JP5345904B2 - Liquid composition and electronics packaging material - Google Patents

Description

The present invention relates to a liquid composition and an electronic packaging material. More specifically, liquid compositions used for various applications such as mounting applications, optical applications, optical device applications, display device applications, mechanical component applications, electrical / electronic component applications, automotive component applications, printing ink applications, and the like, and The present invention relates to an electronic packaging material using the same.

Resin compositions that are in a liquid state at room temperature have various fluidity, such as mounting applications, optical applications, optical device applications, display device applications, mechanical component applications, electrical / electronic component applications, automotive component applications, printing ink applications, etc. Widely used in various applications. Such a liquid composition is usually provided with fluidity by including a volatile component such as an organic solvent or a diluent, but it is desired that the organic solvent is not included as much as possible depending on the application. There is a demand for the development of a composition that can exist in a liquid state at room temperature without being contained.

Therefore, a liquid composition prepared by mixing only low molecular weight raw materials having flowability at room temperature has been developed. For example, Patent Document 1 discloses an epoxy resin, a curing agent, and a compound containing a ketimine structure. Regarding the liquid semiconductor sealing material to be included, it is described that an epoxy compound that is liquid at room temperature is used as an epoxy resin. Patent Document 2 discloses a flame retardant liquid epoxy resin composition for semiconductor encapsulation using a liquid epoxy resin.

On the other hand, as a resin composition that is excellent in various properties such as heat resistance and pressure resistance and can form a cured product having various physical properties even under harsh environments, it includes a silane compound having a siloxane bond and an imide bond, and an organic resin. A resin composition is disclosed (see Patent Document 3).

JP 2008-248099 A (2nd and 4th pages) JP 2008-266512 A (2nd page) International Publication No. 2008/099904 (pages 142-152, 158)

Various liquid compositions have been studied as described above. However, as in Patent Documents 1 and 2, in the case of a liquid composition obtained by mixing only low molecular weight raw materials having fluidity at room temperature, the heat resistance (heat decomposition resistance) is not sufficient. Therefore, there is room for improvement to further improve heat resistance. Patent Document 1 also describes that when a solid raw material is used when obtaining a liquid composition, it is diluted with another liquid resin or diluent so as to show a liquid state. However, the liquid composition obtained by diluting with a diluent cannot be suitably applied to applications where it is desired not to contain volatile components.

Moreover, the resin composition described in Patent Document 3 can exhibit excellent heat resistance without impairing properties such as excellent moldability and flexibility, and is extremely useful for various applications. In Examples of Patent Document 3, a resin composition that is liquid at room temperature is obtained as a resin mixed solution in which an organic resin such as a cresol novolac type epoxy resin and a phenol aralkyl resin or a triphenol type epoxy resin is mixed and dissolved in a solvent. However, in order to be applicable to applications where it is desired not to contain volatile components such as organic solvents and diluents as much as possible, a composition that can exist in a liquid state at room temperature without substantially containing volatile components There was room for ingenuity to do. The organic resin specifically disclosed in Patent Document 3 is an amorphous resin containing an oligomer component and does not have a melting point, but is solid at room temperature and has a high viscosity even when melted. Therefore, there has been room for improvement to use as a liquid composition.

The present invention has been made in view of the above-described present situation, and is excellent in various physical properties such as heat resistance, and can exist in a liquid state at room temperature even when substantially free of volatile components such as an organic solvent and a diluent. An object of the present invention is to provide a composition and an electronic packaging material using the composition.

The inventors of the present invention have studied various types of resin compositions in a liquid state at room temperature, and have reacted with a reactive group-containing compound that is solidified at room temperature and has a melting point of a specific temperature or less, a silane compound, a crosslinking agent, It has been found that the reactive group-containing compound and the silane compound are mixed at the molecular level when used together. This is considered to be derived from the fact that the silane compound has the action of breaking the crystal structure of the reactive group-containing compound, but when these components are used in combination, it is excellent in various physical properties such as heat resistance and an organic solvent. We found that it was possible to demonstrate a very different working effect that would overturn the conventional common sense that a composition that is in a liquid state at room temperature can be obtained without containing volatile components such as a diluent and a diluent, and solve the above problems brilliantly I came up with the idea that I could do it. Such a composition is excellent in various performances such as heat resistance, and can exist in a liquid state at room temperature even without containing a volatile component. It can be particularly suitably used for applications, optical device applications, display device applications, mechanical component applications, electrical / electronic component applications, automobile component applications, and the like. Moreover, it cannot be overemphasized that it can apply suitably also for the use which may contain a volatile component, for example, a printing ink use etc.

As described above, in the present invention, by using a reactive group-containing compound that is solidified at room temperature and has a melting point equal to or lower than a specific temperature, together with a silane compound, not only has excellent thermal decomposition resistance, but also volatilization. Although it is possible to exhibit a unique effect that a composition that can exist in a liquid state at room temperature can be obtained without using a component, such an effect can be said to be a very different effect that overturns conventional technical common sense. Conventionally, when trying to obtain a liquid composition, as described in Patent Documents 1 to 3, it was usual to contain a volatile component or already use a liquid resin at room temperature. In the case where it is desired to contain no volatile component, it cannot be suitably applied to applications where it is desired to contain no volatile component. In addition, when a liquid resin is already used at room temperature, the thermal decomposition resistance is often insufficient. . The liquid composition of the present invention solves these problems at the same time and has important technical significance. In addition, the present invention itself, which uses a reactive group-containing compound solidified at room temperature as a main raw material and can exist as a liquid composition without substantially containing a volatile component, is an unprecedented new technology. I can say that.

（式中、Ｒ^１は、芳香族、複素環及び脂環からなる群より選ばれる少なくとも１種の構造を表す。ｘ及びｚは、同一又は異なって、０以上５以下の整数である。ｙは、０又は１である。）で表される構成単位及びシロキサン骨格を有するシラン化合物とを含む液状組成物であって、該反応性基含有化合物は、室温で固化しており、かつ２００℃以下に融点を有する化合物である液状組成物である。
本発明はまた、上記液状組成物を用いてなるエレクトロニクス実装材料でもある。
以下に本発明を詳述する。 That is, the present invention includes a reactive group-containing compound, a crosslinking agent, and the following formula (1):

(In the formula, R ¹ represents at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings. X and z are the same or different and are integers of 0 or more and 5 or less. Y Is a liquid composition comprising a structural unit represented by formula (1) or a silane compound having a siloxane skeleton, wherein the reactive group-containing compound is solidified at room temperature and is 200 ° C. The following is a liquid composition which is a compound having a melting point.
The present invention is also an electronic packaging material using the above liquid composition.
The present invention is described in detail below.

The liquid composition of the present invention comprises a reactive group-containing compound, a crosslinking agent and a silane compound, and each of these components can be used alone or in combination of two or more. Moreover, as long as these are essential, other components can also be included appropriately. Other components (additives) are as described later.

