50. [ka]

[0116] 25 g of the obtained organic compound (2) and 25 g of toluene were placed in a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, which were prepared separately. While stirring at 70°C, 0.03 g of a toluene solution of the reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane (platinum concentration 0.5 mass%) was added, and 40.90 g of an organosilicon compound represented by CH2=C(CH3)COOC3H6(CH3)2SiO(CH3)2SiH was added dropwise. The reaction was then carried out by stirring at 95°C for 10 hours. After the reaction, the mixture was cooled to 25°C, filtered with activated carbon, and then concentrated under reduced pressure at 110°C and 1 kPa for 2 hours to obtain the addition reaction product (A-2).

[0117] The above addition reaction product (A-2) has a viscosity of 1830 mPa·s. 1 From the 1H-NMR spectrum and GPC, the molar ratio of R in the following equation was expressed as a:b = 50:50. [ka] (In the equation, lines with a wavy line represent connections.)

[0118] [Comparative Synthesis Example 1] In a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, 93.48 g (0.20 mol) of triallyl isocyanurate and 95 g of toluene were placed. While stirring at 70°C, 0.12 g of a toluene solution (platinum concentration 0.5 mass%) of the reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane was added. Then, 40.90 g (0.54 mol) of an organosilicon compound represented by CH2=C(CH3)COOC3H6(CH3)2SiO(CH3)2SiH was added dropwise, and the reaction was carried out by stirring at 95°C for 10 hours. After the reaction, the mixture was cooled to 25°C, filtered with activated carbon, and then concentrated under reduced pressure at 110°C and 1 kPa for 2 hours to obtain the addition reaction product (A-3).

[0119] The above addition reaction product (A-3) has a viscosity of 190 mPa·s. 1 The 1H-NMR spectrum revealed that it was represented by the following formula. [ka]

[0120] [Comparative Synthesis Example 2] In a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, 25.80 g (0.1 mol) of 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane and 25 g of toluene were placed. While stirring at 70°C, 0.03 g of a toluene solution (platinum concentration 0.5 mass%) of the reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane was added. Then, 70.33 g (0.27 mol) of an organosilicon compound represented by CH2=C(CH3)COOC3H6(CH3)2SiO(CH3)2SiH was added dropwise, and the reaction was carried out by stirring at 95°C for 10 hours. After the reaction, the mixture was cooled to 25°C, filtered with activated carbon, and then concentrated under reduced pressure at 110°C and 1 kPa for 2 hours to obtain the addition reaction product (A-4).

[0121] The above addition reaction product (A-4) has a viscosity of 160 mPa·s. 1 The 1H-NMR spectrum revealed that it was represented by the following formula. [ka]

[0122] [Examples 1-4, Comparative Examples 1-4] An organically modified silicone composition was prepared by mixing the following components in the amounts shown in Table 1 below.

[0123] Note that the values ​​for each component in Table 1 below represent parts by mass. The [Si-H] / [Si-Vi] value represents the ratio (molar ratio) of the number of hydrogen atoms (Si-H groups) bonded to silicon atoms in component (C) to the total number of aliphatic unsaturated bonds in components (A) and (B).

[0124] (A) Ingredients: (A-1) Addition reaction product obtained in Synthesis Example 1 (A-2) Addition reaction product obtained in synthesis example 2 (A-3) Addition reaction product obtained in comparative synthesis example 1 (A-4) Addition reaction product obtained in comparative synthesis example 2

[0125] (B) Ingredients: 1,6-bis(tert-butylperoxycarbonyloxy)hexane (Trade name: Kayaren 6-70, manufactured by Kayaku Akzo Co., Ltd.)

