JP7610588B2 - Polyfunctional compound, composition, adhesive composition, adhesive composition set, adhesion method, and structure - Google Patents

Description

The present invention relates to a multifunctional compound, a composition, an adhesive composition, an adhesive composition set, an adhesion method, and a structure.

Structural adhesives are used in a wide variety of applications as highly reliable adhesives that can withstand heavy loads for long periods of time. Known types of structural adhesives include epoxy adhesives, urethane adhesives, and second generation (SGA) acrylic adhesives.

These structural adhesives each have different properties depending on the type. For example, epoxy adhesives tend to have high adhesive strength and low elongation, urethane adhesives tend to have high elongation and low adhesive strength, and acrylic adhesives tend to have performance between epoxy and urethane adhesives.

Structural adhesives are used on a variety of substrates, including automotive structural materials and marine and aerospace structural materials. Structural adhesives used on these substrates are required to bond dissimilar materials such as metals, resins, and glass. For example, due to the demand for lighter components, aluminum and CFRP are used in some automotive components. These components are mainly joined using mechanical joining methods such as riveting, and epoxy-based structural adhesives used to join dissimilar materials are limited to certain areas of application.

This is because there is a problem with the durability and reliability of structural adhesives. Specifically, structural adhesives have poor extensibility after curing, and cannot alleviate the stress caused by the difference in linear expansion coefficients when joining different materials, resulting in durability deterioration and peeling of the adhesive surface (see, for example, Patent Documents 1 to 4).

For this reason, in order to alleviate the stress when joining different materials, a one-part epoxy adhesive that uses an epoxy resin and a latent curing agent and has an elongation rate of 15% after curing has been proposed (see, for example, Patent Document 5). In addition, a curable resin composition that contains a urethane acrylate and a monofunctional unsaturated compound has been reported as a resin composition that has a high elastic modulus and elongation from low to high temperatures and has excellent water resistance and heat resistance (see, for example, Patent Document 6).

Japanese Unexamined Patent Publication No. 4-145185 Japanese Patent Application Publication No. 5-148337 Japanese Patent Application Publication No. 5-156227 Japanese Unexamined Patent Publication No. 7-145225 JP 2009-108278 A Japanese Unexamined Patent Publication No. 63-090525

As mentioned above, structural materials have different thermal expansion coefficients, so structural adhesives that bond dissimilar components together must have not only adhesive strength to each dissimilar component, but also elongation. Furthermore, structural materials used in automotive, marine, and aerospace structures must be able to withstand a wide range of temperatures, from low to high. For this reason, the adhesive strength and elongation of the structural adhesives that bond them together must remain constant over this wide temperature range.

The present invention has been made in consideration of the above problems, and aims to provide a multifunctional compound capable of producing an adhesive having a low temperature dependence of elongation, as well as a composition, adhesive composition, adhesive composition set, bonding method, and structure containing the multifunctional compound.

The present inventors conducted extensive research to solve the above problems. As a result, they discovered that the above problems could be solved by using a polyfunctional compound having a highly symmetrical arrangement of flexible chemical structures (soft segments) and rigid chemical structures (hard segments) in one molecule, and thus completed the present invention.