In the present invention, the “liquid composition” means a composition in a liquid state at room temperature (25 ° C.). Specifically, the crystal is not precipitated and the fluid is not a high-viscosity fluid, and it may be confirmed visually, but it can also be determined by the viscosity. For example, the viscosity at 60 ° C. is preferably 100 Pa · s or less. Thereby, since it becomes a composition in a liquid state at room temperature, processing and molding become easier, and it can be preferably employed for various applications. The viscosity at 60 ° C. is more preferably 80 Pa · s or less, and still more preferably 60 Pa · s or less. Further, 40 Pa · s or more is preferable. The liquid composition is also preferably in a liquid state within a range of -20 to 60 ° C.
The viscosity of the liquid composition can be measured using, for example, a cone plate viscometer (device name “cap2000H”, manufactured by Brookfield) at a measurement temperature of 60 ° C.

In the liquid composition, the reactive group-containing compound is a compound that is solidified at room temperature and has a melting point at 200 ° C. or lower. Solidified at room temperature means solid at room temperature (25 ° C.). Among these, it is preferable to be in a crystalline state. Here, when an amorphous compound is used, a composition that can exist in a liquid state cannot be obtained even if it does not substantially contain a volatile component. More preferably, it is in a solid state within a range of -20 to 60 ° C.

The melting point of the reactive group-containing compound is suitably 200 ° C. or lower. If it has a melting point exceeding 200 ° C., it cannot be sufficiently mixed with the silane compound at the molecular level, and a composition containing this can be present in liquid form at room temperature even without containing volatile components. Can be difficult. Preferably it is 190 degrees C or less, More preferably, it is 180 degrees C or less. In addition, a compound having a melting point that is too low becomes a compound containing a large amount of an aliphatic / alicyclic skeleton in the skeleton, and the heat resistance may not be sufficient. Accordingly, the melting point is preferably 40 ° C. or higher. More preferably, it is 50 degreeC or more, More preferably, it is 80 degreeC or more, Most preferably, it is 90 degreeC or more.
In the present specification, the melting point means a temperature (° C.) at which a crystal melts and becomes liquid under an inert atmosphere. Therefore, an amorphous compound does not have a melting point.

The reactive group-containing compound is a compound containing a reactive functional group (reactive group), and the reactive group means a functional group that can react with a crosslinking agent to form a crosslinked structure. To do. Such a reactive group is preferably, for example, a glycidyl group, an epoxy group, a maleimide group, or the like. This makes it possible to obtain a composition that is superior in various physical properties such as heat resistance. Thus, the form in which the reactive group-containing compound is a compound having at least one functional group selected from the group consisting of a glycidyl group, an epoxy group, and a maleimide group as a reactive group is also included in the present invention. One preferred form.
The reactive group-containing compound is also preferably a compound having an aromatic ring structure or a heterocyclic structure in its structure. Thereby, it becomes possible to further improve the thermal decomposition resistance of the liquid composition of the present invention.

The reactive group-containing compound may also be a compound having one or more reactive groups in one molecule, or one or more of the compounds may be used. Among these, it is preferable to use two or more compounds having one or more reactive groups in one molecule. For example, it is preferable to use a compound having one or more reactive groups among a glycidyl group, an epoxy group, and a maleimide group, and a compound having a reactive group different from the reactive group. As a result, the two types of cross-linked structures in the cured body of the composition form a reciprocal network structure, so that the heat resistance is further improved and various physical properties are excellent, and the liquid that is in a liquid state at room temperature. A composition will be obtained. More preferably, as the reactive group-containing compound, a compound having an epoxy group and / or a glycidyl group and a compound having a maleimide group are used in combination.

As said reactive group containing compound, what has an aromatic ring structure or a heterocyclic structure in the frame | skeleton is suitable. This makes it possible to obtain a liquid composition that is further excellent in thermal decomposition resistance. In addition, although the low molecular weight raw material which has fluidity | liquidity at room temperature like patent document 1 and 2 contains many aliphatic skeletons in the structure, it is thought that the thermal decomposition resistance was not enough for it. Therefore, it is preferable that the skeleton constituent ratio by the aromatic ring or heterocyclic structure in the reactive group-containing compound is high.

The reactive group-containing compound preferably has a molecular weight of 100 to 1,000. If the polymer compound exceeds 1000, the composition containing the polymer compound has a high viscosity and may not be present in liquid form at room temperature. Moreover, when it is less than 100, it becomes a compound which does not contain an aromatic ring or a heterocyclic skeleton substantially, and there exists a possibility that heat resistant decomposition etc. may not become enough. More preferably, it is 100-800, More preferably, it is 100-600.

Specifically, the reactive group-containing compound can be suitably used as long as it is a compound having the characteristics, structure, and the like as described above. For example, the following formulas (a) to (c):

Or an epoxy group-containing compound represented by the following formulas (d) to (f):

However, it is not limited to only these compounds, and the compound represented by the above formula is used as long as it has a reactive group, is solidified at room temperature, and has a melting point of 200 ° C. or lower. It can act in the same manner as the compounds represented by (a) to (f).

In the liquid composition, the crosslinking agent is not particularly limited as long as it is a compound that can react with the reactive group of the reactive group-containing compound described above to form a crosslinked structure, and is also liquid at room temperature, Or what melt | dissolves in another component and becomes a liquid is suitable. For example, 3,4-dimethyl-6- (2-methyl-1-propenyl) -1,2,3,6-tetrahydrophthalic anhydride, 1-isopropyl-4-methyl-bicyclo [2.2.2 ] Oct-5-ene-2,3-dicarboxylic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride, pyromellitic dianhydride, maleated alloocimene Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetrabisbenzophenone tetracarboxylic dianhydride, (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4- Dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, methyl nadic acid, etc. Anhydrides: various phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, terpene phenol resin; various phenols and hydroxybenzaldehyde, crotonaldehyde, glyoxal Various phenol resins such as polyhydric phenol resins obtained by condensation reaction with various aldehydes such as BF ₃ complex; sulfonium salts; imidazoles; methylene dianiline, diaminobenzenes, diaminodiphenyl sulfone, bis (chloroanilino) ) Methane, oxydianilines, bis (hydroxyanilino) methanes, bis [(aminophenoxy) phenyl] sulfones, bis (aminophenoxy) benzenes, Scan (aminophenoxy) biphenyls, amine compounds represented by the aromatic amine compound of the dimethyl amino biphenyl and the like, can be used alone or in combination of two or more thereof.

Among these, amine compounds (preferably aromatic amine compounds), dicarboxylic acid anhydrides and tetracarboxylic acid dianhydrides are particularly preferable. By using these as crosslinking agents, the reactive group-containing compound can be more sufficiently crosslinked. Further, it is possible to obtain a cured product excellent in various physical properties such as heat resistance. Thus, a form in which the cross-linking agent is at least one compound selected from the group consisting of an amine compound, a dicarboxylic acid anhydride, and a tetracarboxylic dianhydride is also a preferred form of the present invention. It is.

