TWI555809B - Adhesive composition containing aromatic polyether derivative - Google Patents

Description

Adhesive composition containing an aromatic polyether derivative

The present invention relates to an adhesive composition. More specifically, it relates to an adhesive composition which is followed by a laminate in a step of forming a laminate such as a semiconductor article such as an IC wafer or an optical system.

In recent years, high-performance and miniaturization of electronic devices such as mobile phones and IC cards have been pursued, and the integration of semiconductor devices has been pursued. This technique is a stacking structure in which the semiconductor itself is miniaturized or the semiconductor elements are stacked in the longitudinal direction.

In the fabrication of the stacked structure, an adhesive is used for bonding between the semiconductor elements.

However, the known acrylic resin, epoxy resin, and fluorenone resin have a heat resistance of only about 250 ° C, and may be used in an electrode bonding or ion diffusion step of a metal bump, and are required to have a high temperature of 250 ° C or higher. The problem with the steps.

On the other hand, it is disclosed that a thick film technical substrate containing 30% by volume or 45% by volume of an undercut film of a polyetheretherketone resin powder and a thermosetting resin is formed on an inorganic insulating substrate impregnated with a fluorenone resin on a glass substrate. (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Special Opening 2009-070875

The substrate on which the undercut film is formed is excellent in that the size of moisture or heat is extremely small, and the moisture resistance is excellent. However, since the polyetheretherketone contained in these undercut films is insoluble in a solvent or a resin solution, it cannot be used as a coating-type adhesive, but a method of coating a substrate by a screen printing method in the form of a paste ink. Further, since the content of the polyetheretherketone resin in the composition is excessively increased, the screen-printable ink cannot be formed. Therefore, the resin can only contain a ratio of 30% by volume or 45% by volume, which has a problem of heat resistance.

An acrylic resin, an epoxy resin, or an anthrone resin which is known as a conventional adhesive agent has a heat resistance of only about 250 ° C and cannot be used at a high temperature of 250 ° C or higher.

On the other hand, in Patent Document 1, an adhesive of a polyetheretherketone-like wholly aromatic polyether is disclosed, but the solvent solubility is extremely low and there is no solubility, and the solvent selectivity is small, and it is difficult to form a thick film. Further, there is a problem that the coatability is also insufficient.

In the method of improving solvent solubility, it is proposed to introduce a soft structure typified by a long-chain alkyl group, but there is a problem that heat resistance is lowered in total.

The present invention has been made in view of the above problems, and an object thereof is to provide an adhesive layer which is easily soluble in various organic solvents and has good coatability and can form a sufficient thickness, and the adhesive layer is bonded by metal bumps, CVD, and ion diffusion. In the high-temperature process such as the step, the composition of the high heat-resistant adhesive having little thermal weight reduction and good adhesion is obtained.

According to a first aspect of the present invention, the method comprises the following formula (1):

【化1】

(wherein X is a sulfonyl group or a carbonyl group, each of Ar ¹ and Ar ² is an exoaryl group having 6 to 30 carbon atoms, and T ¹ is a fluoroalkyl group, a cyclic alkyl group, and a substituent having a substituent. a combination of a aryl group which may have a substituent and a fluorine-extended alkyl group or a cyclic alkyl group, and a binder composition of a polymer having a unit structure represented by the above, and a second aspect, a aryl group The first aspect or the second aspect of the polymer having one type of unit structure, the binder composition described in the first aspect of the present invention, and the third aspect of the present invention. In the fourth aspect of the present invention, the binder composition is a binder composition having a polymer structure having at least two types of unit structures, and a binder composition according to the first aspect or the second aspect. The foregoing Ar ¹ and Ar ² are each represented by the following formula (2):

[Chemical 2]

(wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, a cyano group, a nitro group or a fluorenyl group; a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and n1 is an integer of 0 to 4.) The group represented by the above formula (1) according to any of the first aspect and the fourth aspect of the polymer unit is configured according to one of the adhesive composition, the sixth aspect aspect, containing ^a system containing the following formula T above formula (3) represented by the group ( 1) The unit structure shown in the above, the first viewpoint of the polymer structure represented by the above formula (1) represented by the following formula (4), or the combination of the unit structures of the above T ¹ is even The adhesive composition according to any one of the fifth aspects,

[化3]

(wherein R ² , R ³ and R ⁴ are each an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, and a cyanogen group; a group, a nitro group, a fluorenyl group, a decyloxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and each of n2, n3 and n4 is an integer of 0 to 4, T ² In the above formula (3), R ² is a group containing a group having at least a third-order carbon structure, and n2 is a fluorine-containing alkyl group, a cyclic alkyl group, or a combination thereof. The adhesive composition described in the sixth aspect which is an integer of 1 to 4, and the eighth aspect, further contains the formula (5):

【化4】

(wherein X is a sulfonyl group or a carbonyl group, each of Ar ³ and Ar ⁴ is an exoaryl group having 6 to 30 carbon atoms, and T ³ is an alkylene group, a sulfonyl group, a carbonyl group, or a carbon number of 6 or 30. The arsenic group, or a combination of these, the first embodiment, the second aspect, the fourth aspect, and the seventh aspect of the polymer of the unit structure of the base group, the ninth aspect, and the ninth aspect In view of the above, the above-mentioned exoaryl group is an adhesive composition according to the eighth aspect of the present invention, which is a phenylene group, a naphthyl group, or a mercapto group. The tenth aspect is that the T ³ is a formula (6):

【化5】

(wherein R ⁵ and R ⁶ are each an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, a cyano group, and a nitrate a group, a mercapto group, a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, each of n5 and n6 is an integer of 0 to 4, and T ⁴ is an alkylene group, The sulfonate group, the carbonyl group, the aryl group having 6 to 30 carbon atoms, or the combination thereof; the binder composition according to the eighth aspect or the ninth aspect, and the eleventh aspect, The first aspect of the third aspect of the present invention is the third aspect of the present invention, wherein the polymer has a weight average molecular weight of 500 to 5,000,000. The adhesive composition according to any one of the first aspect of the present invention, the fourth aspect, the fourth aspect, the fourth aspect, and the fourth aspect, An adhesive agent according to any one of the first aspect to the thirteenth aspect, further comprising a solvent and having a viscosity of 0.001 to 5000 Pa s The object of the present invention, the 15th aspect, the 0.1 μm formed of the adhesive composition of at least two of the adherends, and the adhesive composition described in any one of the first aspect to the fourteenth aspect In the laminate of the laminate of 200 μm and the 16th aspect, each of the substrates to be tested is a laminate according to the fifteenth aspect selected from the group consisting of a tantalum substrate, a glass substrate, a resin substrate, and a ceramic substrate.

According to the present invention, the adhesive composition of the present invention can be easily dissolved and obtained in a variety of solvents by a polymer having an aromatic polyether such as an aromatic polyether ether ketone or an aromatic polyether ether oxime. Coating properties. Moreover, the adhesive composition of the present invention can form an adhesive layer of a sufficient thickness to be subsequently required, and has a small thermal weight reduction in a high-temperature process such as a metal bump bonding, a CVD, an ion diffusion step, etc., and a high density can be formed after a high-temperature process. The next layer of sex.

In this way, the adhesive composition containing the polymer having a polyether structure of the present invention can be used for a workpiece such as an electronic substrate used in a semiconductor device or the like necessary for processing in a high-temperature process (for example, by heat treatment or pressure treatment). Followed by processing of laminated materials such as lithography.