（式中、Ｘは、炭素原子又は炭素数１～２０のｎ価の連結基を示し、
Ａｒは、アリーレン基を示し、
Ｒ¹は、各々独立して、重合体ブロックを含む二価の基を示し、
Ｒ²は、各々独立して、グリシジル基、フェノール基、水酸基、カルボキシル基、アミノ基、チオール基、シアノ基、ニトロ基、又は酸無水物基を示し、
ｎは、３～８の整数を示す。）
〔２〕
前記重合体ブロックが、シロキサン結合単位、ウレタン結合単位、エーテル結合単位、スルフィド結合単位、ブタジエン単位、及びイソプレン単位からなる群より選ばれる少なくとも１つの繰り返し単位を有する重合体ブロックである、
〔１〕に記載の多官能化合物。
〔３〕
前記重合体ブロックが、ポリシロキサン骨格を有する、
〔１〕又は〔２〕に記載の多官能化合物。
〔４〕
前記重合体ブロックのガラス転移温度が、５０℃以下である、
〔１〕～〔３〕のいずれか一項に記載の多官能化合物。
〔５〕
前記重合体ブロックが、融点を有しない、
〔１〕～〔４〕のいずれか一項に記載の多官能化合物。
〔６〕
異なるｎを有する複数の前記多官能化合物を含む、
〔１〕～〔５〕のいずれか一項に記載の多官能化合物。
〔７〕
前記多官能化合物の数平均分子量が、８００～１０００００である、
〔１〕～〔６〕のいずれか一項に記載の多官能化合物。
〔８〕
前記多官能化合物の分子量分布（Ｍｗ／Ｍｎ）が、１．５以上である、
〔１〕～〔７〕のいずれか一項に記載の多官能化合物。
〔９〕
前記重合体ブロックの数平均分子量が、２００～２００００である、
〔１〕～〔８〕のいずれか一項に記載の多官能化合物。
〔１０〕
前記Ａｒが、炭素数６～１０のアリーレン基を示す、
〔１〕～〔９〕のいずれか一項に記載の多官能化合物。
〔１１〕
〔１〕～〔１０〕のいずれか一項に記載の多官能化合物と、
硬化促進剤と、を含む、
組成物。
〔１２〕
前記Ｒ²と反応し化学結合を形成する官能基を有する硬化剤をさらに含む、
〔１１〕に記載の組成物。
〔１３〕
〔１１〕又は〔１２〕に記載の組成物を、含む、
接着剤組成物。
〔１４〕
〔１〕～〔１０〕のいずれか一項に記載の多官能化合物を含む第１剤と、
硬化剤を含む第２剤と、を有する、
接着剤組成物セット。
〔１５〕
〔１３〕に記載の接着剤組成物、又は、〔１４〕に記載の接着剤組成物セットを用いて、被着体を接着する工程を有する、
接着方法。
〔１６〕
〔１３〕に記載の接着剤組成物、又は、〔１４〕に記載の接着剤組成物セットを用いて接着された、
構造物。 That is, the present invention is as follows.
[1]
A polyfunctional compound represented by the following formula (1):

(In the formula, X represents a carbon atom or a linking group having 1 to 20 carbon atoms and a valence of n,
Ar represents an arylene group;
Each R ¹ independently represents a divalent group containing a polymer block,
^R2 each independently represents a glycidyl group, a phenol group, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a cyano group, a nitro group, or an acid anhydride group;
n represents an integer of 3 to 8.
[2]
the polymer block is a polymer block having at least one repeating unit selected from the group consisting of a siloxane bond unit, a urethane bond unit, an ether bond unit, a sulfide bond unit, a butadiene unit, and an isoprene unit;
The polyfunctional compound according to [1].
[3]
The polymer block has a polysiloxane skeleton.
The polyfunctional compound according to [1] or [2].
[4]
The glass transition temperature of the polymer block is 50° C. or less.
The polyfunctional compound according to any one of [1] to [3].
[5]
The polymer block has no melting point;
The polyfunctional compound according to any one of [1] to [4].
[6]
A plurality of the polyfunctional compounds having different n are included.
The polyfunctional compound according to any one of [1] to [5].
[7]
The number average molecular weight of the polyfunctional compound is 800 to 100,000.
The polyfunctional compound according to any one of [1] to [6].
[8]
The molecular weight distribution (Mw/Mn) of the polyfunctional compound is 1.5 or more.
The polyfunctional compound according to any one of [1] to [7].
[9]
The number average molecular weight of the polymer block is 200 to 20,000.
The polyfunctional compound according to any one of [1] to [8].
[10]
The Ar represents an arylene group having 6 to 10 carbon atoms.
The polyfunctional compound according to any one of [1] to [9].
[11]
[1] to [10], and
and a curing accelerator,
Composition.
[12]
Further comprising a curing agent having a functional group that reacts with the ^R2 to form a chemical bond;
The composition described in [11].
[13]
The composition according to [11] or [12] is included.
Adhesive composition.
[14]
A first agent containing the polyfunctional compound according to any one of [1] to [10];
and a second agent including a curing agent.
Adhesive composition set.
[15]
The method includes a step of adhering an adherend using the adhesive composition according to [13] or the adhesive composition set according to [14].
Gluing method.
[16]
[13] or the adhesive composition set according to [14],
Structure.

