Composite resin composition of organopolysiloxane having imide function

Abstract

Composite materials are shown and described herein. A composite material includes the reaction product of a resin and an imide-functionalized organopolysiloxane. The imide functionalized organopolysiloxane is a siloxane modified with an imide and an epoxy functional group. The composites may exhibit a number of useful properties, including good spiral flow, coefficient of thermal expansion, hygroscopicity, and / or one or more of others.

Description

Technical Field

[0001] This invention relates to composite compositions comprising resins and imide-functionalized organopolysiloxanes. In particular, this invention relates to the application of resin compositions modified with imide-functionalized organopolysiloxanes, wherein the imide-functionalized organopolysiloxanes are modified with imide and / or epoxy functional groups. Background Technology

[0002] Resin compositions are used in a variety of industries and applications. They can be used, for example, in electronic packaging materials. As an encapsulating method for semiconductor components such as ICs and LSIs, transfer molding of resin compositions is cost-effective and suitable for mass production, and has therefore been widely adopted. In terms of reliability, properties have also been improved by modifying epoxy or phenolic resins used as curing agents. However, due to the market trends of miniaturization, lightweighting, and high performance in electronic devices in recent years, the further integration of semiconductors, and the promotion of surface mount technology for semiconductor devices, the demand for resin compositions for semiconductor encapsulation with narrow path filling capabilities is increasing.

[0003] Epoxy resin compositions are widely used in the electronics industry as electronic encapsulation materials, particularly as encapsulants for semiconductor components and electronic circuits. Due to the wide range of temperature variations encountered in typical use of electronic devices, compositions used as electronic encapsulation materials must possess high reliability, including excellent thermal cycling resistance. Therefore, epoxy resin-based compositions, especially cresol-phenolic varnish (novolac) type epoxy compositions, have been widely used to form molding compositions for use as electronic encapsulation materials.

[0004] The assembly of electronic components typically involves exposing the components to high temperatures to achieve solder reflow, establish electrical interconnects between the chip and substrate, and properly cure any polymeric materials used as underfill materials between the chip and substrate or as adhesives to bond the chip to the substrate. During such processing, any moisture present in the encapsulant molding composition can lead to vapor buildup from this high-temperature exposure. Excessive vapor buildup during this process is believed to cause delamination of the encapsulant electronic packaging material. Therefore, it is important to provide epoxy molding compositions with low hygroscopicity to prevent the molding composition from absorbing moisture, thereby preventing vapor buildup and delamination during processing. Summary of the Invention

[0005] The following is an overview of this disclosure to provide a basic understanding of some aspects. This summary is not intended to identify key or essential elements, nor is it intended to limit the embodiments or any limitations of the claims. Furthermore, this summary provides a simplified overview of some aspects that can be described in more detail in other parts of this disclosure.

[0006] A composite composition comprising a resin and an imide-functionalized organopolysiloxane is provided. The imide-functionalized organopolysiloxane comprises an imide functional group and an epoxy functional group. In embodiments, the imide and / or epoxy functional groups may be side-attached to the siloxane chain. In other embodiments, the imide-functionalized organopolysiloxane may include an imide group bridging the siloxane unit.

[0007] In one aspect, a composition is provided comprising:

[0008] An imide-functionalized organopolysiloxane comprising an imide functional group and at least one functional group selected from epoxy, hydride, aromatic, aliphatic, amine, and / or acryloyl or acryloyloxy groups, wherein the organopolysiloxane is selected from linear siloxanes and nonlinear siloxanes, wherein the nonlinear siloxane comprises at least two of the functional groups selected from epoxy, hydride, aromatic, aliphatic, amine, and / or acryloyl or acryloyloxy groups;

[0009] Polymer resins that react with the imide-functionalized organopolysiloxanes;

[0010] catalyst;

[0011] packing; and

[0012] Optional adhesion promoters, release agents, and plasticizers,

[0013] The composition described therein provides a coefficient of thermal expansion (CTE) value of less than 12 ppm.

[0014] In one embodiment, the imide-functionalized organopolysiloxane is according to formula (I).

[0015]

[0016] (I)

[0017] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 and R 14Each group is independently selected from hydrogen, C1-C15 alkyl, epoxy, C6-C30 aromatic groups, and imide groups, provided that (i) R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 and R 14 At least one of them is selected from an imide group, and (ii) R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 and R 14 At least one of them is selected from epoxy groups;

[0018] A1, A2, A3, and L1, L2, L3, L4, L5, L6, L7, L8, L9, L 10 L 11 and L 12 Each of these is a linking group independently selected from divalent alkyl, divalent alkenyl, and divalent ether groups;

[0019] o≥1;

[0020] w, x, y and z are each ≥ 0, where (w+x+y+z) ranges from 1 to 60;

[0021] k1, k2, k3, k4, k5, k6, k7, k8, k9, k10

[0022] In one implementation, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 At least one of them is selected from imide, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12At least one of them is selected from epoxy groups, and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 At least one of them is selected from C6-C30 aromatic groups.

[0023] In one implementation, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 Independently selected from hydrogen, C1-C15 alkyl groups and C6-C30 aromatic groups, R 13 Selected from imide functional groups, and R 14 Selected from epoxy functional groups.

[0024] In one implementation, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 Each is independently selected from hydrogen and C1-C15 alkyl groups, and R 13 and R 14 Selected from substituted or unsubstituted diimides.

[0025] In one embodiment according to any of the foregoing embodiments, the imide group is selected from groups of formulas (IV), (V), and (VI):

[0026] (IV);

[0027] (V);

[0028] (VI)

[0029] Where R 18 R 19 R 20 and R 21 Independently selected from C2 to C30 divalent hydrocarbons, and R 22 Selected from C1-C10 divalent hydrocarbons.

[0030] In one embodiment according to any of the foregoing embodiments, the imide-functionalized organopolysiloxane has the following formula:

[0031]

[0032] In one embodiment according to any of the foregoing embodiments, the imide-functionalized organopolysiloxane has the following formula:

[0033]

[0034] In one embodiment of any of the foregoing embodiments, the imide-functionalized organopolysiloxane is present in an amount of about 1% to about 10% by weight. In one embodiment of any of the foregoing embodiments, the imide-functionalized organopolysiloxane is present in an amount of about 1% to about 5% by weight. In one embodiment of any of the foregoing embodiments, the imide-functionalized organopolysiloxane is present in an amount of about 1% to about 2% by weight.

[0035] In one embodiment of any of the foregoing embodiments, the polymer resin is a combination of a functional resin and at least one resin curing agent.

[0036] In any of the foregoing embodiments, the functional resin is selected from epoxy resin, polyurethane resin, polyamide resin, polyimide resin, acrylic resin, silicone resin, phenolic resin, or a combination of two or more thereof.

[0037] In one embodiment of any of the foregoing embodiments, the functional resin is present in an amount of about 7% to about 35% by weight. In one embodiment of any of the foregoing embodiments, the functional resin is present in an amount of about 7% to about 20% by weight. In one embodiment of any of the foregoing embodiments, the functional resin is present in an amount of about 10% to about 7% by weight.

[0038] In one embodiment of any of the foregoing embodiments, the resin curing agent is selected from phenolic resins, phenol-derived resins, substituted phenol-derived resins, or acid anhydride resins.