Further, the laminate of the present invention can be processed into an adherend in a high-temperature process and can be used under high temperature conditions due to an adhesive layer having high heat resistance.

[Best Mode for Carrying Out the Invention]

The present invention is an adhesive composition containing a polymer having a unit structure represented by the formula (1).

The above-mentioned adhesive composition contains a polymer containing a unit structure represented by the formula (1) and a solvent, and may further contain an optional component to improve the adhesive performance, a resin, an adhesion-imparting agent, a plasticizer, and an auxiliary agent. , stabilizers, colorants, surfactants, etc.

The solid content of the adhesive composition of the present invention is 0.1 to 80% by mass, preferably 1 to 60% by mass. The solid content relative to the adhesive composition is expressed by the ratio of the residual portion of the solvent removed from the adhesive composition. The proportion of the polymer having a unit structure represented by the formula (1) which is contained in the solid content is from 30 to 100% by mass, preferably from 50 to 100% by mass.

The polymer used in the present invention is preferably a thermoplastic resin.

The molecular weight of the polymer used in the present invention is from 500 to 5,000,000, preferably from 1,000 to 1,000,000, more preferably from 1,000 to 100,000, based on the weight average molecular weight.

In the formula (1), X is a sulfonyl group or a carbonyl group, each of Ar ¹ and Ar ² is an exoaryl group having 6 to 30 carbon atoms, and T ¹ is a fluoroalkyl group, a cyclic alkyl group, and a substituent. A combination of an aryl group or a aryl group which may have a substituent with a fluoroalkyl group or a cyclic alkyl group.

The extended aryl group having a substituent is a substituted aryl group having a substituent as described below.

The extended aryl group which may have a substituent is a substituted or unsubstituted extended aryl group, and for this purpose, a combination of a aryl group and a fluorine alkyl group or a cyclic alkyl group.

The aryl group may, for example, be a phenyl group, a naphthyl group or a fluorenyl group, and a phenyl or naphthyl group is preferred.

The fluorine alkyl group may, for example, be a fluorine alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a fluoromethylene group, a fluorine-extended ethyl group, a fluorine-n-propyl group, and a fluorine-iso-propyl group. , fluoropropane-2,2-diyl, fluoro-n-butylene, fluoroisobutylene, fluoro-s-butylene, fluoro-t-butylene, and the like. Among them, a fluorine alkyl group having 1 to 4 carbon atoms such as perfluoropropane-2,2-diyl may be mentioned. These fluorine alkyl groups may use a fully fluorinated (perfluorinated) alkylene group or a partially fluorinated alkylene group (monofluorinated, difluorinated, etc.).

The cyclic alkyl group may, for example, be a cyclic alkyl group having 3 to 30 carbon atoms, such as a cyclic propyl group, a cyclobutyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, and 2 Methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1, 2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4-Dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclo Propyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2 -ethyl-2-methyl-cyclopropanyl and 2-ethyl-3-methyl-cyclopropyl. Further, a divalent organic group derived from adamantane or norbornene can be used.

The polymer having a unit structure represented by the formula (1) used in the present invention, the functional group of T ¹ or the like may be used singly or in combination.

The above polymer may be used as a repeating unit structure in a single polymer or a repeating unit structure of two or more kinds of copolymers.

In the present invention, a polymer having a unit structure represented by the above formula (1) in which Ar ¹ and Ar ² are each a group represented by the formula (2) may be contained.

In the formula (2), R ¹ is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, a cyano group, a nitro group, A mercapto group, a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and n1 is an integer of 0 to 4.

In the formula (2), the alkyl group representing R ¹ is an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl. , s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1- Dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1 -methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl 1,1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n -butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl Base, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, and the like.

The fluoroalkyl group may, for example, be a fluoroalkyl group having 1 to 10 carbon atoms and a fluoroalkyl group having 1 to 4 carbon atoms. For example, a fluoromethyl group, a fluoroethyl group, a fluorine-n-propyl group, a fluoroisopropyl group, a fluorine-n-butyl group, a fluorine-isobutyl group, a fluorine-s-butyl group, a fluorine-t-butyl group, etc. are mentioned. As such a fluoroalkyl group, a fully fluorinated (perfluorinated) or partially fluorinated alkyl group can be used.

The mercapto group may, for example, be a fluorenyl group having 2 or 10 carbon atoms, such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i-propylcarbonyl, cyclopropylcarbonyl, n-butylcarbonyl, i-. Butylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, cyclobutylcarbonyl, 1-methyl-cyclopropylcarbonyl, 2-methyl-cyclopropylcarbonyl, n-pentylcarbonyl, 1-methyl Base-n-butylcarbonyl, 2-methyl-n-butylcarbonyl, 3-methyl-n-butylcarbonyl, 1,1-dimethyl-n-propylcarbonyl, 1,2-dimethyl Base-n-propylcarbonyl, 2,2-dimethyl-n-propylcarbonyl, 1-ethyl-n-propylcarbonyl, cyclopentylcarbonyl, 1-methyl-cyclobutylcarbonyl, 2- Methyl-cyclobutylcarbonyl, 3-methyl-cyclobutylcarbonyl, 1,2-dimethyl-cyclopropylcarbonyl, 2,3-dimethyl-cyclopropylcarbonyl, 1-ethyl-cyclo Propylcarbonyl, 2-ethyl-cyclopropylcarbonyl, n-hexylcarbonyl, 1-methyl-n-pentylcarbonyl, 2-methyl-n-pentylcarbonyl, 3-methyl-n-pentyl Carbonyl, 4-methyl-n-pentylcarbonyl, 1,1-dimethyl-n-butylcarbonyl, 1,2-dimethyl-n-butylcarbonyl, 1,3-dimethyl-n -butylcarbonyl, 2,2-dimethyl-n-butylcarbonyl, 2,3-dimethyl-n-butylcarbonyl, 3,3-dimethyl -n- butyl carbonyl group, 1-ethyl -n- butyl carbonyl, ethyl carbonyl -n- butyl group, 1,1,2-trimethyl -n- propyl carbonyl group and the like.

The mercaptooxy group may, for example, be a fluorenyloxy group having 2 or 10 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, or a ring. Propylcarbonyloxy, n-butylcarbonyloxy, i-butylcarbonyloxy, s-butylcarbonyloxy, t-butylcarbonyloxy, cyclobutylcarbonyloxy, 1-methyl- Cyclopropylcarbonyloxy, 2-methyl-cyclopropylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyl Oxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1,2-dimethyl-n-propylcarbonyloxy, 2, 2-Dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, cyclopentylcarbonyloxy, 1-methyl-cyclobutylcarbonyloxy, 2-methyl - cyclobutylcarbonyloxy, 3-methyl-cyclobutylcarbonyloxy, 1,2-dimethyl-cyclopropylcarbonyloxy, 2,3-dimethyl-cyclopropylcarbonyloxy, 1-ethyl-cyclopropylcarbonyloxy, 2-ethyl-cyclopropylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n -pentylcarbonyloxy, 3-methyl-n-pentyl Carbonyloxy, 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1 , 3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3 - dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n -propylcarbonyloxy group and the like.

A third butyl group is preferably used as the group having the third-order carbon structure.

The cyclic alkyl group may, for example, be a cyclic alkyl group having 3 to 30 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group or a 2-methyl-cyclopentyl group. , 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1 ,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3 - dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-ring Propyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl- 2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl Wait. Further, a monovalent organic group derived from adamantane or norbornene can be used.