According to the present invention, it is possible to provide a multifunctional compound capable of producing an adhesive having a low temperature dependence of elongation, as well as a composition, adhesive composition, adhesive composition set, bonding method, and structure containing the multifunctional compound.

The NMR data of the compound obtained in Example 1 is shown below.

Below, we will explain in detail the embodiment of the present invention (hereinafter referred to as the "present embodiment"); however, the present invention is not limited to this embodiment, and various modifications are possible without departing from the gist of the present invention.

（式中、Ｘは、炭素原子又は炭素数１～２０のｎ価の連結基を示し、
Ａｒは、アリーレン基を示し、
Ｒ¹は、各々独立して、重合体ブロックを含む二価の基を示し、
Ｒ²は、各々独立して、グリシジル基、フェノール基、水酸基、カルボキシル基、アミノ基、チオール基、シアノ基、ニトロ基、又は酸無水物基を示し、
ｎは、３～８の整数を示す。） [Polyfunctional Compounds]
The polyfunctional compound of the present embodiment is a compound represented by the following formula (1), and may be a mixture containing a plurality of compounds having different n in the following formula (1).

(In the formula, X represents a carbon atom or a linking group having 1 to 20 carbon atoms and a valence of n,
Ar represents an arylene group;
Each R ¹ independently represents a divalent group containing a polymer block,
^R2 each independently represents a glycidyl group, a phenol group, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a cyano group, a nitro group, or an acid anhydride group;
n represents an integer of 3 to 8.

The polyfunctional compound has a structure in which polymer blocks extend from the linking group X via bulky arylene groups. The portion consisting of the linking group X and the arylene group Ar is a portion in which the bond rotation within the molecule is restricted by steric hindrance, and this portion is also called a hard segment. In contrast, the portion consisting of ^R1 representing the polymer block and the reactive group ^R2 arranged at its end is a portion in which the bond rotation within the molecule is not easily restricted by steric hindrance, and this portion is also called a soft segment.

In this embodiment, n represents an integer between 3 and 8, and the polyfunctional compound has a 3- to 8-branched structure in which the arms of the soft segments extend around the hard segment. In this way, a compound having a flexible structure and a rigid structure with high symmetry in one molecule forms a uniform crosslinked structure when cured. In this uniform crosslinked structure, the molecular arrangement is regular and the stress distribution is reduced, so that micro-Brownian motion is equally restricted and the property of low temperature dependency is exhibited. The reason for the low temperature dependency of the elongation is not limited to the above.

Therefore, the multifunctional compound of this embodiment is suitable for use as a structural adhesive for dissimilar materials used over a wide temperature range, such as adhesives for automobile structures and marine and aerospace materials.

（式中、置換基Ｒ^x1は、水素原子が後述する置換基Ｒ^x2により置換されていてもよい炭素数２～８の炭化水素基を示す。） The n-valent linking group X having carbon atoms or 1 to 20 carbon atoms is not particularly limited, and examples thereof include the following saturated hydrocarbon groups having an n-branched structure, arene groups having an n-branched structure, saturated hydrocarbon groups having an n-branched structure in which a carbon atom is substituted with another atom such as oxygen, or groups having an n-branched structure in which a part of the branched chain of these is substituted with a substituent R ^x1 . Here, the terms "n-valent linking group" and "n-branched structure" mean that the linking group X has n soft segments.

(In the formula, the substituent R ^x1 represents a hydrocarbon group having 2 to 8 carbon atoms in which a hydrogen atom may be substituted by a substituent R ^x2 described later.)