The amount of the crosslinking agent used may be appropriately set depending on the type of the reactive group in the crosslinking agent and the reactive group-containing compound. For example, the crosslinking amount is 1 mol of the reactive group in the reactive group-containing compound. It is preferable to set the amount so that the reactive functional group in the agent is 0.1 to 10 mol. This makes the material more suitable as a material excellent in processability, heat resistance, and the like. More preferably, it is 0.3-5 mol, More preferably, it is 0.6-1.5 mol.

In the liquid composition, the silane compound is a compound having a structural unit represented by the above formula (1) (hereinafter also referred to as “structural unit (1)”) and a siloxane skeleton. By using a silane compound having such a structure, it has excellent heat resistance, pressure resistance, mechanical / chemical stability, thermal conductivity, and imparts various properties such as excellent heat resistance to various materials. it can. For example, it is possible to easily impart heat resistance, pressure resistance, etc. by appropriately selecting the structure such as the siloxane skeleton and the structural unit (1) and exhibiting high compatibility with various reactive group-containing compounds. Is possible. Thereby, the hardened | cured material with a low fall of various physical properties can be formed also in severe environments, such as high temperature high pressure, and it can use suitably for a mounting use etc.

In the silane compound, an organic residue having an imide bond and an oxygen atom are bonded to a silicon atom to form a siloxane skeleton through the oxygen atom, and the organic skeleton having the imide bond is at least a structural unit. It is suitable that it is a form containing (1). That is, an organic compound having an imide bond in which an organic skeleton having one or more imide bonds, one or more oxygen atoms, and optionally other skeletons are bonded to a silicon atom to which an organic skeleton having an imide bond is bonded. The total number of bonds of the skeleton, oxygen atom, and other skeleton is 4, and the organic skeleton having an imide bond preferably includes at least the structural unit (1).

In such a form, the number of bonds of the organic skeleton having an imide bond bonded to a silicon atom is suitably 1 to 3, preferably 1 to 2, more preferably 1. The number of bonds of oxygen atoms (oxygen atoms bonded to silicon atoms bonded to an organic skeleton having an imide bond) is suitably 1 to 3, preferably 2 to 3, more preferably 3. . The number of bonds of other organic skeletons is suitably 0 to 2, preferably 0 to 1, and more preferably 0. As a suitable combination (number of bonds) of the skeleton (group) bonded to the silicon atom, (organic skeleton having an imide bond, oxygen atom, other skeleton) is (1, 3, 0), (2, 2, 0 ), (1, 2, 1), (3, 1, 0), (2, 1, 1), (1, 1, 2).

The other skeleton is preferably at least one selected from the group consisting of an organic group having no imide bond, a hydrogen atom, a hydroxyl group, a halogen atom, and an OR group (R is the same or different, an alkyl group, It represents at least one group selected from the group consisting of an acyl group, an aryl group, and an unsaturated aliphatic residue, and may have a substituent.
The organic group having no imide bond is preferably at least one selected from the group consisting of an aromatic residue such as an alkyl group, an aryl group, and an aralkyl group, and an unsaturated aliphatic residue. It may have a substituent. More preferably, it is a C1-C8 alkyl group which may have a substituent, or aromatic residues, such as an aryl group and an aralkyl group. Specifically, for example, methyl group, ethyl group, phenyl group, vinyl group, chloropropyl group, mercaptopropyl group, (epoxycyclohexyl) ethyl group, glycidoxypropyl group, N-phenyl-3-aminopropyl group, (Meth) acryloxypropyl group, hexyl group, decyl group, octadecyl group, trifluoropropyl group and the like are preferable.

As the siloxane skeleton (main chain skeleton requiring a siloxane bond) of the silane compound, any siloxane bond (Si—O—Si bond) may be used. Either a chain shape or a branched shape may be used, and a polysilsesquioxane having a ladder shape, a cage shape, a cubic shape or the like is preferable.

In the silane compound, the proportion of the siloxane skeleton is preferably 80 to 10% by mass in 100% by mass of the silane compound. More preferably, it is 70-15 mass%, More preferably, it is 50-20 mass%.
In the silane compound, the proportion of the organic skeleton having an imide bond including at least the structural unit (1) is preferably 100 to 20 moles with respect to 100 moles of silicon atoms contained in the silane compound. More preferably, it is 100-50 mol, More preferably, it is 100-70 mol.

When a suitable form of the silane compound is represented by an average composition formula, the following average composition formula (2):
XaYbZcSiOd (2)
(Wherein X is the same or different and represents an organic skeleton containing an imide bond and contains at least the structural unit represented by the formula (1). Z is the same or different and does not contain an imide bond. Y represents the same or different and represents at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR group, and R represents the same or different and represents an alkyl group, an acyl group or an aryl group. Represents at least one group selected from the group consisting of a group and an unsaturated aliphatic residue, and may have a substituent, a is a number that is not 0 and 3 or less, and b is 0 or less than 3. C is a number less than 0 or less than 3, d is a number less than 2 that is not 0, and a + b + c + 2d = 4. In the average composition formula (2), the coefficient a of X is a number 0 <a ≦ 3, the coefficient b of Y is a number 0 ≦ b <3, and the coefficient c of Z is 0 ≦ c <Number less than 3. The coefficient d of O is 0 <d <2.

In the above average composition formula (2), X represents an organic skeleton containing an imide bond and contains at least the structural unit (1), but X is preferably the structural unit (1). That is, it is preferable that X in the average composition formula (2) is a structural unit represented by the formula (1).
In the average composition formula (2), Y is preferably a hydroxyl group or an OR group. An OR group is more preferable, and an OR group in which R is an alkyl group having 1 to 8 carbon atoms is more preferable. Z is preferably at least one selected from the group consisting of aromatic residues such as alkyl groups, aryl groups and aralkyl groups, and unsaturated aliphatic residues (these have a substituent). May be.) More preferably, it is an aromatic residue such as an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group which may have a substituent.

The silane compound also includes, for example, the following formula (3):

(In the formula, X, Y and Z are the same as described above. N ₁ and n ₂ represent the degree of polymerization. N ₁ is a non-zero positive integer, and n ₂ is 0 or positive. It is an integer.)
"Y / Z-" represents that Y or Z is bonded, " _X1-2- " represents that one or two X are bonded, and "(Z / Y _1-2 ) "represents that one Z or Y is bonded, two Z or Y are bonded, or two Z and Y are bonded in total. “Si— (X / Y / Z) ₃ ” indicates that any three selected from X, Y, and Z are bonded to a silicon atom.
In the above formula (3), Si—Om1 and Si—Om2 do not define the bonding order of Si—Om1 and Si—Om2, and for example, Si—Om1 and Si—Om2 co-condensate alternately or randomly. Or a polysiloxane composed of Si—Om1 and a polysiloxane composed of Si—Om2 are suitable, and the condensation structure is arbitrary.