Used in the selection of the polymers of the present invention, Ar ¹ and Ar ² of the different selection or the above-described Ar ¹ and Ar ² may contain the same system of formula ¹ having the formula T (3) represented by the group (1) represented by the unit cell structure is configured, the above-described formula T (4) ^a group represented by the Department of the formula (1) represented by the, or the polymer composition of their cell structure of the.

(1) represented by the unit configured i.e., may be used containing Ar and Ar ¹ (2) ² based group represented by the formula above formula, T (3) ^a group represented by the above formula based formula (1) unit construction unit configured represents the, T represented by the ^first system of formula (4) in the above formula (1) represented by the group, Ar ¹ and Ar (2) represented by the group and T ¹ lines of formula (3) ^2-based formula The unit structure represented by the above formula (1), the group represented by the formula (1) of Ar ¹ and Ar ² , and the group represented by the formula (1) represented by the formula (4) of T ¹ represented by the above formula (1) The unit structure, or a combination of such polymers.

In the formulae (3) and (4), each of R ² , R ³ and R ⁴ is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group or an allyloxy group. a group, an amine group, a cyano group, a nitro group, a decyl group, a decyloxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, wherein n2, n3 and n4 are each 0 or even An integer of 4. T ² is a fluoroalkyl group, a cyclic alkyl group, or a combination thereof.

The above-exemplified examples can be used for the alkyl group having 1 to 10 carbon atoms, the fluoroalkyl group having 1 to 4 carbon atoms, the group having the third-order carbon structure, the cyclic alkyl group, the fluorenyl group, and the decyloxy group.

As the fluoroalkylene group and the cyclic alkylene group, the above-exemplified ones can be used, and these can be used singly or in combination.

In the formula (3), it is possible to use a unit structure in which R ² contains at least a group having a third-order carbon structure, and n2 is an integer of 1 to 4.

In addition to the unit structure represented by the formula (1), the present invention can further use a copolymer having a unit structure represented by the formula (5). In the formula (5), X is a sulfonyl group or a carbonyl group, each of Ar ³ and Ar ⁴ is an exoaryl group having 6 to 30 carbon atoms, and T ³ is an alkylene group, a sulfonyl group, a carbonyl group, a carbon number of 6 or even 30 aryl, or a combination of these. The above-exemplified persons can be used for such exoaryl groups and alkylene groups.

In the formula (5), a phenyl group, a substituted or unsubstituted phenyl group, a naphthyl group or a fluorenyl group may be used.

In the formula (5), the alkylene group may, for example, be an alkylene group having 1 to 10 carbon atoms, and the alkylene group may, for example, be a methylene group, an ethyl group, a propyl group or an exo-propyl group. , propane-2,2-diyl, n-butylene, isobutylene, s-butylene, t-butylene, and the like. Among them, an alkylene group having 1 to 4 carbon atoms such as a propane-2,2-diyl group can be mentioned.

In the formula (5), the group represented by the formula (6) can be used for T ³ . In the formula (6), each of R ⁵ and R ⁶ is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group or a cyano group. And a nitro group, a mercapto group, a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and each of n5 and n6 is an integer of 0 to 4. T ⁴ is an alkylene group, a sulfonyl group, a carbonyl group, an extended aryl group having 6 to 30 carbon atoms, or a combination thereof. The above alkyl group, a fluoroalkyl group having 1 to 4 carbon atoms, a mercapto group, a mercaptooxy group, a group having a third-order carbon structure, a cyclic alkyl group, an alkylene group, and an extended aryl group can be used. .

In the present invention, the group having the third-order carbon structure is a functional group having a third-order carbon structure. Substitution of this functional group with a hydrogen atom on a carbon atom produces a fourth-order carbon. The organic group bonded to the third-order carbon atom of the third-order carbon structure may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group or an aryl group such as a phenyl group, wherein a methyl group is preferably used. . A third butyl group having three methyl groups can be suitably used as the group having a third-order carbon structure.

The unit structure represented by the formula (1) used in the present invention is exemplified below.

【化6】

【化7】

The polymer having a unit structure represented by the formula (1) is a terminal hydroxyl group or a halogen group, or a hydrogen atom or a halogen group of a hydroxyl group thereof is substituted with a phenyl group or the like to block the terminal. This blocking group is represented by the following formula (A).

【化8】

In the above formula (A), Q ¹ is the above alkyl group substituted with the above alkyl group or a halogen atom (fluorine, chlorine, bromine or iodine), and k1 is an integer of 0 to 5.

A crosslinking agent can be used in the present invention. The crosslinking agent is not particularly limited, but is preferably a crosslinking agent having two or more substituents reactive with a functional group of the polymer, for example, 2 to 6 or 2 to 4 crosslinking agents. The proportion of the crosslinking agent which is contained in the solid content may be from 0 to 50% by mass, preferably from 5 to 40% by mass.

The crosslinking agent used in the present invention may, for example, be a nitrogen-containing compound having a nitrogen atom substituted with a hydroxymethyl group or an alkoxymethyl group. For example, a nitrogen-containing compound having a nitrogen atom substituted with a group such as a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group, or a hexyloxymethyl group. Further, an epoxy group-containing compound, an epoxy group-containing polymer, an allyl group-containing compound, an allyl group-containing polymer, an isocyanate group-containing compound, and an isocyanate group-containing polymer may be used as a crosslinking agent.

Specific examples of the nitrogen-containing compound include hexamethoxymethyl melamine, tetramethoxymethyl benzo melamine, 1,3,4,6-fluorenyl (butoxymethyl) acetylene urea, 1, 3, 4, 6-fluorene (hydroxymethyl) acetylene urea, 1,3-bis(hydroxymethyl) urea, 1,1,3,3-indole (butoxymethyl) urea, 1,1,3,3-肆(methoxymethyl) urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-tetrahydroimidazolidone and 1,3-bis(methoxymethyl)-4,5 a nitrogen-containing compound such as dimethoxy-2-tetrahydroimidazolium.

The crosslinking agent may, for example, be a methoxymethyl type melamine compound (trade name: Cyme 1300, Cyme 1301, Cyme 1303, Cyme 1350) manufactured by Mitsui Cytec Co., Ltd., or a butoxymethyl type melamine compound (trade name: MYCOAT 506, MYCOAT 508). , acetylene urea compound (trade name Cyme11170, Powderlink 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), Dainippon Ink Chemistry Commercially available compounds such as urea/formaldehyde resins (high condensation type, trade name BECKAMINEJ-300S, BECKAMINEP-955, BECKAMINEN) manufactured by the company.

Further, the crosslinking agent may be a compound obtained by condensing the above-described melamine compound, urea compound, acetylene urea compound, and benzoguanamine compound in which a hydrogen atom of an amine group is substituted with a hydroxymethyl group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound (trade name Cymel 303) and a benzoguanamine compound (trade name Cymel 1123) described in U.S. Patent No. 6,323,310 can be used as a crosslinkable compound.

Further, as the crosslinking agent, N-hydroxymethylpropenylamine, N-methoxymethylmethacrylamide, N-ethoxymethylpropenylamine and N-butoxymethylmethyl can be used. A polymer compound produced by a acrylamide or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as acrylamide. Examples of the polymer compound include poly(N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, and N-hydroxymethyl methacryl oxime. a copolymer of an amine and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and N-butoxymethyl acrylamide and benzyl A copolymer of a methacrylic acid ester and 2-hydroxypropyl methacrylate, and the like.