[0039] In one embodiment according to any of the foregoing embodiments, the resin curing agent is present in an amount of about 5% to about 30% by weight. In one embodiment according to any of the foregoing embodiments, the resin curing agent is present in an amount of about 5% to about 20% by weight. In one embodiment according to any of the foregoing embodiments, the resin curing agent is present in an amount of about 5% to about 10% by weight.

[0040] In one embodiment according to any of the foregoing embodiments, the composition comprises a resin curing agent and a functional resin in a ratio of 1:1 to 1:1.5.

[0041] In one embodiment of any of the foregoing embodiments, the composition is a two-component epoxy curing system.

[0042] In one embodiment of any of the foregoing embodiments, the filler comprises alumina, fused silica, or a combination thereof.

[0043] In one embodiment of any of the foregoing embodiments, the composition has a CTE value of less than 11 ppm. In one embodiment of any of the foregoing embodiments, the composition has a CTE value of less than 10 ppm. In one embodiment of any of the foregoing embodiments, the composition has a CTE value of less than 9 ppm. In one embodiment of any of the foregoing embodiments, the composition has a CTE value of less than 8 ppm.

[0044] In one embodiment according to any of the foregoing embodiments, the composition has a spiral flow of about 50 cm to about 100 cm.

[0045] In another aspect, an epoxy molding compound is provided, which is formed from a composition according to any of the foregoing embodiments.

[0046] On the other hand, articles are provided comprising materials formed from compositions according to any of the foregoing embodiments.

[0047] In one embodiment, the article of manufacture is selected from semiconductor packaging, electronic materials, or electronic coatings.

[0048] In one embodiment, the article is an electronic component containing material.

[0049] The following description and figures disclose various illustrative aspects. Some improvements and novel aspects may be clearly identified, although others are obvious from the description and figures. Detailed Implementation

[0050] Exemplary embodiments and examples illustrated in the accompanying drawings will now be mentioned. It should be understood that other embodiments may be utilized, and structural and functional changes may be made. Furthermore, features of various embodiments may be combined or modified. Therefore, the following description is presented only by illustrative means and should not in any way limit the various substitutions and modifications that may be made to the illustrated embodiments. Numerous specific details in this disclosure provide a thorough understanding of the subject matter. It should be understood that aspects of this disclosure may be practiced through other embodiments, which do not necessarily include all aspects described herein.

[0051] As used herein, the terms “example” and “exemplary” mean instance or illustration. The terms “example” or “exemplary” do not indicate key or preferred aspects or implementations. Unless the context otherwise requires, the word “or” is intended to indicate inclusion rather than exclusivity. For example, the phrase “A employs B or C” includes any inclusive permutation (e.g., A employs B; A employs C; or A employs both B and C). Furthermore, unless the context otherwise requires, the article “a” generally means “one or more”.

[0052] A composite composition comprising a resin and an imide-functionalized organopolysiloxane material is provided. The imide-functionalized organopolysiloxane comprises a siloxane modified with an imide functional group. The imide functional group may be side-attached to a siloxane unit, or the imide group may be disposed in the backbone of the material (to effectively connect two or more siloxane units). In one embodiment, the imide-functionalized organopolysiloxane comprises an imide functional group and at least one functional group selected from epoxy, hydride, aromatic, aliphatic, amine, and / or acryloyl or acryloyloxy groups, wherein the siloxane is selected from linear and nonlinear siloxanes, wherein the nonlinear siloxane comprises at least two of the said functional groups selected from epoxy, hydride, aromatic, aliphatic, amine, and / or acryloyl or acryloyloxy groups. The resin is reactive with the imide-functionalized organopolysiloxane. The resin is a combination of a functionalized resin and a resin curing agent. The composite composition may include other components, such as, but not limited to, catalysts, fillers, and hardeners. In the presence of imide-functionalized organopolysiloxane materials, the composite composition can achieve the desired CTE value (reduction of CTE), reduced hygroscopicity, and improved helical flow, gelation time, and mechanical strength.

[0053] The present invention provides a composition comprising an imide-functionalized organopolysiloxane material containing imide and epoxy functional groups. In one embodiment, the imide-functionalized organopolysiloxane material is a compound having structural formula (I):

[0054]

[0055] (I)

[0056] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 and R 14Each group is independently selected from hydrogen, C1-C15 alkyl, epoxy, C6-C30 aromatic groups, and imide groups, provided that (i) R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 and R 14 At least one of them is selected from an imide group, and (ii) R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 and R 14 At least one of them is selected from epoxy groups;

[0057] A1, A2, A3 and L1, L2, L3, L4, L5, L6, L7, L8, L9, L 10 L 11 and L 12 Each of these is a linking group independently selected from divalent alkyl, divalent alkenyl, or divalent ether groups.

[0058] o≥1;

[0059] w, x, y and z are each ≥ 0, where (w+x+y+z) ranges from 1 to 60;

[0060] k1, k2, k3, k4, k5, k6, k7, k8, k9, k10, k11, and k12 are each independently ≥ 0; and

[0061] a1, a2, and a3 are each independently ≥ 0.

[0062] The C1-C15 alkyl groups may be selected from straight-chain or branched groups. In one embodiment, the C1-C15 alkyl groups are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, and isooctyl.

[0063] The C6-C30 aromatic group may be selected from aryl, aralkyl, and alkylaryl. The term "aryl" means any monovalent aromatic hydrocarbon group; the term "aralkyl" means any alkyl group (as defined herein) in which one or more hydrogen atoms have been substituted by the same number of the same and / or different aryl groups (as defined herein); and the term "arylalkyl" means any aryl group (as defined herein) in which one or more hydrogen atoms have been substituted by the same number of the same and / or different alkyl groups (as defined herein). An aromatic group may contain one or more aromatic rings. In groups having multiple aromatic rings, the rings may be linked by bonds, by linking groups (e.g., divalent hydrocarbon groups or groups having heteroatoms), or may be a fused ring system. An aromatic group may be an array of atoms having at least one monovalent valence and having at least one aromatic group. It may include heteroatoms such as nitrogen, sulfur, selenium, silicon, and oxygen, or may consist only of carbon and hydrogen. Suitable aromatic groups may include phenyl, pyridyl, furanyl, thiophene, naphthyl, phenylene, and biphenyl. Aromatic groups can be cyclic structures with 4n+2 "delocalized" electrons, where "n" can be an integer equal to 1 or greater, such as phenyl (n=1), thiophene (n=1), furanyl (n=1), naphthyl (n=2), azulel (n=2), anthracene (n=3), etc. Aromatic groups can also include non-aromatic components. For example, benzyl can be an aromatic group, which may include a benzene ring (aromatic group) and a methylene group (non-aromatic component). Similarly, tetrahydronaphthyl can be an aromatic group containing an aromatic group (C6H3) fused with a non-aromatic component -(CH2)4-. Aromatic groups may include one or more functional groups, such as alkyl, alkenyl, alkynyl, haloalkyl, haloaromatic, conjugated dienyl, alcohol, ether, aldehyde, ketone, carboxylic acid, acyl (e.g., carboxylic acid derivatives, such as esters and amides), amino, nitro, etc. For example, 4-methylphenyl can be a C7 aromatic group containing a methyl group, where the methyl group is the functional group and can be an alkyl group. Similarly, 2-nitrophenyl can be a C6 aromatic group containing a nitro group, where the nitro group is the functional group. Examples of C6-C30 aromatic groups include, but are not limited to, phenyl, naphthyl; ortho, meta, and para-tolyl, xylyl, ethylphenyl, and benzyl.