In the above examples, the linking group X has one substituent R ^x1 , but the linking group X may have multiple substituents R ^x1 as long as it has a branched structure with 3 to 8 carbon atoms. The hydrocarbon group having 2 to 8 carbon atoms represented by the substituent R ^x1 is not particularly limited, and examples thereof include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, and cyclohexyl groups; and aryl groups such as phenyl and tolyl groups. The substituent R ^x2 that can be bonded to the substituent R ^x1 is not particularly limited, and examples thereof include halogen atoms, hydroxyl groups, alkoxy groups, carbonyl groups, amino groups, imino groups, cyano groups, and thiol groups.

（式中、Ｒ¹～Ｒ²及びｎは、上記と同様であり、置換基Ｒ^arは、各々独立して、水素原子又は炭素数１～５の炭化水素基を示す。） The arylene group represented by Ar is not particularly limited, and examples thereof include a phenylene group and a naphthylene group. In the arylene group Ar, a hydrogen atom may be substituted with a substituent R ^ar . Examples of such polyfunctional compounds include the following. Among these, an arylene group having 6 to 10 carbon atoms is more preferred, and a phenylene group is even more preferred. By using such an arylene group Ar, the rigidity of the hard segment tends to be further improved.

(In the formula, R ¹ to R ² and n are the same as above, and the substituents R ^ar each independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.)

The hydrocarbon group having 1 to 5 carbon atoms represented by the substituent R ^ar is not particularly limited, and examples thereof include linear, branched, or cyclic alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.

^R1 represents a divalent group containing a polymer block. Such a polymer block is not particularly limited, but examples thereof include those having at least one repeating unit selected from the group consisting of a siloxane bond unit, a urethane bond unit, an ether bond unit, a sulfide bond unit, a butadiene unit, and an isoprene unit.

Examples of the polymer block having these repeating units include a polysiloxane skeleton having a siloxane bond unit, a polyurethane skeleton having a urethane bond unit, a polyether skeleton having an ether bond unit, a polysulfide skeleton having a sulfide bond unit, a polybutadiene skeleton having a butadiene unit, and a polyisoprene skeleton having an isoprene unit. Among these, a polysiloxane skeleton having a siloxane bond unit is preferred. By having such ^R1 , the flexibility of the soft segment tends to be further improved.

As described later, examples of the method for producing the polyfunctional compound of this embodiment include a method of reacting the end of a polymer with a polymerization coupling agent, and a method of polymerizing a monomer using a polyvalent initiator capable of generating multiple polymerization initiation ends. In such a case, the hard segment composed of the linking group X and the arylene group Ar can be said to be a portion derived from the polymerization coupling agent or the polyvalent initiator. In addition, the soft segment composed of R ¹ representing a polymer block and the reactive group R ² arranged at its end is a polymer reacted with a polymerization coupling agent, or a portion polymerized from a monomer, and can be said to be a portion derived from one whose polymerization end has been modified as necessary.

From this point of view, the divalent group containing a polymer block represented by R ¹ also includes a polymer block composed of repeating units and a connecting group at the end of the polymer block for connecting to Ar or R ² as necessary.

For example, assume that a polysiloxane skeleton having both ends modified with epoxy groups is used as the polymer block. In this case, the end on the Ar side of ^R1 has a connecting group formed by condensation of a hydroxyl group of a polymerization coupling agent with an epoxy group. In addition, the end on the ^R2 side of ^R1 has a connecting group derived from epoxy group modification, such as the methyl group portion of a glycidyl group. This is also true for polyurethane skeletons having hydroxyl or carboxyl groups at both ends and polyether skeletons having hydroxyl groups at both ends.

In addition, when a polybutadiene skeleton or polyisoprene skeleton not having such functional groups at both ends is used as the polymer block, for example, polybutadiene or polyisoprene modified at both ends with hydroxyl groups or the like can be used. In this case, the end on the Ar side of ^R1 has a connecting group formed by condensation of a hydroxyl group with a carboxyl group or the like of a polymerization coupling agent. In addition, when the hydroxyl group is modified to, for example, a glycidyl group ( ^R2 ), the end on the ^R2 side of ^R1 has a connecting group derived from the modification.