As the crosslinking agent having an epoxy group, for example, a compound having one to six, or two or even four epoxy rings can be used. The compound having an epoxy ring may, for example, be a compound having two or more hydroxyl groups or carboxyl groups such as a diol compound, a triol compound, a dicarboxylic acid compound or a tricarboxylic acid compound, and an epoxy propyl compound such as epichlorohydrin. A compound having two or more epoxypropyl ether structures or a glycidyl ester structure produced. For example, 1,4-propanediol diepoxypropyl ether, 1,2-epoxy-4-(oxiranyl)cyclohexane, glycerol triepoxypropyl ether, diethylene glycol diepoxypropyl Ether, 2,6-diepoxypropyl phenylepoxypropyl ether, 1,1,3-gin[p-(2,3-epoxypropoxy)phenyl]propane, 1,2- Dicyclopropyl propyl cyclohexanedicarboxylate, 4,4'-methylenebis(N,N-diepoxypropylaniline), 3,4-epoxycyclohexylmethyl-3,4- Epoxycyclohexane carboxylate, trimethylolethane triepoxypropyl ether, triepoxypropyl-p-aminophenol, tetraepoxypropylm-xylenediamine, tetra-epoxypropyl Diaminodiphenylmethane, tetraethoxypropyl-1,3-diaminomethylcyclohexane, bisphenol-A-diglycidyl ether, bisphenol-S-diglycidyl ether Pentaerythritol tetraepoxypropyl ether resorcinol diepoxypropyl ether, diepoxypropyl phthalate, neopentyl glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, four Bromobisphenol-A-diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, pentaerythritol diepoxypropyl ether, gins-(2,3-epoxypropyl)isocyanurate Monoallyl epoxypropyl isocyanurate, dipropyl Alcohol polydioxypropyl ether, pentaerythritol polyepoxypropyl ether, 1,4-bis(2,3-epoxypropoxyperfluoroisopropyl)cyclohexane, sorbitol polyepoxypropyl Ether, trimethylolpropane polyepoxypropyl ether, resorcinol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, Phenylepoxypropyl ether, p-t-butylphenylepoxypropyl ether, diepoxypropyl ether of adipic acid, diepoxypropyl ether of o-phthalic acid, dibromophenyl epoxy Propyl ether, 1,2,7,8-diepoxyoctane, 1,6-dimethylol perfluorohexane diepoxypropyl ether, 4,4'-bis(2,3-epoxy Propyloxyperfluoroisopropyl)diphenyl ether, 2,2-bis(4-epoxypropyloxyphenyl)propane, 3,4-epoxycyclohexylmethyl-3', 4'- Epoxycyclohexane carboxylate, 3,4-epoxycyclohexylethylene oxide, 2-(3,4-epoxycyclohexyl)-3',4'-epoxy-1,3-dioxin Alkan-5-spirocyclohexane, 1,2-extended ethylenedioxy-bis(3,4-epoxycyclohexylmethane), 4',5'-epoxy-2'-methylcyclohexyl Base-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol-bis(3,4-epoxycyclohexanecarboxylate), bis-(3,4-epoxy ring) Yl methyl) adipate, and bis (2,3-epoxy cyclopentyl) ether and the like.

The crosslinking agent may be used alone or in combination of two or more compounds.

The adhesive composition of the present invention may contain a crosslinking catalyst. The reaction of the crosslinkable compound is promoted by using a crosslinking catalyst.

For cross-linking catalyst, p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, pyridinium-p-toluenesulfonic acid, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, citric acid, benzoic acid can be used. And an acid compound such as hydroxybenzoic acid.

An aromatic sulfonic acid compound can be used for the crosslinking catalyst. Specific examples of the aromatic sulfonic acid compound include p-toluenesulfonic acid, pyridinium-p-toluenesulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, and benzenedisulfonic acid. , 1-naphthalenesulfonic acid, and pyridinium-1-naphthalenesulfonic acid, and the like.

When a crosslinking agent having an epoxy group is used, a phenol resin, an amine, a polyamide resin, an imidazole, a polythiol, an acid anhydride or the like can be used as the crosslinking catalyst.

Examples of the phenol resin include a phenol novolak resin and a cresol novolak resin.

The amines may, for example, be piperidine, N,N-dimethylpiperazine, tri-ethylenediamine, 2,4,6-gin(dimethylaminomethyl)phenol, benzyldimethylamine, 2-(Dimethylaminomethyl)phenol, di-ethyltriamine, tri-ethyltetramine, tetraethylamamine, diethylaminopropylamine, N-aminoethylpiper Pyrazine, bis(1-methyl-2-aminocyclohexyl)methane, montanyl diamine, isophorone diamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, Xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylphosphonium, and the like. Among these, diethyltriamine, triethylamine, tetraethylamamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl) 2-Aminocyclohexyl)methane, montanyldiamine, isophoronediamine, diaminodicyclohexylmethane or the like is preferably used.

The polyamine resin may, for example, be produced by condensation of a dimer acid and a polyamine, and a polyamine amine having a primary amine and a secondary amine in the molecule.

Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitic acid, and epoxy imidazole adducts.

The polythiol may, for example, be a thiol group at the terminal of the polypropylene glycol chain or a thiol group at the terminal of the polyethylene glycol chain.

The anhydride is preferably an anhydride of a compound having a plurality of carboxyl groups in one molecule. Examples of such acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic acid, glycerol, trimellitic acid, and maleic anhydride. , tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrobenzene Formic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, hexachlorotetramethylene anhydride, and the like.

Further, as another cross-linking catalyst, for example, an organophosphorus compound such as triphenylphosphine or tributylphosphine, ethyltriphenylphosphonium bromide or tetrabutylphosphonium dithiophosphate diethyl salt may be used. Onium salt, 1,8-diazabicyclo(5,4,0) undecane-7-ene, 1,8-diazabicyclo(5,4,0) undecane-7-ene and octanoic acid a fourth-order ammonium salt of a salt, zinc octoate, tetrabutylammonium bromide or the like.

When a crosslinking agent having an allyl group is used, the curing catalyst may be, for example, a radical polymerization initiator and a cationic polymerization initiator.

The radical polymerization initiator may, for example, be an imidazole compound, a diazo compound, a diimidazole compound, an N-arylglycine compound, an organic azide compound, a titanocene compound, an aluminate compound, or an organic peracid compound. , an N-alkoxypyridinium salt compound, a thioxanthone compound, and the like.

The organic azide compound may, for example, be p-azidaldehyde benzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzylidene acetophenone, 4,4'-diazide Chalcone, 4,4'-diazide diphenyl sulfide, and 2,6-bis(4'-azidobenzylidene)-4-methylcyclohexanone.

The diazo compound may, for example, be 1-diazo-2,5-diethoxy-4-p-tolylnonylbenzene boron fluoride, 1-diazo-4-N,N-dimethyl Amino phenyl chloride, and 1-diazo-4-N,N-diethylaminophenyl boron fluoride, and the like.

The biimidazole compound may, for example, be 2,2'-bis(o-chlorophenyl)-4,5,4',5'-fluorene (3,4,5-trimethoxyphenyl) 1,2'- Biimidazole and 2,2'-bis(o-chlorophenyl) 4,5,4',5'-tetraphenyl-1,2'-bisimidazole.

The titanocene compound may, for example, be dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-diphenyl, dicyclopentadienyl-titanium-bis (2,3,4) ,5,6-pentafluorophenyl),dicyclopentadienyl-titanium-bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-titanium-bis (2,4 ,6-trifluorophenyl),dicyclopentadienyl-titanium-bis(2,6-difluorophenyl), dicyclopentadienyl-titanium-bis(2,4-difluorophenyl) , bis(methylcyclopentadienyl)-titanium-bis(2,3,4,5,6-pentafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis (2,3 ,5,6-tetrafluorophenyl), bis(methylcyclopentadienyl)-titanium-bis(2,6-difluorophenyl), and dicyclopentadienyl-titanium-bis (2, 6-Difluoro-3-(1H-pyrrol-1-yl)-phenyl) and the like.