[0064] In one implementation, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 At least one of them is selected from imide, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 At least one of them is selected from epoxy groups, and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R12 At least one of the groups is selected from C6-C30 aromatic groups. In this embodiment, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 The residues are each independently selected from C1-C15 alkyl groups.

[0065] In one implementation, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 R13 is selected independently from hydrogen, C1-C15 alkyl and C6-C30 aromatic groups, R14 is selected from an imide functional group and R15 is selected from an epoxy functional group.

[0066] In one implementation, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 Each is independently selected from hydrogen and C1-C15 alkyl groups, and R13 and R14 are selected from substituted or unsubstituted diimides.

[0067] The epoxy group is not particularly limited and can be selected according to the needs of a specific purpose or intended application. In one embodiment, the epoxy group is selected from glycidyl or glycidyl ether groups. The epoxy group may have formula (II) or (III):

[0068] (II)

[0069] (III)

[0070] Where R 15 R 16 and R 17 Each is independently selected from C1-C10 divalent hydrocarbon groups.

[0071] The imide group can be selected from groups containing an imide functional group. In the examples, the imide functional group is selected from groups of formulas (IV), (V), and (VI):

[0072] (IV);

[0073] (V);

[0074] (VI)

[0075] Where R 18 R 19 R 20 and R21 Independently selected from C2 to C30 divalent organic groups, and R 22 It is selected from bonds, C1-C30 divalent organic groups or O atoms. The C2 to C30 divalent groups can be saturated, unsaturated, straight-chain, branched, cyclic, aromatic, etc., and can be unsubstituted or substituted.

[0076] In one implementation, R 18 R 20 and R 21 Each is independently selected from C2 to C30 bivalent chains to form a single ring. In one embodiment, R 18 R 20 and R 21 Independently selected from C2 to C6 bivalent chains. In one implementation, R 18 R 20 and R 21 The group is independently selected from C2 or C3 divalent groups to provide a five- or six-membered imide ring.

[0077] In one implementation, R 19 It is a hydrocarbon containing C5-C30 rings. In one embodiment, the cyclic hydrocarbon can be an unsaturated ring, a saturated ring, a saturated or unsaturated fused ring system, or a polycyclic system separated by bonds or other connecting groups. In another embodiment, the ring can be an aromatic ring.

[0078] In one implementation, R 18 R 20 and R 21 Each is independently selected from C5-C30 cyclic hydrocarbons. In one embodiment, the cyclic hydrocarbon may be an unsaturated ring, a saturated ring, a saturated or unsaturated fused ring system, or a polycyclic system separated by bonds or other connecting groups. In another embodiment, the ring may be an aromatic ring.

[0079] R 18 Some non-limiting examples include:

[0080]

[0081]

[0082] R 19 Non-restrictive examples include:

[0083]

[0084]

[0085] R 20 and R 21 Non-restrictive examples include:

[0086]

[0087]

[0088] R 22 The organophosphate group is selected from bonds, C1 to C30 divalent organic groups, or O atoms. The divalent organic group can be straight-chain, branched, or contain one or more cyclic groups, including, for example, C6 to C30 aromatic groups. The C1 to C30 divalent organic group can be unsubstituted or substituted. Substituted organic groups may include, for example, one or more heteroatoms selected from N, O, S, and / or halogen groups (e.g., F). In one embodiment, R... 22 Selected from divalent C1-C10 groups. In one embodiment, R 22 Selected from -CH2-, -CH2CH2-, or -CH2CH2CH2-. In one embodiment, R 22 Selected from ---O--- key (linkage). In one implementation, R 22 Selected from C1-C10 groups that optionally contain at least one COC bond. In one embodiment, R 22 Selected from divalent C1-C10 groups, wherein one or more hydrogen atoms are replaced by fluorine atoms. In one embodiment, R 22 Selected from –(CF2)n-, where n is 1 to 10. In one embodiment, R 22 Selected from (-C(CF3)(CF3)-)m, where m is from 1 to 10.

[0089] Some examples of suitable imide groups include, but are not limited to:

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] Where R 23 and R 24 It can be selected from hydrogen, C1-C15 alkyl, epoxy, C4-C20 cyclic groups, and C6-C30 aromatic groups, which can be substituted or unsubstituted, and wherein the carbon atom in the cyclic or aromatic group can be replaced by a heteroatom selected from O, N, or S. b is an integer from 0 to 4. R 23’ It is a divalent organic group containing epoxypropoxy and imide substituents, and R 23’’ It is an amino-terminated siloxane.

[0103] In one implementation, R 1 To R 12 Independently selected from hydrogen, epoxy group, C1-C15 alkyl group, C6-C30 aryl group and imide group, and R 13 and R 14 Selected from C1-C15 alkyl groups, wherein R 1 To R 12 At least one of them is selected from imides, and R 1 To R 12 At least one of them is selected from epoxy groups. In one embodiment, R 1 R 2 R 3 R 4 R 5 R 7 R 9 R 10 R 11 and R 12 Independently selected from hydrogen, C1-C15 alkyl groups and C6-C30 aromatic groups, R 6 Selected from imide functional groups, and R 8 Selected from epoxy functional groups. In one exemplary embodiment, the imide-functionalized organopolysiloxane contains an imide functional group, an epoxy functional group, and an alkenyl aryl group at the side-mounted position, as shown in structure A:

[0104]

[0105] Structure A

[0106] In one implementation, R1 to R 12 Independently selected from hydrogen or C1-C15 alkyl, and R 13 and R 14 The groups are independently selected from those containing imide. In one exemplary embodiment, the imide-functionalized organopolysiloxane is a linear molecule comprising an imide functional group linked to a siloxane backbone having a terminal epoxy functional group, as shown in structure B:

[0107]

[0108] Structure B

[0109] In one exemplary embodiment, the imide-functionalized organopolysiloxane comprises a triazine-substituted diimide functional group, as shown in structure C:

[0110]

[0111] Structure C

[0112] In another exemplary embodiment, the imide-functionalized organopolysiloxane comprises a diphenyl ether-substituted bisimide functional group, wherein R 19 It is a benzene ring, as shown in structure D:

[0113]

[0114] Structure D

[0115] In another exemplary embodiment, the imide-functionalized organopolysiloxane comprises a diphenyl ether-substituted bisimide functional group, wherein R 19 It is a polycyclic system, such as biphenyl, as shown in structure E:

[0116]

[0117] Structure E

[0118] In another exemplary embodiment, the imide-functionalized organopolysiloxane comprises a plurality of imides and substituted diimide functional groups, wherein R 14 It is a diimide-substituted organopolysiloxane (structure (I)), and R 13 It is an imide-substituted organopolysiloxane (structure (I)), and R 14 and R 13The ethylene linkers (A1 and A2) are attached to the siloxane backbone, as shown in structure F:

[0119]

[0120] Structure F

[0121] In another exemplary embodiment, the imide-functional organopolysiloxane comprises a siloxane backbone having two linking groups at both ends, including a substituted divalent alkyl group, such as an aminoalkyl linking group (A1), at one end, and a -CH(OH)-CH2-O-CH2-substituted aminoalkyl linking group (A2) at the other end, wherein R 13 It is a substituted imide, wherein the substituted imide contains R 23’ It is a divalent organic group containing epoxypropoxy and imide substituents, and the substituted imide also contains R. 23’’ It is an amino-terminated siloxane, as shown in structure G:

[0122]

[0123] Structure G

[0124] In another exemplary embodiment, the imide-functionalized organopolysiloxane comprises a plurality of imides and substituted diimide functional groups, wherein R 14 R13 is a diimide-substituted organopolysiloxane (structure (I)), and R13 is an imide-substituted organopolysiloxane (structure (I)). 14 and R 13 The ethylene linkers (A1 and A2) are attached to the siloxane backbone, as shown in structure H:

[0125]

[0126] Structure H

[0127] In another exemplary embodiment, the imide-functionalized organopolysiloxane comprises a plurality of imides and substituted diimide functional groups, wherein R 14 It is a diimide-substituted organopolysiloxane (structure (I)), and R 13 It is an imide-substituted organopolysiloxane (structure (I)), and R 14 and R 13 Attached to the siloxane backbone via ethylene linkers (A1 and A2), and R 22 It is -C(CF3)2, as shown in structure J:

[0128]

[0129] Structure J

[0130] In another exemplary embodiment, the imide-functionalized organopolysiloxane comprises a plurality of imide and triazine-substituted diimide functional groups, wherein R 14 R13 is a triazine-substituted diimide (structure (I)), and R13 is an imide-substituted organopolysiloxane (structure (I)), and R 14 and R 13 Attached to the siloxane backbone via ethylene linkers (A1 and A2), and R 22 It is -C(CF3)2, as shown in structure K:

[0131]

[0132] Structure K

[0133] Structure AK illustrates an example of an embodiment of an imide-functionalized organopolysiloxane according to aspects of the present technology as described above.

[0134] In one embodiment, the compound according to the present technology can be prepared by introducing an imide group and an epoxy group into a siloxane unit via a hydrosilylation reaction. In one embodiment, an alkenyl-functionalized imide reacts with a hydride-functionalized siloxane to provide an imide-functionalized siloxane. The reaction can be controlled such that a molar excess of the hydride functional group is present after the reaction with the imide, such that the imide-functionalized siloxane contains the hydride functional group. The imide-functionalized siloxane containing the hydride functional group is then reacted with an alkenyl-functionalized epoxy group (epoxy resin) to produce an imide-functionalized organopolysiloxane.

[0135] The reaction can be carried out in a solvent. A solvent may be required, for example, to dissolve the alkenyl-functionalized imide. The reaction can also be carried out at elevated temperatures. In embodiments, the reaction for adding the imide and the epoxy group can be carried out at temperatures of about 50°C to about 110°C, about 60°C to about 100°C, or about 75°C to about 90°C.

[0136] Alkenyl-functionalized imides can be selected, for example, from compounds of the following formula:

[0137] ;

[0138] ; and / or

[0139]

[0140] Where R 18 R 19 R 20 R 21 and R 22As described above, and R' is independently selected from C2-C30 alkenyl functional groups. Generally, alkenyl functional groups include terminal alkenyl groups. In the examples, R' is selected from vinyl, allyl, methyl allyl, butenyl, isobutenyl, sec-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl functional groups and branched groups with 6 or more carbon atoms.

[0141] Hydrosilylation catalysts are used in each reaction. The catalysts used in the reactions of alkenyl-functionalized imides can also be used in the reactions of alkenyl-functionalized epoxy groups with imide-functionalized siloxanes. There are no particular limitations on the hydrosilylation catalysts, and any suitable hydrosilylation catalyst can be used in the reaction. In one embodiment, the catalyst is selected from platinum group metal-based hydrosilylation catalysts. For the purposes of this invention, the term "platinum group metals" means ruthenium, rhodium, palladium, osmium, iridium, and platinum. In one embodiment, the hydrosilylation catalyst is platinum-based. A further preferred hydrosilylation catalyst is a platinum-alkenylsiloxane complex. Particularly preferred are hydrosilylation catalysts selected from platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes (Karstedt complexes), platinum-1,3-diallyl-1,1,3,3-tetramethyl-disiloxane complexes, platinum-1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane complexes, platinum-1,1,3,3-tetraphenyldisiloxane complexes, and platinum-1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane complexes. More preferably, the hydrosilylation catalyst is platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes (Karstedt complexes).

[0142] In an alternative embodiment, the alkenyl-functionalized siloxane can be used with a hydride-functionalized imide to provide an imide-functionalized siloxane. The reaction can be controlled such that a molar excess of alkenyl functional group is present after the reaction with the imide, such that the imide-functionalized siloxane comprises the alkenyl functional group. The imide-functionalized siloxane comprising the alkenyl functional group is then reacted with a hydride-functionalized epoxide to produce an imide-functionalized organopolysiloxane.

[0143] In another embodiment, the imide-functionalized organopolysiloxane according to the present technology can be prepared by an imidization reaction. The imidization reaction involves adding a dianhydride substituted with an aliphatic or aromatic group; a diamino or dianhydride-functionalized siloxane; and an aliphatic or aromatic-functionalized amine to produce an imide-functionalized siloxane comprising one or more substituents. The imidization reaction involves reacting a diaminosiloxane with a dianhydride and optionally a functionalized amino organic group and / or anhydride and heating the mixture. This reaction can be carried out as a "one-pot" reaction. In embodiments, the reaction can be carried out at temperatures of approximately 100°C to approximately 200°C, approximately 120°C to approximately 180°C, approximately 130°C to approximately 170°C, or approximately 150°C to approximately 160°C.

[0144] Diaminosiloxanes are siloxanes with the desired chain length having a terminal amino group.

[0145] A dianhydride can be selected to provide an imide with the desired structure. In embodiments, the dianhydride is selected from compounds of the following formula:

[0146]

[0147]

[0148] Where R 19 R 20 R 21 and R 22 As stated above.

[0149] Functional amines may contain organic groups, including but not limited to aliphatic, cyclic, acyclic, alicyclic, heterocyclic, aromatic, and heteroaromatic groups. In some embodiments, functional amines include, but are not limited to, monoamines, diamines, and triamines. In such embodiments, each of these amines may be a primary, secondary, or tertiary amine.

[0150] The imidization reaction can optionally use anhydride-terminated siloxanes, wherein the anhydride-terminated siloxane is obtained by hydrosilylation of an alkenyl-functional anhydride with a hydride-functionalized siloxane. The alkenyl-functionalized anhydride can have the following formula:

[0151]

[0152] Where R 18 As mentioned above, and R 25 It is an alkenyl functional group. The alkenyl functional group can be selected from C2-C30 alkenyl functional groups. R 25 Examples include, but are not limited to, vinyl, allyl, methyl allyl, butenyl, isobutenyl, sec-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl functional groups and branched groups with six or more carbon atoms.

[0153] The imide-functional organopolysiloxane may be present in the composition in amounts of about 1% to about 10% by weight, about 1% to about 5% by weight, or about 1% to about 2% by weight.

[0154] Functional resins

[0155] Functional resins can be selected according to the specific purpose or intended application requirements. There are no particular limitations on functional resins, except that the resin should be reactive with imide-functionalized organopolysiloxanes.

[0156] Examples of suitable functional resins include, but are not limited to, epoxy resins, polyurethane resins, polyamide resins, polyimide resins, acrylic resins, siloxane resins, phenolic resins, etc.