The silane compound can be represented by the above average composition formula (2) as described above, and the siloxane skeleton (main chain skeleton in which a siloxane bond is essential) of the silane compound is represented by (SiO _m ) _n. You can also. The structure other than (SiO _m ) _n in such a silane compound includes at least the structural unit (1), an organic skeleton having an imide bond (a structure in which an imide bond is essential) X, Y such as a hydrogen atom or a hydroxyl group, And it is the organic group Z which does not contain an imide bond, and these will be bonded to the silicon atom of the main chain skeleton.
X, Y and Z may or may not be included in the repeating unit in the form of a “chain”. For example, one or more Xs may be contained in one molecule as a side chain. In the above (SiO _m ) _n , n represents the degree of polymerization, and the degree of polymerization represents the degree of polymerization of the main chain skeleton, and n organic skeletons having an imide bond may not necessarily exist. In other words, an organic skeleton having one imide bond in one unit of (SiO _m ) _n is not necessarily present. In addition, one or more organic skeletons having an imide bond may be included in one molecule, but when a plurality of organic skeletons are included, as described above, an organic skeleton having two or more imide bonds in one silicon atom. It may be bonded. The same applies to the following.

In the main chain skeleton (SiO _m ) _n , m is preferably a number of 1 or more and less than 2. More preferably, m = 1.5 to 1.8.
The above n represents the degree of polymerization and is preferably 1 to 5000. More preferably, it is 1-2000, More preferably, it is 1-1000, Most preferably, it is 1-200.
The silane compound in the case where n is 2 includes a form containing two structural units in which at least one organic skeleton (X) having an imide bond is bonded to a silicon atom, and only one such structural unit. Examples include forms that are not included. Specifically, the following formula:

(Wherein A is Y or Z, and X, Y and Z are the same as defined above), respectively, and the like, and the same structural unit (at least one X is bonded to a silicon atom). There are a homopolymer form containing two structural units), a homopolymer form containing two different structural units, and a copolymer form (cocondensed structure form) containing only one of the structural units.

In the structural unit (1), that is, the structural unit represented by the formula (1), x and z are the same or different and are integers of 0 or more and 5 or less. Moreover, y is 0 or 1, and is preferably 0. x + y may be an integer of 0 or more and 10 or less, but is preferably 3 to 7, more preferably 3 to 5, and particularly preferably 3.

Also in the above formula (1), R ¹ represents at least one structure selected from the group consisting of aromatic, heterocyclic, and alicyclic. That is, R ¹ is composed of a group having a ring structure (aromatic ring) of an aromatic compound, a group having a ring structure (heterocycle) of a heterocyclic compound, and a group having a ring structure (alicyclic ring) of an alicyclic compound. It represents at least one group selected from the group.
Specifically, R ¹ is preferably a phenylene group, a naphthylidene group, a divalent group of norbornene, an (alkyl) cyclohexylene group, a cyclohexenyl group, or the like.
The structural unit (1) is a structural unit represented by the following formula (1-2) when R ¹ is a phenylene group, and the following structural unit (1) when R ¹ is an (alkyl) cyclohexylene group. When the structural unit is represented by the formula (1-3) and R ¹ is a naphthylidene group, the structural unit is represented by the following formula (1-4), and R ¹ is a divalent group of norbornene Is a structural unit represented by the following formula (1-5), and when R ¹ is a cyclohexenyl group, it is a structural unit represented by the following formula (1-6).

In the above formulas (1-2) to (1-6), x, y and z are the same as in the above formula (1).
In the above formula (1-2), R ^{2 to} R ⁵ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic.
In the above formula (1-3), R ^{6 to} R ⁹ and R ^{6 ′ to} R ^{9 ′} are the same or different and are at least one selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. Represents the structure. As the ^R 6 to R ⁹ and ^{R 6'to R 9',} form all ^{R 7} or ^{R 8} are the remaining methyl group is a hydrogen atom, ^or, R 6 to R ⁹ and ^R 6'to R ^{9 'all} are hydrogen atom form ^or embodiment R 6 to R ⁹ and ^{R 6'to R 9'all} are a fluorine atom is preferable. More preferably, R ⁷ or R ⁸ is a methyl group and the rest are all hydrogen atoms.

In the above formula (1-4), R ^{10 to} R ¹⁵ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. As said R < ¹⁰ > -R < ¹⁵ >, the form whose all are hydrogen atoms or the form whose all are fluorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In said formula (1-5), R < ¹⁶ > -R < ²¹ > is the same or different and represents at least 1 sort (s) of structure chosen from the group which consists of a hydrogen atom, an alkyl group, a halogen atom, and aromatic. As said R < ¹⁶ > -R < ²¹ >, the form in which all are hydrogen atoms, the form in which all are fluorine atoms, or the form in which all are chlorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In the above formula (1-6), R ^{22 to} R ²⁵ , R ^{22 ′} and R ^{25 ′} are the same or different and are at least one selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. Represents the structure. As the ^R 22 ^{~R 25, R 22'} and ^{R 25 ',} forms all are hydrogen atom, and all are a fluorine atom form or any form of embodiment all is a chlorine atom is preferable. More preferred is a form in which all are hydrogen atoms.

Among the structural units (1), the following formula (1-7):

(Wherein R ²⁶ represents a structural unit represented by at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings). That is, a form in which the silane compound is a compound having a structural unit represented by the above formula (1-7) and a siloxane skeleton is also a preferred form of the present invention. R ²⁶ in the above formula (1-7) is preferably the same as R ¹ described in the above formula (1).

As a particularly preferable form of the silane compound, poly (γ-phthalopropylpropylsilsesquioxane) in which R ²⁶ is a phenylene group, poly {γ- (hexahydro-4-methyl) in which R ²⁶ is a methylcyclohexylene group. phthalimido) propyl ^{silsesquioxane},} poly {.gamma. poly ^{R 26} is naphthylidene group {.gamma. (1,8-naphthalimide) propyl ^{silsesquioxane}, R 26} is divalent norbornene ( 5-norbornene-2,3-imido) propylsilsesquioxane}, poly [(cis-4-cyclohexene-1,2-imido) propylsilsesquioxane] in which R ²⁶ is a cyclohexenyl group. The structures of these compounds can be identified by measuring ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS.