The radical polymerization initiator may, for example, be 1,3-bis(tert-butyldioxycarbonyl)benzophenone or 3,3',4,4'-fluorene (tert-butyldioxycarbonyl). Benzophenone, 3-phenyl-5-isoxazolinone, 2-mercaptobenazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- Hydroxy-cyclohexyl-phenyl-ketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone and the like.

The cationic polymerization initiator may, for example, be a sulfonate, a sulfonimide compound, a disulfonyldiazomethane compound, a dialkyl-4-hydroxyindole salt, or an arylsulfonic acid-p-nitrobenzyl group. Ester, stanol-aluminum complex, (η6-benzene) (η5-cyclopentadienyl) iron (II), and the like.

The sulfonimide compound may, for example, be N-(trifluoromethanesulfonyloxy) succinimide, N-(nonafluoro-n-butanesulfonyloxy) succinimide, N-( camphor Sulfhydryloxy) succinimide and N-(trifluoromethanesulfonyloxy)naphthylimine.

The disulfonyldiazomethane compound may, for example, be bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane or bis(phenylsulfonyl) Nitrogen methane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyl Diazomethane and the like.

The cationic polymerization initiator may, for example, be 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one.

Further, an aromatic iodonium salt compound, an aromatic sulfonium salt compound, an aromatic diazonium salt compound, an aromatic sulfonium salt compound, a triazine compound, and an iron aromatic hydrocarbon compound compound can be used as a radical polymerization initiator. Or a cationic polymerization initiator.

The aromatic iodonium salt compound may, for example, be diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate or diphenyl. Iodine perfluoro-n-octane sulfonate, diphenyl iodonium sulfonate, bis(4-tert-butylphenyl) iodonium sulfonate and bis(4-tert-butylphenyl) Iodine trifluoromethanesulfonate and the like.

The aromatic onium salt compound may, for example, be triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluorobutanesulfonate, triphenyl camphorsulfonate or triphenylsulfonium trifluoromethanesulfonate. Salt and so on.

The cross-linking catalyst may be used singly or in combination of two or more kinds.

The cross-linking catalyst may be 0 to 10 parts by mass, or 0.01 to 10 parts by mass, or 0.05 to 8 parts by mass, or 0.1 to 5 parts by mass, or 0.3 to 3 parts by mass, or 0.5 to 1 mass, relative to the polymer. Use it.

Moreover, examples of the object to be used in the present invention include a ruthenium substrate, a glass substrate, a resin substrate, and a ceramic substrate. These substrates can be used as a support for the laminate of the present invention.

The material to be used in the present invention may, for example, be an inorganic material such as ruthenium, iridium oxide, glass or tantalum nitride, a metal material such as aluminum or copper, a polyamide resin, a polyimide resin, an epoxy resin or a poly A resin material such as an acrylic resin, a polymethacrylic resin, a polybenzoxazole resin, a polyhydroxystyrene resin, or a benzocyclobutene resin.

The subsequent composition can be dissolved by an organic solvent for spin coating. The polymer is dissolved in an organic solvent, and the viscosity of the solution is in the range of 0.001 to 5000 Pa s. The polymer solution can be used as a coating liquid having spin coating properties.

The organic solvent is not particularly limited as long as it can be used in another semiconductor step, and a ketone such as cyclohexanone, methyl isoamyl ketone or 2-heptanone; ethylene glycol or ethylene glycol; Monomethyl ether, monoethyl ether, monopropyl, monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate Polyols such as ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid Esters such as ester, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate and the like are preferred. These may be used singly or in combination of two or more.

In the adhesive composition of the present embodiment, a mixed additive such as an additive resin for improving the performance of the adhesive, an adhesive imparting agent, a plasticizer, and the like may be further added without impairing the essential characteristics of the present invention. Conventional agents such as agents, stabilizers, colorants, surfactants, and the like.

As the resin (polymer) to be used for improving the performance of the adhesive, polyester, polystyrene, polyimide, propylene-based polymer, methacryl-based polymer, polyvinyl ether, phenol novolac can be used. An addition polymerized polymer or a polycondensation polymer of a naphthol novolac, a polyether, a polyamide, and a polycarbonate. A polymer having an aromatic ring structure such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, or a quinoxaline ring is preferably used.

The resin (polymer) thus added may, for example, be a benzyl acrylate, a benzyl methacrylate, a phenyl acrylate, a naphthyl acrylate, a decyl methacrylate or a decyl methyl group. Addition polymerizable monomer such as acrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as an addition polymerization polymer or phenol novolac of its structural unit, And a polycondensation polymer such as naphthol novolac.

Further, as the added resin (polymer), a polymer having no aromatic ring structure can be used. Such a polymer may, for example, contain only alkyl acrylate, alkyl methacrylate, vinyl ether, alkyl vinyl ether, acrylonitrile, maleimide, N-alkyl malayan An addition polymerizable monomer having no aromatic ring structure such as an amine or maleic anhydride as an addition polymerizable polymer of the structural unit thereof.

Where the addition resin (polymer) is an addition polymerized polymer, the polymer may be a single polymer or a copolymer. An addition polymerizable monomer is used in the production of the addition polymerization polymer. Examples of the addition polymerizable monomer include acrylic acid, methacrylic acid, acrylate compound, methacrylate compound, acrylamide compound, methacrylamide compound, vinyl compound, styrene compound, and Malay. An imine compound, maleic anhydride, acrylonitrile, and the like.

Examples of the acrylate compound include methacrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, mercapto methacrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloro Acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-propenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, 3-propenyloxypropyltriethoxydecane, and epoxypropyl acrylate.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylic acid. Ester, phenyl methacrylate, mercaptomethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethylmethyl Acrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrogen Mercapto methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methylpropenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, 3 -Methyl propylene methoxy propyl triethoxy decane, epoxy propyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate Ester and the like.

The acrylamide compound may, for example, be acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-benzyl acrylamide, N-phenyl acrylamide, N, N-dimethyl Acrylamide, and N-mercaptopropenylamine.

The methacrylamide compound may, for example, be methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenyl. Methyl acrylamide, N,N-dimethyl methacrylamide, and N-mercapto acrylamide.

The vinyl compound may, for example, be vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyl trimethoxy decane, 2 -Chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene.

Examples of the styrene compound include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and ethyl styrene styrene.

The maleidin compound may, for example, be maleimine, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzyl Maleic imine, and N-hydroxyethyl maleimide, and the like.

The molecular weight of the addition resin (polymer) used in the adhesive composition of the present invention is, for example, 1000 to 1,000,000, or 3,000 to 300,000, and further, for example, 5,000 to 200,000, or 10,000 to 100,000, by weight average molecular weight.

When the adhesive composition of the present invention contains an added resin (polymer), the content thereof is, for example, 0 to 40% by mass, or 0 to 20% by mass, or 1 to 19% by mass in the solid content.