[0157] In one embodiment, the functional resin is an epoxy resin. The epoxy resin component can be any type of epoxy resin suitable for use in molding compositions, including any material containing two or more reactive ethylene oxide groups. The epoxy resin can have more than two epoxy groups in one molecule, including glycidyl ether type; glycidyl ester type; alicyclic type; heterocyclic type; and halogenated epoxy resins, etc. Non-limiting examples of suitable epoxy resins include epoxy cresol phenolic varnish resins, phenolic varnish epoxy resins, biphenyl epoxy resins, hydroquinone epoxy resins, piracene epoxy resins, and mixtures and combinations thereof. Epoxy cresol phenolic varnish resins are particularly suitable for use in this invention. Epoxy resins can be used alone or as a mixture of two or more resins, such as a combination of epoxy cresol phenolic varnish and biphenyl epoxy resin.

[0158] Specific examples of other epoxy resins that may be preferably used in combination include bisphenol or bisphenol crystalline epoxy resins or mixtures thereof, such as YX-4000 from Japan Epoxy Resins and CER-3000 (trade name) from NIPPON KAYAKU CO., LTD.; bisphenol S crystalline epoxy resins; bisphenol fluorene crystalline epoxy resins; hydroquinone crystalline epoxy resins; heterocyclic crystalline epoxy resins, such as TEPIC (trade name) from NISSAN CHEMICAL INDUSTRIES, LTD.; crystalline epoxy resins of glyoxal-phenol condensates; triphenol methane crystalline epoxy resins; and biphenyl phenolic varnish crystalline epoxy resins (e.g., crystalline epoxy resins having a backbone similar to NC-3000 from NIPPON KAYAKU CO., LTD.). These can be used alone or in combination of two or more. The resin may be an epoxy resin (or a mixture of resins) to form an epoxy molding composition.

[0159] The resin may be present in the composition in amounts of about 7% to about 35% by weight, about 7% to about 20% by weight, or about 10% to about 7% by weight.

[0160] Resin hardener

[0161] The composite composition includes a resin curing agent to promote crosslinking of the resin. The resin curing agent can be selected based on the resin used in the composition, according to the needs of a specific purpose or intended application. In one embodiment, the curing agent is selected from phenol-derived or substituted phenol-derived phenolic varnishes or acid anhydrides. Non-limiting examples of suitable curing agents include phenolic varnish curing agents, cresol phenolic varnish curing agents, dicyclopentadiene phenol curing agents, limonene-type curing agents, acid anhydrides, and mixtures thereof.

[0162] Suitable anhydride curing agents include, but are not limited to, maleic anhydride; methyltetrahydrophthalic anhydride; methyl-4-endomethylenetetrahydrophthalic anhydride; hexahydrophthalic anhydride; tetrahydrophthalic anhydride; and dodecenylsuccinic anhydride. An exemplary anhydride curing agent is methyltetrahydrophthalic anhydride (MTHPA).

[0163] The resin hardener may be present in the composition in an amount of about 5% to about 30% by weight, about 5% to about 20% by weight, or about 5% to about 10% by weight.

[0164] In one embodiment, the resin curing agent and the functional resin are present in the composition such that the ratio of the resin curing agent to the functional resin is 1:1 to 1:1.5; 1:1.1 to 1:1.4; or 1:1.2 to 1:1.3.

[0165] catalyst

[0166] The composition comprises a catalyst. The terms "catalyst" and "curing accelerator" are used interchangeably and generally refer to a material that catalyzes or accelerates the curing reaction between the resin and the siloxane additive. The catalyst may be selected in part based on the resin. Examples of suitable catalysts include, but are not limited to, basic and acidic catalysts, such as metal halide Lewis acids, including boron trifluoride, tin chloride, zinc chloride, etc.; metal carboxylates, such as stannous octoate, etc.; and amines, such as triethylamine, imidazole derivatives, etc.

[0167] Examples of suitable curing accelerators include, but are not limited to, polyamines such as diaminodiphenylmethane, m-phenylenediamine, diaminodiphenyl sulfone, cyclohexylamine, m-phenylenediamine, 4,4'-diamino-3,3'-diethyldiphenylmethane, diethylenetriamine, tetraethylenepentamine, N-aminoethylpiperazine, isophorone diamine, dicyandiamide, urea, urea derivatives, melamine, polyhydrazides and their organic acid salts and / or epoxy adducts; amine complexes of boron trifluoride; trimethylamine, triethanolamine, N,N-dimethyloctylamine, N,N-dimethylaniline, N-benzyldimethylamine, pyridine, N-methylpyridine, N-methylmorpholine, hexamethoxymethylmelamine, 2,4,6-tris(dimethylamino) Tertiary amines such as phenol, N-cyclohexyldimethylamine, tetramethylguanidine, and m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenolic varnish, and alkylphenolic varnish; organophosphorus compounds such as tributylphosphine, triphenylphosphine, and tri-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyltributylammonium chloride, and benzyltrimethylammonium bromide; anhydrides of the above polybasic acids; photocationic polymerization catalysts such as diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyranium hexafluorophosphate, products of Ciba-Geigy Ltd. under the registered trademark "IRGACURE" 261, and styrene-maleic acid resin.

[0168] The catalyst may be present in the composition in an amount of about 0.1 wt% to about 0.5 wt%, about 0.1 wt% to about 0.3 wt%, or about 0.1 wt% to about 0.2 wt%.

[0169] plasticizer

[0170] The composite composition may include a plasticizer. Examples of suitable plasticizers include, but are not limited to, sulfonate plasticizers, phosphate plasticizers, sulfonamide plasticizers, triglyceride plasticizers, dialkyl esters of aliphatic dicarboxylic acids, glycol esters of benzoic acid, glycols, etc. In one embodiment, the plasticizer may be a glycol, including glycols that are solid at room temperature. The plasticizer essentially functions as a toughening agent.

[0171] Examples of diols include, but are not limited to, aromatic diols such as bisphenol A and bisphenol F, aliphatic monomers or polymeric diols such as polyethylene glycol (PEG) or polypropylene glycol (PPG), or neopentyl glycol. One exemplary embodiment specifies that bisphenol A, bisphenol F, and neopentyl glycol, or mixtures of these compounds, may be used as diols. For example, neopentyl glycol and bisphenol A, or mixtures of these compounds, may be used.

[0172] Examples of sulfonate plasticizers include, but are not limited to, alkyl sulfonates of phenolic compounds, such as phenyltoluene ester of pentadecyl sulfonic acid. Suitable commercially available sulfonate plasticizers include those sold by Bayer under the trade name MESAMOLL.

[0173] Examples of phosphate ester plasticizers include, but are not limited to, organic esters of phosphoric acid, such as, for example, phenolic esters of phosphoric acid, such as tricresyl phosphate, toluene diphenyl phosphate, isopropylated triphenyl phosphate, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, and triphenyl phosphate, as well as other triaryl phosphates and alkyl diaryl phosphates. Other suitable phosphate ester plasticizers include, but are not limited to, tributoxyethyl phosphate, tributyl phosphate, etc.

[0174] Suitable triglyceride plasticizers include, but are not limited to, the compounds described in U.S. Patent No. 6,652,774, which is incorporated herein by reference in its entirety.