As described above, the divalent group containing a polymer block represented by ^R1 is a concept including a connecting group at its terminal for bonding to Ar and ^R2, respectively. Note that the description of the connecting group above is merely an example, and the terminal of ^R1 is not limited to the connecting group exemplified above. In addition, the number of atoms (excluding hydrogen atoms) constituting each connecting group is preferably 1 to 10, more preferably 1 to 5, from the viewpoint of functioning as a connecting group.

The glass transition temperature of the polymer block is preferably 50°C or lower, more preferably -150 to 25°C, even more preferably -150 to 0°C, even more preferably -150 to -10°C, even more preferably -150 to -50°C, and particularly preferably -150 to -75°C. When the glass transition temperature of the polymer block is 50°C or lower, the flexibility of the soft segment tends to be further improved. Furthermore, when the glass transition temperature of the polymer block is -150°C or higher, the hardness of the obtained cured product tends to be further improved. The glass transition temperature can be adjusted by the repeating units that constitute the polymer block.

It is preferable that the polymer block does not have a melting point. When the polymer block does not have a melting point, i.e., the polymer block is amorphous, the flexibility of the soft segment in the low temperature range tends to be improved. An example of an amorphous polymer block is a polysiloxane skeleton having a siloxane bond unit. An example of a polysiloxane skeleton is a polydimethylsiloxane skeleton.

The number average molecular weight of the polymer block is preferably 200 to 20,000, more preferably 300 to 10,000, and even more preferably 300 to 5,000. When the number average molecular weight of the polymer block is 300 or more, the length of the soft segments connecting the hard segments becomes longer when cured, and the stress distribution tends to be further reduced. Also, when the number average molecular weight of the polymer block is 20,000 or less, the length of the soft segments connecting the hard segments becomes shorter when cured, and the hardness of the cured product tends to be further improved.

^R2 represents a glycidyl group, a phenol group, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a cyano group, a nitro group, or an acid anhydride group. Among these, a glycidyl group, a phenol group, a hydroxyl group, a carboxyl group, or an amino group is preferred, and a glycidyl group or a hydroxyl group is more preferred.

The weight-average molecular weight (Mw) of the polyfunctional compound is preferably 1500 to 250,000, more preferably 4,500 to 100,000, and even more preferably 7,000 to 450,000. When the weight-average molecular weight of the polyfunctional compound is 1,500 or more, the length of the soft segments connecting the hard segments becomes longer when cured, and the stress distribution tends to be further reduced. Also, when the weight-average molecular weight of the polyfunctional compound is 250,000 or less, the length of the soft segments connecting the hard segments becomes shorter when cured, and the hardness of the cured product tends to be further improved.

The number average molecular weight (Mn) of the polyfunctional compound is preferably 800 to 100,000, more preferably 1,000 to 80,000, even more preferably 2,000 to 50,000, and even more preferably 3,000 to 20,000. When the number average molecular weight of the polyfunctional compound is 800 or more, the length of the soft segments connecting the hard segments becomes longer when cured, and the stress distribution tends to be further reduced. Also, when the number average molecular weight of the polyfunctional compound is 100,000 or less, the length of the soft segments connecting the hard segments becomes shorter when cured, and the hardness of the cured product tends to be further improved.

The molecular weight distribution (Mw/Mn) of the polyfunctional compound is preferably 1.5 or more, more preferably 1.5 to 4.0, and even more preferably 2.0 to 3.5. When the molecular weight distribution of the polyfunctional compound is within the above range, the symmetry of the polyfunctional compound tends to be uniform overall.

In addition, the weight average molecular weight, number average molecular weight, and molecular weight distribution of a polyfunctional compound refer to the weight average molecular weight, number average molecular weight, and molecular weight distribution of the polyfunctional compound when the polyfunctional compound is a type of polyfunctional compound having a specific n value, and refer to the weight average molecular weight, number average molecular weight, and molecular weight distribution of the multiple polyfunctional compounds when the polyfunctional compound is a mixture of multiple compounds having different n values.

In this embodiment, the weight average molecular weight, number average molecular weight and molecular weight distribution can be measured by gel permeation chromatography (GPC).