The adhesion imparting agent is added for the elastic modulus, viscosity control, and surface state control of the adhesive layer. The type of the adhesion-imparting agent is preferably determined in consideration of the adhesiveness of the adhesive layer, and specific examples thereof include an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic ‧ aromatic copolymerized petroleum resin, and an alicyclic group. Hydrogenated petroleum resin, alkylphenol resin, xylene resin, coumarone oxime resin, terpene resin, terpene phenol resin, aromatic modified terpene resin, hydrogenated terpene resin, rosin resin, hydrogenated rosin resin One type or a combination of two or more types of the rosin-based resin, the second-quantized rosin-based resin, and the esterified rosin-based resin. The adhesion-imparting agent may contain a ratio of 0 to 100 parts by weight based on 100 parts by weight of the polyether as a main component of the adhesive composition.

Therefore, the value of the addition amount of the adhesion-imparting agent is preferably in the range of 0 to 100 parts by weight, more preferably in the range of 0 to 50 parts by weight.

Further, the present invention relates to a laminate of an adhesive layer comprising at least two binders and an adhesive composition of the present invention provided between the binders.

In the present invention, the adhesive composition of the present invention is applied by spin coating on the first adherend, and is fired at 50 to 300 ° C to form an adhesive layer, and the formed adhesive layer is formed. 2 A method in which the substrate is followed by the step of the first substrate to obtain a substrate. Further, a step of processing the layer of the layer of the laminate may be included.

Further, the step of forming a subsequent layer on the second object to be repeated, the step of passing the formed subsequent layer to form the third object to be attached to the second object, and the subsequent article to be formed as needed The step of layer processing may also form a laminate of a plurality of substrates to be bonded and an adhesive layer formed therebetween.

In the present invention, the thickness of the adhesive applied by spin coating on the semiconductor wafer may be 0.1 μm or more and 200 μm or less. When the thickness is less than 0.1 μm, the surface unevenness cannot be bonded, and there is a possibility that a hole is formed in the subsequent case, and if it is thicker than 200 μm, there is a possibility that cracks may occur in the adhesive layer. More preferably, the thickness of the adhesive layer is from 1 μm to 50 μm.

[Examples]

Hereinafter, examples of confirming the characteristics of the adhesive composition of the present invention will be described.

However, the invention is not limited to the embodiments.

The GPC analysis of the polymer compound obtained in the synthesis example described below was carried out using the following apparatus, and the following measurement conditions were used.

Device: Integrated high-speed GPC system HLC-8220GPC made by Tosoh Corporation

Column: KF-G, KF804L

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0mL/min

Standard sample: polystyrene

Detector: R1

Synthesis Example 1

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 24.10 g of 4,4'-dichlorodiphenyl-anthracene and 24.77 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane were placed. Potassium carbonate 29.02 g, N-methyl-2-pyrrolidone 369.50 g. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 1 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum dried at 85 ° C for 1 day to obtain an aromatic polyether ether oxime (equivalent formula (1-1)) used in the present invention. The obtained aromatic polyether was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 18,600.

Synthesis Example 2

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 4,4'-dichlorodiphenyl-anthracene 68.20 g, 2,2-bis(4-hydroxyphenyl)hexafluoropropane 84.06 g, 103.68 g of potassium carbonate and 456.98 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. Thereafter, 32.83 g of 4-fluorobenzene trifluoride as a blocking agent was dropped, and a sample of 160.48 g of N-methyl-2-pyrrolidone was added thereto, followed by stirring for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 100 ml of a mixed solution of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a group in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyether ether oxime (equivalent formula (1-1)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 17,000.

Synthesis Example 3

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 16.37 g of 4,4'-dichlorodiphenyl-anthracene, 9.97 g of tert-butyl hydroquinone, and 24.90 g of potassium carbonate, N- were placed. Methyl-2-pyrrolidone 79.04 g. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. Thereafter, 7.90 g of 4-fluorobenzene trifluoride as a blocking agent was added dropwise to a sample of 28.94 g of N-methyl-2-pyrrolidone, followed by stirring for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a group in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyether ether oxime (equivalent formula (1-2)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 14,800.

Synthesis Example 4

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 13.4 g of 4,4'-dichlorodiphenyl-anthracene and 13.42 g of 1,1-bis(4-hydroxyphenyl)cyclohexane were placed. 20.78 g of potassium carbonate and 81.23 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. Thereafter, a sample of 6.55 g of 4-fluorobenzene trifluoride dissolved in N-methyl-2-pyrrolidone (28.75 g) was added dropwise thereto, followed by stirring for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a block in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyether ether oxime (equivalent formula (1-3)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 14,600.

Synthesis Example 5

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 14.4 g of 4,4'-dichlorodiphenyl-anthracene and 8.41 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane were placed. 5.71 g of 2,2-bis(4-hydroxyphenyl)propane, 34.56 g of potassium carbonate, and 83.44 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. Thereafter, a sample of 6.56 g of 4-fluorobenzene trifluoride dissolved in N-methyl-2-pyrrolidone (29.56 g) was added dropwise thereto, followed by stirring for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a group in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyether ether oxime (equivalent formula (1-4)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 17,700.

Synthesis Example 6

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 14.4 g of 4,4'-dichlorodiphenyl-anthracene and 8.41 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane were placed. Tert-butyl hydroquinone 4.16 g, potassium carbonate 34.55 g, and N-methyl-2-pyrrolidone 78.95 g. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. Thereafter, a sample of 6.56 g of 4-fluorobenzene trifluoride dissolved in N-methyl-2-pyrrolidone 28.06 g was added dropwise, followed by stirring for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a group in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyether ether oxime (equivalent formula (1-5)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 17,300.

Synthesis Example 7

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 94.26 g of 4,4'-difluorobenzophenone, 44.88 g of tert-butyl hydroquinone, and 33.52 g of methyl hydroquinone were placed. 82.10 g of potassium carbonate and 764.27 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was subjected to nitrogen substitution, and then heated to 140 ° C and reacted for 20 hours. After cooling the synthesized aromatic polyetheretherketone to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain a group in which the aromatic polyether used in the present invention was blocked with a substituent. The obtained aromatic polyetheretherketone (equivalent formula (1-6)) was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 15,200.

Synthesis Example 8

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 14.07 g of 4,4'-dichlorodiphenyl fluorene and 1.40 g of 1,1-bis(4-hydroxyphenyl)hexafluoropropane were placed. There were 6.71 g of 1-bis(4-hydroxyphenyl)cyclohexane, 20.75 g of potassium carbonate, and 87.68 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was poured into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum dried at 85 ° C for 1 day to obtain an aromatic polyether ether oxime (equivalent formula (1-7)) used in the present invention. The obtained aromatic polyether was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 43,000.

Synthesis Example 9

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 74.19 g of 4,4'-difluorobenzophenone and 94.14 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane were placed. 18.26 g of methyl hydroquinone, 60.81 g of potassium carbonate, and 742.22 g of N-methyl-2-pyrrolidone. Thereafter, the inside of the flask was subjected to nitrogen substitution, and then heated to 140 ° C and reacted for 20 hours. After cooling the synthesized aromatic polyetheretherketone to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum dried at 85 ° C for 1 day to obtain an aromatic polyether ether ketone (equivalent formula (1-8)) used in the present invention. The obtained aromatic polyether was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 24,700.

Synthesis Example 10

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 40.42 g of 4,4'-difluorobenzophenone and 73.97 g of 2,2-bis(4-hydroxyphenyl)hexafluoropropane were placed. 4-(4-hydroxy-3,5-dihydroxymethylphenyl)propane 4.03 g, potassium carbonate 32.01 g, and N-methyl-2-pyrrolidone 752.16 g. Thereafter, the inside of the flask was subjected to nitrogen substitution, and then heated to 140 ° C and reacted for 20 hours. After cooling the synthesized aromatic polyetheretherketone to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum dried at 85 ° C for 1 day to obtain an aromatic polyether ether ketone (equivalent formula (1-9)) used in the present invention. The obtained aromatic polyether was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 19,000.