[0175] Examples of sulfonamide plasticizers include, but are not limited to, aromatic sulfonamides such as N-(2-hydroxypropyl)benzenesulfonamide (sold by Unitex Chemical Co. under the trade name UNIPLEX 225), N-ethyltoluenesulfonamide, N-(n-butyl)benzenesulfonamide, N-cyclohexyl-p-toluenesulfonamide, etc.

[0176] Other plasticizers suitable for use in this invention include, for example, C3-C20 dialkyl esters of aliphatic dicarboxylic acids such as adipic acid, such as dioctyl adipate, dibutyl adipate, di(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, and di(heptyl,nonyl) adipate, as well as diol esters of benzoic acid, such as dipropylene glycol dibenzoate and dipropylene glycol monobenzoate.

[0177] The plasticizer may be present in the composition in amounts of about 0% to about 20% by weight, about 0% to about 10% by weight, or about 0% to about 5% by weight.

[0178] filler

[0179] The composite composition may include fillers. Fillers may be included to impart specific properties to the composite material, including reinforcement, strength, color, conductivity, etc. Fillers may be organic or inorganic, and examples of suitable fillers include, but are not limited to, clay, nanoclay, organoclay, ground calcium carbonate, precipitated calcium carbonate, colloidal calcium carbonate, calcium carbonate treated with a compound containing a stearate fraction or stearic acid, fumed silica, precipitated silica, crushed quartz, ground quartz, alumina, aluminum hydroxide, ceramics and glass beads, titanium dioxide, titanium hydroxide, zirconium oxide, zinc oxide, kaolin, bentonite, montmorillonite, diatomaceous earth, iron oxide, PTFE powder, carbon black and graphite, talc, mica, pumice, wollastonite, dolomite, feldspar, and combinations thereof. In one embodiment, the composition comprises fillers including fused silica.

[0180] The filler may be present in the composition in an amount of about 30% to about 85% by weight, about 60% to about 85% by weight, or about 75% to about 85% by weight.

[0181] Depending on the specific purpose or intended application, the composition may be provided as a one-component or two-component system. The choice of resin determines whether the composition is provided as a one-component or two-component system. In one embodiment, the composition is selected to provide an epoxy resin composition, such as one that can be used to form epoxy molding compounds. The epoxy resin composition may be provided as a one-component or two-component system. In one embodiment, the composition is a two-component composition comprising (i) a first component comprising an epoxy resin; and (ii) a second component comprising a resin curing agent and a catalyst, wherein an imide-functionalized polyorganosiloxane may be provided in the first and / or second components. Additionally, other components, such as fillers, plasticizers, etc., may be provided in the first or second component.

[0182] The composite composition may have a CTE of less than 12 ppm. In some embodiments, the CTE of the composite may be less than 12 ppm, less than 11 ppm, less than 10 ppm, less than 9 ppm, or less than 8 ppm. In examples, the CTE of the composite composition is about 5 ppm to about 12 ppm, about 7 ppm to about 11 ppm, or about 8 to about 10 ppm. The CTE value used for the above range refers to the CTE α1 value, which represents the coefficient of thermal expansion below the Tg temperature. CTE can be measured by: (i) extruding the material into a rod (80 mm × 10 mm × t4 mm) at a molding temperature of 175°C using a molding machine for 5 minutes; (ii) placing the rod in an oven at 175°C for 5 hours; (iii) cutting the rod to a size of (10 mm × 5 mm × t4 mm) for TMA; and (iv) heating the sample from room temperature to 300°C at a rate of 5°C / min under a load of 0.1 N. The standard calculation temperature range for CTE α1 is 25°C to 80°C.

[0183] In one embodiment, the material formed from the composition has a glass transition temperature (Tg) of about 110°C to about 140°C, about 115°C to about 135°C, or about 120°C to about 130°C.

[0184] In one embodiment, the composition has a spiral flow of at least about 50 cm, at least about 60 cm, or at least about 70 cm. In one embodiment, the composition has a spiral flow of about 50 cm to about 100 cm, about 60 cm to about 90 cm, or about 70 cm to about 80 cm.

[0185] The composite material can be formed by mixing the composition using a planetary mixer and a kneader or rolling mill. The mixture is then extruded and heated at 175°C for 5 minutes, using a transfer molding machine, to obtain a cured composite material. The compositions of the present invention can be used in various applications in electronic device manufacturing, such as underfill, encapsulant, and solder bump reinforcement materials. Electronic assemblies can be formed by the following steps: providing electronic components and substrates, wherein one of the electronic components and the substrate has a plurality of interconnect structures and the other has a plurality of conductive bonding pads; electrically connecting the electronic components and the substrate; forming an underfill composition between the electronic components and the substrate; and curing the underfill composition; wherein the underfill composition comprises a liquid cyclic siloxane comprising a plurality of glycidyl ether moieties; an aromatic thermosetting resin; and a curing agent. The compositions of the present invention can be cured by any suitable means, for example by heating the composition at a suitable temperature.

[0186] In one embodiment, the compositions of the present invention can be used as capillary bottom filler encapsulants in semiconductor packaging materials, for example, to protect fragile electronic components, such as flip-chip ball grid arrays (FC-BGAs) and chip-scale packages (CSPs).

[0187] The present technology has been described in the foregoing detailed description and with reference to various aspects and embodiments. The present technology can be further understood with reference to the following embodiments. These embodiments are intended to further illustrate aspects and implementations of the present technology, and are not necessarily limited to these aspects or implementations.

[0188] Example

[0189] Composite materials were prepared using epoxy resin and imide-functionalized organopolysiloxanes. The composite materials were prepared as follows: 5.56 g YX-4000H, 1.39 g NC-3000, 5.82 g MEHC-7800, 1.91 g ETM90 (Momentive Performance Materials), 0.14 g Silquest A-187, 0.09 g triphenylphosphine, and 85.00 g FB560 (fused silica, Denka) were added to a planetary mixer. The mixture was stirred at 25°C for 10 minutes. The mixture was then uniformly dispersed using a roller mill at 105°C for 5 minutes. The mixture was extruded using a transfer molding machine and heated at 175°C for 5 minutes. Properties such as CTE, modulus, and flexural strength were measured using the cured composite material. The imide-functionalized organopolysiloxanes used in the preparation of the composition were described below.

[0190] Example 1; E2-1: Synthesis of organopolysiloxanes with side groups, structure A, having an average chemical formula where w=44, x=1, y=5, and z=5. (1) Side-attached hydride siloxane MD 44 D' 11M (150 g), 2-allyl isoindoline-1,3-dione (7.4 g), and toluene (150 mL) were placed in a three-necked round-bottom flask of appropriate size equipped with a thermopocket, condenser, and dropping funnel. The temperature of the reaction mixture was raised to 93 °C, and then 10 ppm of platinum catalyst was added to the reaction mixture. (2) After step 1 was completed, α-methylstyrene (25.69 g) was placed in the dropping funnel and added dropwise to the reaction mixture. After the α-methylstyrene was completely added and the reaction mixture was exothermically stabilized, the internal temperature of the reaction mixture was raised to 96.5 °C. (3) After step 2 was completed, allyl glycidyl ether (33.9 g) was placed in the dropping funnel and added dropwise to the reaction mixture. After the reaction was completed, the mixture was carbonized to remove colloidal Pt while stirring at 50 °C for 4 hours. The treated material was filtered and separated from the carbon by using a sintering funnel with a diatomaceous earth bed, and the filtrate was collected. The solvent was then removed from the filtrate to obtain the product, which was a yellow, viscous product with structure A.