[Method for producing polyfunctional compounds]
The method for producing the polyfunctional compound of the present embodiment is not particularly limited, and examples thereof include method A in which an end of a polymer is reacted with a polymerization coupling agent, and method B in which a monomer is polymerized using a polyvalent initiator capable of generating a plurality of polymerization initiation ends.

(Method A)
Method A in which the terminal of a polymer is reacted with a polymer coupling agent will now be described. First, the raw materials used in the reaction will be described.

（式中、Ｘは、炭素原子又は炭素数２～２０のｎ’価の連結基を示し、Ａｒは、各々独立して、アリーレン基を示し、Ｒ³は、各々独立して、グリシジル基、フェノール基、水酸基、カルボキシル基、アミノ基、チオール基、シアノ基、ニトロ基、又は酸無水物基を示し、ｎ’は、３～１０の整数を示す。） The polymerizable coupling agent is not particularly limited, but for example, a compound represented by the following formula (2) can be used.

(In the formula, X represents a carbon atom or a linking group having a valence of n' and having 2 to 20 carbon atoms; each Ar independently represents an arylene group; each ^R3 independently represents a glycidyl group, a phenol group, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a cyano group, a nitro group, or an acid anhydride group; and n' represents an integer of 3 to 10.)

The linking group X and the arylene group Ar in the above formula (2) can be the same as those exemplified in the above polyfunctional compound.

Furthermore, ^R3 in the above formula (2) represents a group capable of bonding to the terminal group R2 ^' of the polymer described below. Such a group is not particularly limited, but examples thereof include a glycidyl group, a phenol group, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a cyano group, a nitro group, and an acid anhydride group.

In addition, n' in the above formula (2) can be the same value as or greater than the n exemplified in the above polyfunctional compound. This makes it easier to obtain a polyfunctional compound with n being 3 or more even if the reaction rate of the reaction between the polymerization coupling agent and the polymer is not 100%.

（式中、Ｒ^1'は、各々独立して、二価の重合体ブロックを示し、Ｒ^2'は、各々独立して、グリシジル基、フェノール基、水酸基、カルボキシル基、アミノ基、チオール基、シアノ基、ニトロ基、又は酸無水物基を示す。２個のＲ^2'は、同一でも良く、異なっても良い。） The polymer to be coupled with the polymerization coupling agent is not particularly limited, but for example, a polymer represented by the following formula (3) can be used.

(In the formula, each R ^1' independently represents a divalent polymer block, and each R ^2' independently represents a glycidyl group, a phenol group, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a cyano group, a nitro group, or an acid anhydride group. The two R ^2' may be the same or different.)

R ^1' in the above formula (3) can be exemplified by the same polymer blocks as those exemplified in the above polyfunctional compound.Specifically, the polymer block is not particularly limited, but examples thereof include those having at least one repeating unit selected from the group consisting of a siloxane bond unit, a urethane bond unit, an ether bond unit, a sulfide bond unit, a butadiene unit, and an isoprene unit.

Furthermore, R2 ^' in the above formula (3) is a terminal group of the polymer block R1 ^' and represents a connecting functional group for connecting to ^R3 . Such connecting functional groups are not particularly limited, but examples thereof include a glycidyl group, a phenol group, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a cyano group, a nitro group, and an acid anhydride group.

In addition, ^R3 in the above formula (2) and R2 ^' in the above formula (3) can be appropriately selected from a combination of known functional groups that can react with each other to form a bond, such as a hydroxyl group and an epoxy group, or a hydroxyl group and a carboxyl group.

Next, the reaction conditions will be explained. Stoichiometrically, a polyfunctional compound having n soft segments can be obtained by reacting n moles of polymer with 1 mole of polymerizing coupling agent. However, taking into consideration the actual reaction efficiency, the amount of polymer added per mole of polymerizing coupling agent is preferably 1.0n to 1.5n moles. In addition, since a polyfunctional compound has three or more soft segments as described in formula (1), the amount of polymer added per mole of polymerizing coupling agent may preferably be 3.0 to 6.0 moles.