[0126] (C) Component: Organohydrogenpolysiloxane derivative represented by the following structural formula [ka]

[0127] (D) Component: Toluene solution of the reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane (platinum concentration 0.5% by mass)

[0128] (E) Ingredients: Humed silica (manufactured by Tokuyama Corporation, Leosilol DM-30S)

[0129] Other ingredients: (F-1) Reaction control agent: 3-methyl-1-dodecine-3-ol (F-2) Reaction control agent: Triallyl isocyanurate (G) Adhesion improver: Compound represented by the following formula [ka]

[0130] [Table 1]

[0131] The physical properties of the cured products made from the organically modified silicone compositions obtained in Examples 1-4 and Comparative Examples 1-4 were measured according to the following measurement method. The results are shown in Table 2.

[0132] [Shore D hardness] The composition was poured into a mold to a thickness of 2 mm, and the Type D hardness of the cured product, which was cured at 150°C for 4 hours, was measured in accordance with JIS K 6253-3:2023.

[0133] [Die share strength] Using a die bonder (ASM, AD-830), each composition was stamped onto the silver-plated electrode portion of an SMD3020 package (I-CHIUN PRECISION INDUSTRY Co., polyphthalamide resin). A photoelectronic element (0.23 × 0.18 mm) was then mounted on top and heated at 150°C for 4 hours. After curing, die shear strength was measured at 25°C and 150°C using a bond tester (Dage, Series 4000).

[0134] [Table 2]

[0135] As shown in Table 2 above, Examples 1 to 4 exhibited excellent die shear strength at 25°C and 150°C, and showed no surface tack due to oxygen inhibition during peroxide curing, making them excellent die bond materials. Furthermore, they exhibited excellent die shear strength even when the [Si-H] / [Si-Vi] value was relatively low at 0.3, which is thought to be due to the presence of the norbornane skeleton of component (A) causing intermolecular interactions during curing and resulting in a higher crosslinking density.

[0136] On the other hand, in Comparative Examples 1-4, where component (A) was changed to one without a norbornane skeleton, the die shear strength was inferior even when the [Si-H] / [Si-Vi] value was high.

[0137] As described above, the organically modified silicone composition of the present invention provides a silicone cured product with excellent hardness and die shear strength, and is particularly useful as a die bonding material used for die bonding of optical semiconductor devices and the like. In particular, since problems such as chip peeling or inability to bond are less likely to occur in the wire bonding process performed after the die bonding process, the productivity of optical semiconductor devices in which optical semiconductor devices are die-bonded with a cured product of the organically modified silicone composition of the present invention is also improved. For this reason, the organically modified silicone composition of the present invention and its cured product have high utility value in the field of optical semiconductor devices.

[0138] This specification includes the following embodiments. [1]: Organic modified silicone composition, (A) Addition product of an organic compound represented by the following general formula (1) and an organosilicon compound represented by the following general formula (2), X(-Z 1 -R 1 ) n (1) (In the formula, X is an n-valent organic group that contains a cyclic structure and does not contain a silicon atom, R 1 These are independently an allyl group or a norborneylmethyl group, however, R 1 One or more of these are norborneylmethyl groups, Z 1(where n is a single bond, -O-, or -C(=O)O-, and n is a number between 2 and 4.) [ka] (In the formula, R 4 R is a hydrogen atom or a methyl group, 5 These are monovalent hydrocarbon groups having 1 to 12 carbon atoms that do not have aliphatic unsaturated bonds, and Z 2 (where m is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may have an ether bond, and m is a number from 0 to 8) (B) organic peroxide, (C) Organohydrogenpolysiloxane derivatives represented by the following general formula (3), [ka] (In the formula, Z 3 (Each is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may contain silicon atoms, independently of each other; r is independently 0 or 1; and s is an integer from 0 to 5.) and (D) platinum group metal catalysts, An organically modified silicone composition characterized by containing the following: [2]: The organic modified silicone composition according to [1], characterized in that the organic compound represented by general formula (1) is one or more of the organic compounds represented by the following general formulas (4), (5), and (6). [ka] (In the formula, R 1 R is an allyl group or a norborneylmethyl group, 2 These are, independently of each other, a hydrogen atom, an allyloxycarbonyl group, or a norbornenylmethyloxycarbonyl group. [ka] (In the formula, R 1 R is an allyl group or a norborneylmethyl group, 3 (This is a hydrogen atom, an allyl group, or a norbornenylmethyl group.) [Chemical formula] (wherein, R 1 is an allyl group or a norbornenylmethyl group.) [3]: In the organosilicon compound represented by the general formula (2), R 4 and R 5 are methyl groups, Z 2 is a trimethylene group, and m is 1, and the organomodified silicone composition according to [1] or [2]. [4]: The organomodified silicone composition according to any one of [1] to [3], wherein the component (B) is one or more selected from peroxy esters and diacyl peroxides. [5]: In the organohydrogenpolysiloxane derivative represented by the general formula (3), Z 3 is a divalent hydrocarbon group represented by the following formula (7), and the organomodified silicone composition according to any one of [1] to [4]. [Chemical formula] (wherein, the wavy line represents a bond.) [6]: The organomodified silicone composition according to any one of [1] to [5], which contains (E) a filler. [7]: A die bond material comprising the organomodified silicone composition according to any one of [1] to [6]. [8]: A cured product of the organomodified silicone composition according to any one of [1] to [6]. [9]: An optical semiconductor device comprising the cured product according to [8].