Comparative Synthesis Example 1

In a flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank, 15.00 g of 4,4'-dichlorodiphenyl-fluorene, 12.56 g of 2,2-bis(4-hydroxyphenyl)propane, and potassium carbonate were placed. 8.37 g of 82.61 g of N-methyl-2-pyrrolidone, and then the inside of the flask was substituted with nitrogen, and then heated to 160 ° C for 20 hours. After the synthesized aromatic polyether ether was cooled to room temperature, the filtrate was collected by filtration, and mixed with 30 ml of a mixture of N-methyl-2-pyrrolidone and 2 mol/l hydrochloric acid in a volume ratio of 90:10. Thereafter, the mixed solution was introduced into methanol for reprecipitation purification.

Thereafter, the obtained precipitate was washed with methanol and water, and vacuum-dried at 85 ° C for 1 day to obtain an aromatic polyether ether oxime (Comparative Formula (2-1)) used in Comparative Example 1. The obtained aromatic polyether was subjected to GPC analysis, and the weight average molecular weight in terms of standard polystyrene was 16,700.

【化9】

Comparative Synthesis Example 2

Polymethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) of an acrylic resin synthesized in a commercial product was prepared.

(solvent solubility evaluation)

With respect to the aromatic polyether obtained in Synthesis Example 1 to 10 and Comparative Synthesis Example 1 and 5 parts by mass of the acrylic resin of Comparative Synthesis Example 2, (1) propylene glycol monomethyl ether (PGME) and (2) were used as the respective solvents. Propylene glycol monomethyl ether acetate (PGMEA), (3) ethyl lactate (EL), (4) cyclohexanone (Cy), (5) N-methyl-2-pyrrolidone (NMP), (6) Dimethylacetamide (DMAC), (7) 4-methyl 2-pentanone (MIBK), (8) 5-methyl-2-hexanone (MIAK), (9) ethyl acetate (EAA), (10) γ-butyl lactone (GBL), and (11) cyclopentanone (Cp) were added in a ratio of 95 parts by mass to evaluate solubility.

The results are shown in Table 1. ○ is dissolved, Δ is slightly soluble, and × is insoluble.

The aromatic polyether obtained in Synthesis Example 1 to 10 had the same solubility as the acrylic resin used in Comparative Synthesis Example 2, and was more soluble than the polyhydrazine obtained in Comparative Synthesis Example 1.

(heat resistance evaluation)

TG-DTA (manufactured by Bruker AXS Co., Ltd., TG/DTA2010SR) was used for the heat resistance of the aromatic polyether obtained in Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 and the polymethyl methacrylate used in Comparative Synthesis Example 2 The temperature rise of 10 ° C / min produced a temperature reduction of 5% by mass. The results are shown in Table 2.

The aromatic polyether of Synthesis Example 1 to 10 used in the present invention is similar to the aromatic polyether of Comparative Synthesis Example 1 in that the temperature at which the mass by 5% by weight is reduced to 450 ° C or higher, which is comparable to the acrylic resin of Comparative Synthesis Example 2. High heat resistance.

(adjustment of the composition of the adhesive)

The aromatic polyether obtained in Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 and the acrylic resin in Comparative Synthesis Example 2 were used, and each of the following compositions was used to prepare an adhesive composition.

Example 1

The aromatic polyether obtained in Synthesis Example 1 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

Example 2

The aromatic polyether obtained in Synthesis Example 2 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

Example 3

The aromatic polyether obtained in Synthesis Example 3 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

Example 4

The aromatic polyether obtained in Synthesis Example 4 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

Example 5

The aromatic polyether obtained in Synthesis Example 5 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

Example 6

The aromatic polyether obtained in Synthesis Example 6 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

Example 7

The aromatic polyether obtained in Synthesis Example 7 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

Example 8

The aromatic polyether obtained in Synthesis Example 8 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

Example 9

The aromatic polyether obtained in Synthesis Example 9 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

Example 10

The aromatic polyether obtained in Synthesis Example 10 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

Example 11

The Cymel 303 (crosslinking agent) having a 5% by mass of the aromatic polyether obtained in Synthesis Example 10 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content.

Example 12

Pine crystal KE100 (plasticizer, manufactured by Arakawa Chemical Industries Co., Ltd., trade name, and esterified rosin resin) was dissolved in cyclohexanone in an amount of 5% by mass of the aromatic polyether obtained in Synthesis Example 7. 20% by mass of the solid component of the adhesive composition.

Comparative example 1

The aromatic polyether obtained in Comparative Synthesis Example 1 was dissolved in N _- methyl _- 2-pyrrolidone to prepare an adhesive composition containing 10% by mass of a solid content.

Comparative example 2

The polymethyl methacrylate of Comparative Example 2 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid component.

(coating evaluation)

Each of the adhesive compositions obtained in Examples 1 to 12, Comparative Example 1 and Comparative Example 2 was spin-coated on a ruthenium wafer at a coating condition of 1000 rpm for 30 seconds, and each was applied at 100 ° C and 250 ° C for each. The film formed by baking for 2 minutes was evaluated. The results are shown in Table 3.

The adhesive composition of the aromatic polyether adjusted in Examples 1 to 12 of the present invention was compared with the adhesive composition adjusted in Comparative Example 1, and a coating film was not formed, and a uniform film could not be formed. The adhesive composition of the acrylic resin to be used can form a uniform film of 1 μm or more.

(subsequent assessment)

The adhesive compositions obtained in Examples 1 to 12 and Comparative Examples 1 and 2 were applied on a ruthenium wafer at a coating condition of 1000 rpm and 30 seconds, and then each was carried out at 100 ° C and 250 ° C for 2 minutes. Baking and forming a coating film on each of the germanium wafers. The tantalum wafer was cut into a 2 cm square, and the coating was placed face down on a preheated glass wafer on a hot plate of 270 ° C to be pressure-bonded from above, and the adhesion was evaluated. The results are shown in Table 4. It was evaluated that the state of the glass wafer surface was observed and no holes (holes) were followed.

The adhesive composition obtained in Comparative Example 1 was defective in adhesion and could not be uniformly followed. The adhesive compositions of Examples 1 to 12 of the present invention and the adhesive composition of Comparative Example 2 had good adhesion.

(Follow the force evaluation sample production)

The adhesion test samples of the aromatic polyether adjusted in Synthesis Example 7 and Synthesis Example 9 and the acrylic resin of Comparative Synthesis Example 2 were produced by the following method.

Example 13

The aromatic polyether obtained in Synthesis Example 7 was dissolved in cyclohexanone to prepare an adhesive composition containing 27% by mass of a solid component. The adhesive composition was spin-coated on a 4 Å wafer at a coating condition of 1500 rpm for 60 seconds, and each was baked at 100 ° C and 230 ° C for 2 minutes to form a film having a film thickness of 5.5 μm. Thereafter, using a bonding apparatus (manufactured by Ayumi Industries Co., Ltd., VJ-300), the ruthenium wafer permeable film was bonded to a 4 Å glass wafer under the conditions of a vacuum of 10 Pa or less, a temperature of 250 ° C, and a bonding pressure of 300 kg. The wafer was cut into a 1 cm square by a cutting device (manufactured by DISCO Corporation, DAD321) to prepare a sample.