Although it does not specifically limit as a method to obtain the said silane compound, For example, the following manufacturing method etc. are mentioned as a method in the case of obtaining the silane compound represented by the said average compositional formula (2).
(A) An intermediate (consisting of a silane compound) represented by an average composition formula X′aYbZcSiOd having an organic skeleton X ′ having an amide bond corresponding to the organic skeleton X containing an imide bond in the silane compound and a siloxane bond The manufacturing method including the process of imidating.
(B) The organic skeleton having an imide bond corresponding to the organic skeleton X containing an imide bond in the silane compound is hydrolyzed / condensed by an intermediate composed of a silane compound bonded to a silicon atom and having a hydrolyzable group. A manufacturing method including a process.

As content of the silane compound in the said liquid composition, it is suitable that it is 10-200 weight part with respect to 100 weight part of total amounts of a reactive group containing compound and a crosslinking agent. If it is less than 10 parts by weight, it may be difficult to obtain a composition in a liquid state at room temperature. If it exceeds 200 parts by weight, the silane compound cannot be sufficiently dispersed, and the crosslinked structure of the cured product is not uniform. Therefore, the heat resistance may not be sufficiently high. More preferably, it is 15-150 weight part, More preferably, it is 20-120 weight part.

The liquid composition of the present invention may also contain additives other than the above essential components. For example, volatile components such as organic solvents and diluents, curing accelerators, stabilizers, mold release agents, coupling agents, colorants, plasticizers, flexible agents, various rubber-like materials, photosensitizers, fillers, A flame retardant, a pigment, etc. are mentioned, These 1 type (s) or 2 or more types can be used.

It does not specifically limit as said volatile component, What is necessary is just to use what is normally used.
Here, as described above, the liquid composition of the present invention can exist in a liquid state at room temperature without containing a volatile component, and can be suitably used for applications where it is desired not to contain a volatile component. is there. Therefore, the content of the volatile component in 100% by mass of the liquid composition is preferably 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it does not contain a volatile component substantially. “Substantially free of volatile components” means that the content of volatile components is less than the amount capable of dissolving the composition, for example, 1% by mass or less in 100% by mass of the liquid composition. It is preferable that Thus, the form in which the liquid composition does not substantially contain a volatile component is also one of the preferred forms of the present invention. In addition, when using for the use which may contain a volatile component, such as a printing ink use, the said liquid composition may contain the volatile component, and such a form is also one of suitable embodiment of this invention. One.
As described above, the liquid composition of the present invention has a very unique property that it can exist in a liquid state at room temperature regardless of whether or not it contains a volatile component. Has significant significance.

As said hardening accelerator, 1 type (s) or 2 or more types, such as organic phosphorus compounds, such as a triphenyl phosphine, a tributyl hexadecyl phosphonium bromide, a tributyl phosphine, a tris (dimethoxyphenyl) phosphine, are suitable, for example.

The liquid composition also preferably has a 5% mass reduction temperature of the cured product of 290 ° C. or higher. Since the 5% mass reduction temperature is high, that is, the heat decomposition resistance (heat resistance) is excellent, it is more suitable when used as a member used at a high temperature. The 5% mass reduction temperature is more preferably 300 ° C. or higher, still more preferably 310 ° C. or higher.
The above-mentioned 5% mass reduction temperature is obtained by using, for example, a differential thermal balance (equipment name “TG-DTA2000SA”, manufactured by Bruker) for the cured liquid composition. It can be measured as lower 100 ml / min.

The liquid composition of the present invention may be prepared so as to include a reactive group-containing compound, a crosslinking agent, and a silane compound. For example, the liquid composition is preferably prepared as follows. That is, a reactive group-containing compound, a silane compound, and an organic solvent are charged into a reaction vessel, heated and mixed at 40 to 200 ° C., and then desolvated, and then a crosslinking agent is charged and stirred to room temperature. It is preferable to obtain the liquid composition of the present invention by cooling. As a result, the reactive group-containing compound and the silane compound are mixed at the molecular level, and a composition that can exist in a liquid state at room temperature without containing a volatile component such as a solvent is obtained. Thus, including the step of heating and mixing the reactive group-containing compound, the silane compound and the organic solvent, the solvent removal step, the step of adding the crosslinking agent, and the step of cooling to room temperature (preferably in this order, A method for producing a liquid composition (including these steps) is also one preferred embodiment of the present invention. In addition, when using for the use which may contain a volatile component, it does not need to pass through a desolvent process.

In the above production method, as the organic solvent used in the heating and mixing step, for example, a compound having at least one structure selected from the group consisting of an ether bond, an ester bond and a nitrogen atom is suitably used.
Examples of the compound having an ether bond include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, anisole, phenetole, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, and benzyl ethyl. Ether, diphenyl ether, dibenzyl ether, peratrol, propylene oxide, 1,2-epoxybutane, dioxane, trioxane, furan, 2-methylfuran, tetrahydrofuran, tetrahydropyran, thionel, 1,2-dimethoxyethane, 1,2-di Ethoxyethane, 1,2-dibutoxyethane, glycerin ether, crown ether, methylal, acetal, methyl cellosol , Ethyl cellosolve, butyl cellosolve, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, Triethylene glycol monomethyl ether, tetraethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol methyl ether, propylene glycol dimethyl ether, propylene glycol propyl ether Propylene glycol butyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, 2- Methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, 2-phenoxyethanol, 2- (Benzyloxy) ethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc. are preferred It is.

Examples of the compound having an ester bond include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-acetate Butyl, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate , Ethylene glycol monoacetate, diethylene glycol monoacetate, monoacetin, diacetin, triacetin, monobutyrin, dimethyl carbonate, diethyl carbonate, dipropyl carbonate Dibutyl carbonate, butyric acid ester, isobutyric acid ester, isovaleric acid ester, stearic acid ester, benzoic acid ester, ethyl cinnamate, abietic acid ester, adipic acid ester, γ-butyrolactone, shu Acid esters, malonic acid esters, maleic acid esters, tartaric acid esters, citric acid esters, sebacic acid esters, phthalic acid esters, ethylene diacetate and the like are suitable.

Examples of the compound containing the nitrogen atom include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, acetonitrile, propionitrile, succinonitrile, butyronitrile, isobutyronitrile, valeronitrile, Benzonitrile, α-tolunitrile, formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, 2 -Pyrrolidone, N-methylpyrrolidone, ε-caprolactam and the like are preferred.

Examples of the compound having a plurality of structures selected from the group consisting of the ether bond, ester bond and nitrogen atom include N-ethylmorpholine, N-phenylmorpholine, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate. , Phenoxyethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether Acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol butyl ether acetate, tripropylene glycol methyl ether acetate are preferable.

As the usage-amount of the said organic solvent, 5 weight part or more is preferable with respect to 100 weight part of total amounts of a reactive group containing compound and a silane compound (solid content), and 1000 weight part or less is preferable. More preferably, it is 10 parts by weight or more and 300 parts by weight or less.