[0139] Note that the present invention is not limited to the above embodiments. The above embodiments are illustrative, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Claims

1. Organically modified silicone composition, (A) Addition product of an organic compound represented by the following general formula (1) and an organosilicon compound represented by the following general formula (2), X(-Z １ -R １ ) ｎ (1) (In the formula, X is an n-valent organic group that contains a cyclic structure and does not contain a silicon atom, R １ These are independently an allyl group or a norborneylmethyl group, however, R １ One or more of these are norborneylmethyl groups, Z １ (The bond is a single bond, -O-, or -C(=O)O-, and n is a number between 2 and 4.) 【Chemistry 1】 (wherein, R ４ is a hydrogen atom or a methyl group, and R ５ are each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms and no aliphatic unsaturated bond, and Z ２ is a divalent hydrocarbon group having 1 to 10 carbon atoms which may have an ether bond, and m is a number from 0 to 8) (B) organic peroxide, (C) Organohydrogenpolysiloxane derivatives represented by the following general formula (3), 【Chemistry 2】 (In the formula, Z ３ (Each is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may contain silicon atoms, independently of each other; r is independently 0 or 1; and s is an integer from 0 to 5.) and (D) platinum group metal catalysts, An organically modified silicone composition characterized by containing the following:

2. The organic modified silicone composition according to claim 1, characterized in that the organic compound represented by the general formula (1) is one or more of the organic compounds represented by the following general formulas (4), (5), and (6). 【Transformation 3】 (In the formula, R １ R is an allyl group or a norborneylmethyl group, ２ These are, independently of each other, a hydrogen atom, an allyloxycarbonyl group, or a norbornenylmethyloxycarbonyl group. 【Chemistry 4】 (In the formula, R １ R is an allyl group or a norborneylmethyl group, ３ (This is a hydrogen atom, an allyl group, or a norbornenylmethyl group.) 【Transformation 5】 (In the formula, R １ (This is either an allyl group or a norbornenylmethyl group.)

3. In the organosilicon compound represented by the general formula (2) above, R ４ and R ５ The group is a methyl group, Z ２ The organically modified silicone composition according to claim 1, characterized in that is a trimethylene group and m is 1.

4. The organically modified silicone composition according to claim 1, characterized in that the (B) component is one or more selected from peroxyesters and diacyl peroxides.

5. In the organohydrogenpolysiloxane derivative represented by the general formula (3), Z ３ The organically modified silicone composition according to claim 1, characterized in that it is a divalent hydrocarbon group represented by the following formula (7). 【Transformation 6】 (In the equation, lines with a wavy line represent connections.)

6. (E) The organic modified silicone composition according to claim 1, characterized in that it contains a filler.

7. A die bond material characterized by comprising an organically modified silicone composition according to any one of claims 1 to 6.

8. A cured product of an organically modified silicone composition according to any one of claims 1 to 6.

9. An optoelectronic device characterized by comprising the cured product described in claim 8.

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