[0191] Example 2, E2-2: Synthesis of organopolysiloxanes with side groups, structure A, having an average chemical formula where w=11, x=0.5, y=1.8, and z=1.7. (1) Side-attached hydride siloxane MD 11 D'4M (150 g), 2-allyl isoindoline-1,3-dione (8.52 g), and toluene (50 mL) were placed in a three-necked round-bottom flask of appropriate size equipped with a thermometer, condenser, and dropping funnel. The temperature of the reaction mixture was raised to 90 °C, and then 10 ppm of platinum catalyst was added to the reaction mixture. (2) After step 1 was completed, α-methylstyrene (28.77 g) was placed in a dropping funnel and added dropwise to the reaction mixture. After the α-methylstyrene was completely added, the temperature of the reaction mixture was raised to 95 °C. (3) After step 2 was completed, allyl glycidyl ether (37.91 g) was placed in a dropping funnel and added dropwise to the reaction mixture. After the reaction was completed, the mixture was carbonized to remove colloidal Pt while stirring the mixture at 50 °C for 4 hours. The treated material was filtered and separated from the carbon using a sintering funnel with a diatomaceous earth bed, and the filtrate was collected. The solvent was then removed from the filtrate to obtain a yellow viscous product, structure A. Examples E2-3 to E2-5 were prepared using similar experimental methods.

[0192] Example 3, E1-X: Synthesis of organopolysiloxane, structure B. N,N-diallylpyromellitic diaimide (20 g) was placed in a round-bottom flask equipped with a thermometer, condenser, and dropping funnel. Toluene was added to dissolve the diaimide. The mixture was then heated to 75°C, followed by the addition of telechelic hydride siloxane M'D. 12M' (150 g) was added to a round-bottom flask (RBF). Then, 10 ppm of platinum catalyst was added to the reaction mixture, and exothermic reaction was observed during the addition of the hydride. After stirring the mixture for 2 hours, proton NMR was recorded. Following the consumption of N,N-diallylpyromellitic diimide, the imide-modified siloxane hydride was further capped with allyl glycidyl ether (25 g). The reaction mixture was stirred thoroughly at 75 °C. Proton NMR was then recorded to verify complete hydride consumption. After the reaction was complete, the mixture was carbonized to remove colloidal Pt while stirring at 50 °C for 4 hours. The treated material was filtered and separated from the carbon using a sintering funnel with a diatomaceous earth bed, and the filtrate was collected. The solvent was then removed from the filtrate to obtain a pale yellow viscous substance, structure B.

[0193] Table 1 Examples of imide-functionalized organopolysiloxanes

[0194]

[0195] The compositions of the examples consist of a combination of epoxy resin and bisphenol or bisphenol crystalline epoxy resin or mixtures thereof, such as YX-4000, available from Japan Epoxy Resins, with an epoxy equivalent of 197 g / eq and a melting point of 105°C, and CER-3000, available from NIPPON KAYAKU CO.,LTD, with an epoxy equivalent of 275 g / eq and a melting point of 58°C. These have been used in combination. Along with the epoxy-based functional resin, the polyphenol resin curing agent MEHC-7800, available from Meiwa Kasei, with a hydroxyl equivalent of 175 g / eq and a melting point range of 61-90°C, is used. Furthermore, the compositions contain Momentive's proprietary silane Silquest A-187 and fused silica (FB560, Denka, 17.5 μm, 3.8 m). 2 Fillers, waxes and control additives (siloxane 1 / siloxane 2 or reference additive) or imide-functionalized organopolysiloxanes ( / g).

[0196] The composite material was prepared according to the formulation described in Table 2.

[0197] Table 2 Formulations used in various embodiments

[0198]

[0199] Evaluate various properties of composite materials, including helical flow, compressibility, gelation time, glass transition temperature, coefficient of thermal expansion, and hygroscopicity. The test methods used to assess these properties are described below.

[0200] Spiral Flow

[0201] In the helical flow test, the flow properties of the epoxy molding compound were determined by measuring the length of resin flowing along the path of the helical cavity using a transfer molding machine (MF-0 15, Technomarushichi Inc.). The sample used for the helical flow test was a compressed tablet of the epoxy molding compound powder. The helical flow test was performed according to method EMI-1-66. The test conditions were set as follows: temperature 175°C, pressure 6.9 MPa, molding time 3 min, plunger speed 5 cm / s, and injection volume ~30 g per injection.

[0202] Compression ratio (molding compression ratio and curing shrinkage)

[0203] The sample from the extruder was molded into a strip (80 mm × 10 mm × 4 mm) using a molding machine. The molding temperature was 175°C, the molding time was 5 minutes, the pressure was 6.9 MPa, the plunger speed was 5 cm / s, and the injection volume was ~32 g per injection. The molding compression ratio was calculated by comparing the dimensions of the mold with the dimensions of the bar removed from the mold (before the curing process), as follows:

[0204] Molding compression ratio (%) = (mold size - size of the bar removed from the mold) / mold size × 100.

[0205] After measuring the sample of the rod removed from the mold, the rod was placed in an oven at 175°C for 5 hours, and then left to stand overnight at room temperature. The curing shrinkage rate was calculated by comparing the dimensions of the rod removed from the mold (before the curing process) with the dimensions of the rod after the curing process, as follows:

[0206] Molding compression ratio (%) = (size of the rod removed from the mold before the curing step - size of the rod after the curing process) / mold size × 100.

[0207] gelation time

[0208] In the gelation time test, the gelation point of the epoxy molding compound is measured. In the test, a hot plate is heated to 175°C. A powdered sample of the epoxy molding compound is placed on the hot plate and allowed to stand until gelation is complete. The gelation time is measured using a stopwatch (started immediately when the sample is placed on the hot plate and stopped when gelation is complete).

[0209] Glass transition temperatures Tg, E', and E'' determined by DMA

[0210] The glass transition temperature (Tg) of epoxy molding compounds can be determined by various methods, such as dynamic mechanical analyzer (DMAEXTEAR DMS6100, Hitachi high-tech science Inc.) and thermomechanical analyzer (TMA). Specifically, in this application, the sample in the extruder was molded into a strip (80 mm × 10 mm × t4 mm) by a molding machine at a molding temperature of 175 °C for 5 minutes. After molding, the rod was placed in an oven at 175 °C for 5 hours. The cured rod was cut into dimensions (50 mm × 3 mm × t4 mm) for DMA. The Tg of the cut rod was measured using DMA, wherein the sample was placed in the DMA machine, heated at a rate of 5 °C / min, heated to 300 °C with a nitrogen flow of 300 mL / min, at a frequency of 10 Hz, in bending mode, and the Tg was obtained from the peak of tanδ.