The reaction temperature, reaction time, and reaction atmosphere are not particularly limited as long as they are conditions that allow R ³ in the above formula (2) and R ^2′ in the above formula (3) to react and form a bond, and can be appropriately selected from known reaction conditions. As an example of these reaction conditions, the reaction can be performed at 100° C. for 24 hours under a nitrogen atmosphere, but the reaction conditions are not limited thereto.

（式中、Ｘは、炭素原子又は炭素数１～２０のｎ価の連結基を示し、Ａｒは、各々独立して、アリーレン基を示し、Ｒ¹は、各々独立して、重合体ブロックを含む二価の基を示し、Ｒ^2'は、各々独立して、グリシジル基、フェノール基、水酸基、カルボキシル基、アミノ基、チオール基、シアノ基、ニトロ基、又は酸無水物基を示す。ｎは、３～８の整数を示す。） By the above reaction, a compound represented by the following formula (4) can be obtained.

(In the formula, X represents a carbon atom or an n-valent linking group having 1 to 20 carbon atoms, each Ar independently represents an arylene group, each R ¹ independently represents a divalent group containing a polymer block, and each R ^2' independently represents a glycidyl group, a phenol group, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a cyano group, a nitro group, or an acid anhydride group. n represents an integer of 3 to 8.)

The linking group X, the arylene group Ar, and the divalent group ^R1 in the above formula (4) can be exemplified by the same ones as those exemplified for the polyfunctional compound. Also, R2 ^' in the above formula (4) is the terminal group of the polymer block R1 ^' of the polymer used as the raw material, and can be exemplified by the same ones as those exemplified for the polymer.

R ^2' in the above formula (4) may be used as it is as R ² in the above polyfunctional compound, or may be modified to any functional group and used as R ² in the above polyfunctional compound. The modification method is not particularly limited, and a conventionally known method can be used.

The polyfunctional compound obtained as described above may be a single compound having a specific n value in formula (1), or may contain multiple compounds having different n values in formula (1). As the polyfunctional compound of this embodiment, a compound containing one or multiple such polyfunctional compounds may be used as is, or a compound having a specific n value isolated from multiple polyfunctional compounds may be used.

In addition, the method for purifying a polyfunctional compound having a specific n independently is not particularly limited, but examples include a method of separating the compounds based on differences in molecular weight using recycled gel permeation chromatography, etc.

(Method B)
Next, a method B in which a monomer is polymerized using a polyvalent initiator capable of generating a plurality of polymerization initiation terminals will be described. The polyvalent initiator used in this method is not particularly limited, but for example, one having the same structure as the above-mentioned polymerization coupling agent and having a group R that functions as a polymerization initiator for anionic polymerization, cationic polymerization, living polymerization, etc. can be used.

The monomers are not particularly limited, but examples include monomers capable of forming siloxane bond units, urethane bond units, ether bond units, sulfide bond units, butadiene units, and isoprene units.

[Composition]
The composition of the present embodiment includes the polyfunctional compound and a curing accelerator, and may further include a curing agent having a functional group that reacts with ^R2 of the polyfunctional compound to form a chemical bond, if necessary. Such a composition has curability and can be suitably used as an adhesive composition described below. The use of the composition of the present embodiment is not particularly limited to adhesive applications, and can be appropriately used for other applications in which curing properties are expected. The curing accelerator and the curing agent will be described below.

[Adhesive Composition]
The adhesive composition of the present embodiment can be broadly divided into one-component adhesive compositions and two-component adhesive compositions. The one-component adhesive composition can be further divided into homopolymerization adhesive compositions and curing agent reaction adhesive compositions. Each aspect will be described below.

(One-component type: homopolymerization type adhesive composition)
The homopolymerization type adhesive composition of this embodiment contains the above-mentioned polyfunctional compound and a curing accelerator. In this adhesive composition, the homopolymerization of the polyfunctional compound is promoted by the curing accelerator, and the adhesive composition functions as an adhesive. More specifically, the curing accelerator promotes the bonding between ^R2 of the polyfunctional compound, so that the ends of the soft segments are bonded together. This allows the formation of a cured product having a network-type molecular structure in which the soft segments are connected to each other at the intersections of the hard segments.