The heating and mixing step is preferably performed, for example, under a temperature condition of 40 to 200 ° C. As a result, the silane compound can be more sufficiently dispersed. More preferably, it is 60-180 degreeC, More preferably, it is 80-160 degreeC.
Further, the mixing method, the solvent removal step and the cooling step to room temperature may be carried out by ordinary methods and are not particularly limited.

The liquid composition can be made into a cured product by adding a curing accelerator or the like as necessary and thermosetting. 70-220 degreeC is suitable for hardening temperature, More preferably, it is 80-200 degreeC. Moreover, 1-15 hours are suitable for hardening time, More preferably, it is 2-10 hours.
Examples of the shape of the cured product include molded products such as deformed products, films, sheets, pellets, and the like, and thus a cured product using the liquid composition of the present invention (formed from the liquid composition of the present invention). Cured product) is also one of the preferred forms of the present invention.

The liquid composition is suitably used for various applications such as mounting applications, optical applications, optical device applications, display device applications, mechanical component applications, electrical / electronic component applications, automotive component applications, printing ink applications, and the like. It is what Specifically, it is preferably used for electronics mounting materials, potting materials, underfill materials, conductive pastes, insulating pastes, die pond materials, printing inks and the like. Among these, the liquid composition is a composition that can exist in a liquid state at room temperature without containing a volatile component such as an organic solvent. Therefore, the liquid composition is particularly suitably used for an application that requires no volatile component such as an electronic packaging material. Will be. Thus, the electronic packaging material using the said liquid composition is also one of this invention.

The electronic packaging material is not particularly limited as long as it is a material that can be used for an electronic component or the like. For example, a liquid semiconductor sealing material used when sealing a semiconductor component is suitable. In such an electronic packaging material, for example, a curing accelerator, a stabilizer, a mold release agent, a coupling agent, a colorant, a plasticizer, and a flexible agent may be used as long as the effects of the present invention are not impaired. Agents, various rubbery materials, photosensitizers, fillers, flame retardants, pigments and the like. Moreover, since the said electronics mounting material may produce a malfunction, when a volatile component is contained in large quantities, it is desired not to contain a volatile component, for example, content of the volatile component in 100 mass% of the said electronics mounting materials The amount is preferably 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it does not contain a volatile component substantially.

Since the liquid composition of the present invention has the above-described configuration, it is excellent in various physical properties such as heat resistance, and can exist in a liquid state at room temperature without substantially containing volatile components such as organic solvents and diluents. It is. Therefore, it is useful for various applications in addition to electronic packaging materials.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by mass”. In addition, n in the chemical formula described later indicates that the siloxane bond in parentheses is repeated, and the chemical formula of the compound obtained in each synthesis example indicates the main composition of the synthesized compound.
In the following Examples and Comparative Examples, the melting points of the reactive group-containing compound and the comparative reactive group-containing compound are measured by DSC (“EXSTAR6000”, manufactured by Seiko Instruments Inc.) and a melting point measuring instrument (“B-535”). ", Manufactured by BUCHI Co., Ltd.). DSC measurement was performed at a heating rate of 5 min / ° C. under nitrogen flow, a temperature region where an endothermic peak was generated was confirmed in advance, and the melting point was examined by visual observation from room temperature to the temperature region.

Synthesis Example 1 (Preparation of Silane Compound Solution 1)
Synthesis of poly (γ-phthaloimidopropylsilsesquioxane) Into a 500 mL four-necked flask equipped with a stirrer, a temperature sensor, and a condenser tube, 86.6 g of diglyme previously dried with molecular sieve and 3-aminopropyltrimethoxysilane 179.4 g was added, and the temperature was raised to 100 ° C. under a flow of dry nitrogen while stirring to remove moisture in the system. Next, 148.2 g of phthalic anhydride was added in four portions over 30 minutes while maintaining the reaction solution temperature at 80 ° C. It was confirmed by high performance liquid chromatography that phthalic anhydride was completely consumed in 3 hours after the completion of the addition.
The reaction product was sampled and ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS were measured, and the following chemical formula (i-1):

It confirmed that it contained the compound represented by these.
¹ H-NMR: 0.72 (t, 2H), 1.81 (m, 2H), 3.48 (dd, 2H), 3.72 (s, 9H), 4.71 (bs, 1H), 7.56-7.72 (m, 2H), 7.73-7.86 (m, 2H), 11.0 (bs, 1H)
¹³ C-NMR: 9.1, 22.2, 40.6, 50.5, 122.3, 122.4, 122.5, 132.4, 134.0, 134.2, 168.7, 172 .0
MALDI-TOF-MS: 334 (M + Li)

Subsequently, 54.2 g of deionized water was added all at once, and the temperature was raised so that by-product methanol was refluxed in the cooling pipe. After holding for 6 hours, the cooling pipe was replaced with a partial condenser, and the temperature was raised again. The reaction liquid temperature was allowed to reach 120 ° C. over 3 hours while collecting raw methanol and condensed water. When the temperature reached 120 ° C., 7.9 g of pyridine was added and the temperature was raised as it was. The temperature reached 160 ° C. over 3 hours while collecting condensed water, and the temperature was maintained at the same temperature for 2 hours and cooled to room temperature. The reaction product thus obtained is designated as “Silane Compound Solution 1” (solid content concentration 80.6%).
The reaction product was a dark brown high-viscosity liquid with a non-volatile content of 80.6%. The molecular weight measured by GPC was a number average molecular weight of 2310 and a weight average molecular weight of 2830. ¹ H-NMR and ¹³ C-NMR were measured, and the following chemical formula (i-2):

It was confirmed that the compound represented by the formula (poly (γ-phthalimidopropylsilsesquioxane)) was contained.
¹ H-NMR: 0.3-0.9 (bs, 2H), 1.5-1.8 (bs, 2H), 3.4-3.6 (bs, 2H), 7.1-7. 7 (bs, 4H)
¹³ C-NMR: 10.0, 22.1, 40.4, 123.1, 132.3, 133.7, 168.1

Synthesis Example 2 (Preparation of Silane Compound Solution 2)
Synthesis of poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane} 35.1 g of diglyme previously dried with molecular sieves in a 300 mL four-necked flask equipped with a stirrer, temperature sensor, and condenser. Then, 30.8 g of 3-aminopropyltrimethoxysilane was added, and the temperature was raised to 100 ° C. under a flow of dry nitrogen while stirring to remove moisture in the system. Next, 28.2 g of 5-norbornene-2,3-dicarboxylic acid anhydride was added in 4 portions over 30 minutes while maintaining the temperature of the reaction solution at 100 ° C. It was confirmed by high performance liquid chromatography that 5-norbornene-2,3-dicarboxylic anhydride was completely consumed in 9 hours after the completion of the addition.
The reaction product was sampled to measure ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS, and the following chemical formula (ii-1):