Example 14

The aromatic polyether obtained in Synthesis Example 9 was dissolved in cyclohexanone to prepare an adhesive composition containing 27% by mass of a solid component. The adhesive composition was spin-coated on a 4 Å wafer at a coating condition of 1500 rpm for 60 seconds, and baked at 100 ° C and 230 ° C for 2 minutes to form a film having a film thickness of 4.9 μm. Thereafter, using a bonding apparatus (manufactured by Ayumi Industries Co., Ltd., VJ-300), the ruthenium wafer permeable film was bonded to the 4 Å glass wafer under the conditions of a vacuum of 10 Pa or less, a temperature of 270 ° C, and a bonding pressure of 300 kg. The wafer was cut into a 1 cm square by a cutting device (manufactured by DISCO Corporation, DAD321) to prepare a sample.

Comparative example 3

The acrylic resin of Comparative Synthesis Example 2 was dissolved in cyclohexanone to prepare an adhesive composition containing 20% by mass of a solid content. The adhesive composition was spin-coated on a 4 Å wafer at a coating condition of 1300 rpm for 60 seconds, and baked at 100 ° C and 200 ° C for 2 minutes to form a film having a film thickness of 5.0 μm. Thereafter, using a bonding apparatus (manufactured by Ayumi Industries Co., Ltd., VJ-300), the ruthenium wafer permeable film was bonded to the 4 Å glass wafer under the conditions of a vacuum of 10 Pa or less, a temperature of 270 ° C, and a bonding pressure of 400 Kg. The wafer was cut into a 1 cm square by a cutting device (manufactured by the company DISCO, DAD321) to prepare a sample.

(Continue to force evaluation 1)

ARALDITE 2014 (manufactured by Huntsman Advanced Materials Co., Ltd., trade name) was applied to both surfaces of the adhesion evaluation samples obtained in Example 13 and Example 14 and Comparative Example 3, and the special jig for the measurement of the force (shear) was applied to both sides. After that, the adhesion force (cutting) was evaluated by a universal material testing machine (manufactured by Shimadzu Corporation, a universal material testing machine AGS-100NX). Then, the force was measured at a tensile speed of 1 mm/min. The results are shown in Table 5.

In Table 5, the value of the subsequent force is 1000 N or more and is equal to or higher than the measurement limit of the above-described adhesion measuring machine.

The samples obtained in Examples 13 and 14 had higher adhesion than the samples obtained in Comparative Example 3.

(Continue to force evaluation 2)

The adhesion evaluation samples obtained in Example 13 and Example 14 and Comparative Example 3 were placed on a hot plate at 350 ° C for 1 hour, and ARALDITE 2014 (manufactured by Huntsman Advanced Materials Co., Ltd., trade name) was applied to both sides of the sample after standing. After the two sides of the cutting force measurement tester were used, the adhesive force (shearing) was evaluated by a universal material testing machine (manufactured by Shimadzu Corporation, a universal material testing machine AGS-100NX). Then, the force was measured at a tensile speed of 1 mm/min. The results are shown in Table 6.

In Table 6, the value of the subsequent force is 1000 N or more, which means that it is more than the measurement limit of the above-mentioned adhesion measuring machine.

The high adhesion was maintained for the samples obtained in Example 13 and Example 14, and the sample obtained in Comparative Example 3 had a lower adhesion force.

[Industrial use]

It can be made into an adhesive layer which is easily soluble in various organic solvents and has good coatability and can form a sufficient thickness, and the adhesive layer has little thermal weight reduction and adhesion in a high-temperature process such as metal bump bonding, CVD, ion diffusion step and the like. A highly heat resistant adhesive composition having good properties.

Claims (16)

An adhesive composition characterized by containing the following formula (1): (wherein X is a sulfonyl group or a carbonyl group, each of Ar ¹ and Ar ² is an exoaryl group having 6 to 30 carbon atoms, and T ¹ is a fluoroalkyl group, a cyclic alkyl group, having a carbon number of 1 or even a polymer and a solvent of a unit structure represented by an alkyl group of 10, or a combination of a aryl group which may have a substituent and a fluorine alkyl group or a cyclic alkyl group, and the solvent is removed from the composition The solid content is a ratio of 0.1 to 80% by mass relative to the composition of the adhesive. The adhesive composition according to claim 1, wherein the exoaryl group is a phenylene group, a naphthyl group, or a fluorenyl group. The adhesive composition according to claim 1 or claim 2, wherein the polymer is a single polymer having one type of unit structure. The adhesive composition according to claim 1 or claim 2, wherein the polymer is a copolymer having at least two types of unit structures. The adhesive composition according to claim 1 or claim 2, characterized in that each of Ar ¹ and Ar ² is contained in the following formula (2): (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, a cyano group, a nitro group or a fluorenyl group; a unit represented by the above formula (1), which is a group represented by a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and n1 is an integer of 0 to 4) Constructed polymer. The requested item described in item 1 or 2 requests the adhesive composition, which system contains containing T ¹ is the cell structure (1) represented by the above formula (3) the group represented by the following formula, T ¹ is the next a polymer having a unit structure represented by the above formula (1) represented by the formula (4) or a combination of unit structures thereof, (wherein R ² , R ³ and R ⁴ are each an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, and a cyanogen group; a group, a nitro group, a fluorenyl group, a decyloxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, and each of n2, n3 and n4 is an integer of 0 to 4, T ² It is a fluoroalkyl group, a cyclic alkyl group, or a combination thereof. The adhesive composition according to claim 6, wherein, in the above formula (3), R ² is a third butyl group, and n 2 is an integer of 1 to 4. The adhesive composition according to claim 1 or claim 2, which further comprises the formula (5) in addition to the unit structure represented by the formula (1): (wherein X is a sulfonyl group or a carbonyl group, each of Ar ³ and Ar ⁴ is an exoaryl group having 6 to 30 carbon atoms, and T ³ is an alkylene group, a sulfonyl group, a carbonyl group, or a carbon number of 6 or 30. A copolymer of a unit structure represented by an aryl group or a combination thereof. The adhesive composition according to claim 8, wherein the exoaryl group is a phenylene group, a naphthyl group, or a fluorenyl group. The adhesive composition according to claim 8, wherein the T ³ formula (6): (wherein R ⁵ and R ⁶ are each an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a hydroxyl group, an allyl group, an allyloxy group, an amine group, a cyano group, and a nitrate a group, a mercapto group, a mercaptooxy group, a carboxyl group, a group having a third-order carbon structure, a cyclic alkyl group, or a combination thereof, each of n5 and n6 is an integer of 0 to 4, and T ⁴ is an alkylene group, a group represented by a sulfonyl group, a carbonyl group, a aryl group having 6 or 30 carbon atoms, or a combination thereof. The adhesive composition according to claim 1 or claim 2, wherein the group having the third-order carbon structure is a third butyl group. The adhesive composition according to claim 1 or claim 2, wherein the polymer has a weight average molecular weight of 500 to 5,000,000. The adhesive composition according to claim 1 or claim 2, which further contains a crosslinking agent. The adhesive composition as claimed in claim 1 or claim 2, which has a 0.001 to 5000 Pa. s viscosity. A laminate comprising at least two adherends, and 0.1 μm or even 200 μm formed of the adhesive composition described in claim 1 or claim 2 disposed between the substrates Floor. The laminate according to claim 15, wherein each of the substrates to be bonded is selected from the group consisting of a ruthenium substrate, a glass substrate, a resin substrate, or a ceramic substrate.