[0211] Coefficient of thermal expansion (CTE) measured by TMA

[0212] CTEα1 and CTEα2 values ​​were determined using a TMA 8311 thermomechanical analyzer (TMA) from Rigaku Inc., under the following test conditions:

[0213] In this application, the sample in the extruder is molded into a strip (80 mm × 10 mm × 4 mm) by a molding machine at a molding temperature of 175°C for 5 minutes. After molding, the bar is placed in an oven at 175°C for 5 hours. The cured bar is cut into dimensions (10 mm × 5 mm × 4 mm) for TMA. The sample is heated from room temperature to 300°C at a rate of 5°C / min with a load of 0.1 N. Specifically, CTEα1 represents the coefficient of thermal expansion below the Tg temperature, and CTEα2 represents the coefficient of thermal expansion above the Tg temperature. The standard calculation temperature range for CTEα1 is 25°C to 80°C, and the calculation temperature range for CTEα2 is 150°C to 250°C. The value of Tg can also be calculated by determining the intersection of data from CTEα1 and CTEα2, based on the test chart that determines the values ​​of CTEα1 and CTEα2.

[0214] hygroscopic

[0215] The moisture absorption rate test method was performed according to "PCT24", where the sample size was set to φ 50. The sample was 3mm thick, and the test conditions were 121℃ / 100RH% / 2atm / 24 hours. The moisture absorption rate can be calculated as follows: weight increment of the sample after 24 hours of PCT / weight of the sample × 100%.

[0216] The test results are shown in Table 3.

[0217] Table 3:

[0218]

[0219] LHD: Long arm direction; SHD: Short arm direction

[0220] DMA: Dynamic Mechanical Analysis

[0221] TMA: Thermomechanical Analyzer

[0222] E': Energy storage modulus

[0223] E”: Loss modulus

[0224] Tg: Glass transition temperature

[0225] CTE: Coefficient of thermal expansion

[0226] For imide-functionalized organopolysiloxanes, the results for the compositions prepared in Table 3 show that the CTEα1 (25–80 °C) is significantly lower than that of the control and baseline samples, with a minimum value of 8.4 ppm. Furthermore, a decrease in CTEα2 (150–250 °C) was also observed in the imide-functionalized organopolysiloxane compositions compared to the control. In cases where the CTE values ​​of compositions with imide-functionalized organopolysiloxanes (e.g., E1-2, E2-4, E2-5) were found to be comparable to those based on the control or baseline compositions, this was compensated for by improved spiral flow properties, reduced water absorption, or reduced curing shrinkage, as shown in Table 3. Additionally, the mechanical properties of the compositions with imide-functionalized organopolysiloxanes were found to be improved compared to the baseline compositions.

[0227] The foregoing description includes examples from this specification. Of course, for the purposes of describing this specification, it is impossible to describe all conceivable combinations of components or methods, but those skilled in the art will recognize that many further other combinations and arrangements are possible. Therefore, this specification is intended to cover all such substitutions, modifications, and variations, provided they fall within the spirit and scope of the appended claims. Furthermore, with respect to the use of the term "comprising" in the detailed description or claims, such a term is intended to be inclusive, and is used in a manner similar to the term "including," since "including" is interpreted as inclusive when used as a transitional word in a claim.

[0228] The foregoing description identifies various non-limiting embodiments of the composite resin composition. Modifications can be made by those skilled in the art, as well as those who can manufacture and use the invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or the subject matter set forth in the claims.

Claims

1. A composition comprising: An imide-functionalized organopolysiloxane comprising an imide functional group and at least one functional group selected from epoxy, hydride, aromatic, aliphatic, amine and / or acryloyl or acryloyloxy groups, wherein the organopolysiloxane is selected from linear siloxanes and nonlinear siloxanes, wherein the nonlinear siloxane comprises at least two of the functional groups selected from epoxy, hydride, aromatic, aliphatic, amine and / or acryloyl or acryloyloxy groups; Polymer resins that react with the imide-functionalized organopolysiloxanes; catalyst; packing; and Optional adhesion promoters, release agents, and plasticizers, The composition described therein provides a coefficient of thermal expansion (CTE) value of less than 12 ppm.

2. The composition according to claim 1, wherein the imide-functionalized organopolysiloxane is according to formula (I). (I) Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 and R 14 Each is independently selected from hydrogen, C1-C15 alkyl, epoxy, C6-C30 aromatic groups and imide groups, provided that (i)R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 and R 14 At least one of them is selected from an imide group, and (ii)R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 and R 14 At least one of them is selected from epoxy groups; A1, A2, A3 and L1, L2, L3, L4, L5, L6, L7, L8, L9, L 10 L 11 and L 12 Each of these is a linking group independently selected from divalent alkyl, divalent alkenyl, and divalent ether groups; o≥1； w, x, y and z are each ≥ 0, where (w+x+y+z) ranges from 1 to 60; k1, k2, k3, k4, k5, k6, k7, k8, k9, k10.

3. The composition according to claim 2, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 At least one of them is selected from imide, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 At least one of them is selected from epoxy groups, and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 At least one of them is selected from C6-C30 aromatic groups.

4. The composition according to claim 2, wherein R1, R2, R3, R4, R5, R7, R9, R 10 R 11 and R 12 Independently selected from hydrogen, C1-C15 alkyl groups and C6-C30 aromatic groups, R 13 Selected from imide functional groups, and R 14 Selected from epoxy functional groups.

5. The composition according to claim 2, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and / or R 12 Each is independently selected from hydrogen and C1-C15 alkyl groups, and R 13 and R 14 Selected from substituted or unsubstituted diimides.

6. The composition according to any one of claims 2-5, wherein the imide group is selected from groups of formula (IV), (V) and (VI): (IV); (V)； (WE) Where R 18 R 19 R 20 and R 21 Independently selected from C2 to C30 divalent hydrocarbons, and R 22 Selected from C1-C10 divalent hydrocarbons.

7. The composition according to any one of claims 1-6, wherein the imide-functionalized organopolysiloxane has the following formula: 。 8. The composition according to any one of claims 1-6, wherein the imide-functionalized organopolysiloxane has the following formula: 。 9. The composition according to any one of claims 1-8, wherein the imide-functionalized organopolysiloxane is present in an amount of about 1% to about 10% by weight.

10. The composition according to any one of claims 1-9, wherein the polymer resin is a combination of a functional resin and at least one resin curing agent.

11. The composition according to any one of claims 1-10, wherein the functional resin is selected from epoxy resin, polyurethane resin, polyamide resin, polyimide resin, acrylic resin, silicone resin, phenolic resin, or a combination of two or more thereof.

12. The composition of claim 11, wherein the functional resin is present in an amount of about 7% by weight to about 35% by weight.

13. The composition according to any one of claims 1-10, wherein the resin curing agent is selected from phenolic resins, phenol-derived resins, substituted phenol-derived resins, or acid anhydride resins.

14. The composition of claim 13, wherein the resin hardener is present in an amount of about 5% by weight to about 30% by weight.

15. The composition according to claims 1-10, wherein the composition comprises the resin curing agent and the functional resin in a ratio of 1:1 to 1:1.

5.

16. The composition according to claims 1-15, wherein the composition is a two-component epoxy curing system.

17. The composition according to any one of claims 1-16, wherein the filler comprises alumina, fused silica, or a combination thereof.

18. The composition according to claims 1-17, wherein the composition has a CTE value of less than 11 ppm.

19. The composition according to any one of claims 1-18, having a spiral flow of about 50 cm to about 100 cm.

20. An epoxy molding compound formed from the composition of any one of claims 1-19.

21. An article comprising a material formed from the composition according to any one of claims 1-20.

22. The article of claim 21, wherein the article is selected from semiconductor packaging, electronic materials or electronic coatings.

23. The article of claim 22, wherein the article of claim 22 is an electronic component comprising the material.

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