It confirmed that it contained the compound represented by these.
¹ H-NMR: 0.40 (t, 2H), 1.35 (m, 2H), 1.46 (dd, 2H), 3.08-3.17 (m, 1H), 3.20 (dd 2H), 3.28-3.37 (m, 1H), 3.40 (s, 9H), 3.42 (m, 1H), 3.48 (m, 1H), 5.91 (s, 2H), 6.22 (bs, 1H), 11.0 (bs, 1H)
¹³ C-NMR: 8.1, 11.2, 40.6, 44.9, 45.8, 50.3, 50.6, 52.3, 134.5, 177.8, 178.1
MALDI-TOF-MS: 350 (M + Li)

Subsequently, 9.3 g of deionized water was added all at once, and the temperature was raised so that by-product methanol was refluxed in the cooling pipe. After holding at 95 ° C. for 10 hours, the cooling pipe was replaced with a partial condenser and the temperature was raised again. The reaction liquid temperature was allowed to reach 120 ° C. over 3 hours while collecting by-product methanol and condensed water. When the temperature reached 120 ° C., 1.4 g of pyridine was added and the temperature was raised as it was, and while recovering the condensed water, the temperature reached 160 ° C. over 3 o'clock, kept at the same temperature for 2 hours, and cooled to room temperature. The reaction product thus obtained is designated “Silane Compound Solution 2” (solid content concentration: 58.2%).
The reaction product was a dark brown high-viscosity liquid with a non-volatile content of 58.2%. When the molecular weight was measured by GPC, the number-average molecular weight was 2340 and the weight-average molecular weight was 2570. ¹ H-NMR and ¹³ C-NMR were measured, and the following chemical formula (ii-2):

It was confirmed that the compound represented by the formula (poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane}) was contained.
¹ H-NMR: 0.25-0.45 (bs, 2H), 1.2-1.45 (bs, 2H), 1.47 (dd, 2H), 3.0-3.2 (bs, 4H), 3.4-3.6 (bs, 2H), 5.8-6.0 (bs, 2H)
¹³ C-NMR: 9.7, 21.5, 40.4, 44.9, 45.7, 50.1, 134.2, 178.0

Synthesis Example 3 (Preparation of Silane Compound Solution 3)
Synthesis of poly [(cis-4-cyclohexene-1,2-imido) propylsilsesquioxane] In a 500 mL four-necked flask equipped with a stirrer, a temperature sensor, and a condenser tube, 103.7 g of diglyme previously dried with molecular sieves. Then, 177.6 g of 3-aminopropyltrimethoxysilane was added, and the temperature was raised to 100 ° C. under a flow of dry nitrogen while stirring to remove moisture in the system. Next, 150.7 g of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride was added in four portions over 30 minutes while maintaining the temperature of the reaction solution at 80 ° C. It was confirmed by high performance liquid chromatography that cis-4-cyclohexene-1,2-dicarboxylic anhydride was completely consumed within 3 hours after the completion of the addition.
The reaction product was sampled to measure ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS, and the following chemical formula (iii-1):

It confirmed that it contained the compound represented by these.
¹ H-NMR: 0.72 (t, 2H), 1.81 (m, 2H), 2.23 (dd, 4H), 2.74 (m, 1H), 2.91 (dd, 1H), 3.48 (dd, 2H), 3.72 (s, 9H), 5.74 (m, 2H), 11.0 (bs, 1H)
¹³ C-NMR: 9.1, 22.2, 25.5, 26.8, 40.6, 42.3, 43.1, 44.7, 131.7, 168.8, 172.7,
MALDI-TOF-MS: 338 (M + Li)

Subsequently, 53.4 g of deionized water was added all at once, and the temperature was raised so that by-product methanol was refluxed in the cooling pipe. After holding for 6 hours, the cooling pipe was replaced with a partial condenser, and the temperature was raised again. The reaction liquid temperature was allowed to reach 120 ° C. over 3 hours while collecting raw methanol and condensed water. When the temperature reached 120 ° C., 7.9 g of pyridine was added and the temperature was raised as it was. The temperature reached 160 ° C. over 3 hours while collecting condensed water, and the temperature was maintained at the same temperature for 2 hours and cooled to room temperature. The reaction product thus obtained is designated as “silane compound solution 3” (solid content concentration: 74.3%).
The reaction product was a dark brown high-viscosity liquid with a non-volatile content of 74.3%. The molecular weight measured by GPC was a number average molecular weight of 2041 and a weight average molecular weight of 2838. ¹ H-NMR and ¹³ C-NMR were measured, and the following chemical formula (iii-2):

(Poly [(cis-4-cyclohexene-1,2-imido) propylsilsesquioxane]).
¹ H-NMR: 0.25-0.55 (bs, 2H), 1.3-1.5 (bs, 2H), 2.0-2.5 (dd, 4H), 2.9-3. 1 (bs, 2H), 3.2-3.35 (bs, 2H), 5.65-5.8 (bs, 2H)
¹³ C-NMR: 10.0, 21.0, 23.8, 39.0, 41.1, 127.8, 180.5

Example 1 (Composition 1)
In a 500 mL flask equipped with a partial condenser, a collecting tube, a vacuum pump, a temperature sensor, and a stirring device, 121.1 g of 4,4′-bis (glycidyloxy) biphenyl and the silane compound solution 1 obtained in Synthesis Example 1 (solid content) 229.7 g (concentration 80.6%) was charged and stirred while heating to 140 ° C. to obtain a uniform solution. Subsequently, the pressure in the flask was reduced to 5 kPa with a vacuum pump, and volatile components were collected over 7 hours. Thereafter, the flask internal temperature was lowered to 90 ° C., 64.1 g of tetrahydromethyl phthalic anhydride was added, and the mixture was stirred until it became completely uniform, and then cooled to 25 ° C. to obtain composition 1.
The composition 1 thus prepared was evaluated for properties at room temperature (25 ° C.), 60 ° C. viscosity, and 5% mass reduction temperature as follows. The results are shown in Table 1.

(1) Property at room temperature and viscosity at 60 ° C. After cooling the resin composition (liquid composition) prepared as described above to room temperature (25 ° C.), the property at room temperature was confirmed visually. The viscosity at a measurement temperature of 60 ° C. was measured using a cone plate viscometer (device name “cap2000H”, manufactured by Brookfield).
(2) 5% mass reduction temperature To 100 parts of the resin composition (liquid composition) prepared as described above, 0.5 part of tolylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred well, and then PTFE. Poured into a mold frame and left under a temperature condition of 120 ° C. × 30 minutes + 180 ° C. × 3 hours to obtain a cured product. The mass reduction temperature at the time of heating of the obtained cured product was measured using a differential thermal balance (device name “TG-DTA2000SA”, manufactured by Bruker). The measurement conditions were a heating rate of 10 ° C./min and an air flow of 100 ml / min.

Examples 2 to 11 and Comparative Examples 1 to 11 (Compositions 2 to 22)
4,4′-bis (glycidyloxy) biphenyl, silane compound solution 1 and tetrahydromethyl used in Example 1 as a reactive group-containing compound (or comparative reactive group-containing compound), a silane compound solution and a crosslinking agent, respectively. Compositions 2 to 22 were obtained in the same manner as in Example 1 except that the compounds described in Tables 1 to 3 were used instead of phthalic anhydride (in Comparative Examples 3 to 4 and 7 to 11). No silane compound solution was added.) The amount of each compound used is such that the functional group equivalent ratio of the reactive group-containing compound (or comparative reactive group-containing compound) and the crosslinking agent is equal, and the blending ratio of the silane compound is as follows: It set so that the solid content of a silane compound might be 100 weight part with respect to 100 weight part of total mass of a reactive group containing compound and a crosslinking agent. In Examples 9 to 11 and Comparative Examples 9 to 11, two compounds were used as the reactive group-containing compound (or the reactive group-containing compound for comparison), but the compounding ratio of these two compounds was 1. : 1 (molar ratio).
About composition 2-22 prepared in this way, it carried out similarly to Example 1, and evaluated the property in room temperature (25 degreeC), 60 degreeC viscosity, and 5% mass reduction | decrease temperature. The results are shown in Tables 1-3.

In Tables 1 to 3, symbols and the like are as follows.
Silane compound solution 1: Solution containing poly (γ-phthalimidopropylsilsesoxane) obtained in Synthesis Example 1 Silane compound solution 2: Poly [γ- (5-norbornene-2,3- Solution containing imide) propylsilsesoxane] Silane compound solution 3: Solution containing poly [(cis-4-cyclohexene-1,2-imido) propylsilsesquioxane] obtained in Synthesis Example 3 * 1: Measurement Since crystals precipitated even at a temperature (60 ° C.), the viscosity could not be measured.
* 2: Since the cured product still contained the precipitated crystals, it was judged that a cured product worthy of measurement could not be produced.

From the results of Tables 1 to 3, the following was confirmed.
In Table 1, from the comparison between Examples 1 and 3 and Comparative Examples 3 and 4, even when the same reactive group-containing compound and crosslinking agent were used, the room temperature was different depending on whether or not the silane compound was added. It can be seen that the properties at are completely different. That is, in Examples 1 and 3, a liquid composition was obtained at room temperature, but in Comparative Examples 3 and 4, crystals were precipitated at room temperature and 60 ° C., and a liquid composition could not be obtained. In Examples 1 to 4, a reactive group-containing compound that was solidified at room temperature and had a melting point of 200 ° C. or lower was used, whereas in Comparative Examples 1 and 2, the compound was used instead of the compound at room temperature. A liquid compound was used, and in each of Examples 1 to 4 and Comparative Examples 1 and 2, a liquid composition could be obtained at room temperature. In Comparative Examples 1 and 2, the mass decreased by 5%. It can be seen that the temperature is 280 ° C. or lower, and the thermal decomposition resistance is remarkably inferior compared to Examples 1 to 4.

In Examples 2 to 8 and Comparative Examples 5 to 8 in Table 2, instead of the crosslinking agent (acid anhydride) used in Examples 1 to 4 and Comparative Examples 1 to 4 in Table 1, an amine compound was used as a crosslinking agent. Although it is an example used, it can be said that in this case as well, the same results as in the comparison between Examples 1 to 4 and Comparative Examples 1 to 4 in Table 1 can be said. That is, even when the same reactive group-containing compound and the crosslinking agent as in Examples 5 to 8 were used, when no silane compound was added (Comparative Examples 7 to 8), crystals were precipitated at room temperature, and the liquid composition at room temperature. Could not get. Moreover, in Comparative Examples 5-6 using the compound which is in a liquid state at room temperature as in Comparative Examples 1-2, the 5% mass reduction temperature is 270 ° C. or less, which is significantly more resistant to thermal decomposition than Examples 5-8. You can see that it is inferior.

In Examples 9 to 11 in Table 3, two types of compounds (specifically, a compound containing an epoxy group and a compound containing a maleimide group) were used as the reactive group-containing compound, and a silane compound was used in combination. In contrast to Examples, Comparative Examples 9 to 10 use a compound in liquid form at room temperature and a reactive group-containing compound (a compound having a maleimide group) of the present invention, and no silane compound was added. It is an example. In Comparative Example 11, two types of compounds (specifically, a compound containing an epoxy group and a compound containing a maleimide group) were used as the reactive group-containing compound, and no silane compound was added. It is. Also in this case, when the silane compound was not added (Comparative Examples 9 to 11), crystals precipitated at room temperature or became a high-viscosity fluid, and a composition showing a state that could be said to be liquid at room temperature could not be obtained. . Among these, Comparative Examples 9 and 10 are examples in which a part of the liquid compound was used at room temperature, but even in such a case, a liquid composition could not be obtained at room temperature. Moreover, in Examples 9-11, compared with Comparative Examples 9-11, 5% mass reduction | decrease temperature is remarkably high, and it turns out that thermal decomposition resistance is more excellent.
Moreover, Example 9 and Example 10 of Table 3 are respectively the same reactivity as Example 6 and Example 7 of Table 2 except having used together another reactive group containing compound (maleimide compound). In this example, a group-containing compound, a crosslinking agent, and a silane compound are used, but Examples 9 and 10 have a higher 5% mass reduction temperature than Examples 6 and 7, that is, the thermal decomposition resistance is higher. It can be seen that the result is better.

Claims (4)

A reactive group-containing compound, a crosslinking agent, and the following formula (1):

(In the formula, R ¹ represents at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings. X and z are the same or different and are integers of 0 or more and 5 or less. Y Is a liquid composition comprising a structural unit represented by 0) and a silane compound having a siloxane skeleton,
The reactive group-containing compound is in a crystalline state at room temperature, has a melting point of 80 ° C. or higher and 200 ° C. or lower, has a molecular weight of 100 to 1,000, and has an aromatic ring structure or a heterocyclic structure in its skeleton. And the reactive group is a compound having at least one functional group selected from the group consisting of a glycidyl group, an epoxy group, and a maleimide group,
The crosslinking agent is at least one compound selected from the group consisting of amine compounds, dicarboxylic acid anhydrides and tetracarboxylic acid dianhydrides,
Content of this silane compound is 10-200 weight part with respect to 100 weight part of total amounts of a reactive group containing compound and a crosslinking agent, The liquid composition characterized by the above-mentioned. The liquid composition according to claim 1, wherein the liquid composition has a viscosity at 60 ° C. of 100 Pa · s or less. The liquid composition according to claim 1 or 2, wherein a content of a volatile component in the liquid composition is 10% by mass or less with respect to 100% by mass of the liquid composition. Electronics Packaging material characterized by using a liquid composition according to any of claims 1-3.