The curing accelerator is not particularly limited as long as it promotes the bonding between R ² , and a known curing agent can be selected and used depending on the R ² used. As an example, when R ² is an epoxy group, the curing accelerator may be, for example, imidazole-based compounds such as 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 2-methylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, and 1-(2-cyanoethyl)-2-phenylimidazole; phosphorus-based compounds such as triphenylphosphine; tertiary amine-based compounds such as piperidine, dimethylpiperazine, triethylenediamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6,-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo[5.4.0]undec-7-ene; and organometallic compounds. The curing accelerator may be used alone or in combination of two or more types. Among the curing accelerators, imidazole compounds are preferred, and among the imidazole compounds, one or more selected from the group consisting of 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and 2-methylimidazole are preferred.

The content of the curing accelerator is preferably 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass, and preferably 0.5 to 5 parts by mass, per 100 parts by mass of the polyfunctional compound. By having the content of the curing accelerator within the above range, the curability tends to be further improved.

(One-component type: hardener reaction type adhesive composition)
The curing agent reaction type adhesive composition of this embodiment further contains a curing agent having a functional group that reacts with ^R2 to form a chemical bond in addition to the composition described in the homopolymerization type adhesive composition. In this adhesive composition, the curing accelerator promotes the reaction between the polyfunctional compound and the curing agent, and functions as an adhesive. More specifically, the curing accelerator promotes the bond between ^R2 of the polyfunctional compound and the functional group of the curing agent. This makes it possible to form a cured product having a network-type molecular structure in which the intersections of the hard segments and the residues of the curing agent are connected to each other by the soft segments.

The curing agent is not particularly limited as long as it has a functional group that reacts with ^R2 to form a chemical bond, and a known curing agent can be selected and used depending on the ^R2 used. For example, when ^R2 is an epoxy group, examples of the curing agent include bisphenols, biphenol, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 4,4,4-trihydroxytriphenylmethane, 1,1,1-tris(4-hydroxyphenyl)ethane, 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene}bisphenol, α,α,α',α'-tetrakis(4-hydroxyphenyl)-p-xylene, 2,6-bis(dihydroxybenzyl)-4-methylphenol, 1,1,2,2-tetrakis(4 Examples of the curing agent include phenolic compounds such as 1-hydroxy-3-methylphenyl)ethane, hydroquinone, resorcinol, naphthalenediol, phenol novolac resin, and cresol novolac resin; acid anhydride compounds such as methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; aromatic amine compounds such as diaminodiphenylmethane and methylaniline; aliphatic amine compounds such as triethylenetetramine; and amine compounds such as isophoronediamine and methylcyclohexylamine. The curing agent may be used alone or in combination of two or more kinds.

The content of the curing agent is preferably 0.1 to 100 parts by mass, preferably 0.3 to 50 parts by mass, and preferably 0.5 to 30 parts by mass, per 100 parts by mass of the polyfunctional compound. By having the content of the curing agent within the above range, the curability tends to be further improved.

The curing accelerator is not particularly limited as long as it accelerates the bond between ^R2 and the curing agent, and a known curing agent can be selected and used depending on the ^R2 and the curing agent used.

The ratio of the content of the curing agent to the curing accelerator (content of curing agent/content of curing accelerator) is preferably 0.8 to 10, more preferably 1.0 to 7.5, and even more preferably 1.2 to 5. By having the ratio (content of curing agent/content of curing accelerator) within the above range, the curability tends to be further improved.

(Two-component type: adhesive composition set)
The two-part adhesive composition set of this embodiment has a first part containing the above-mentioned polyfunctional compound and a second part containing a curing agent. The curing agent is not particularly limited as long as it has a functional group that reacts with ^R2 to form a chemical bond, and a known curing agent can be selected and used. In addition, the first part and/or the second part may further contain a curing accelerator.

[Adhesion method]
The adhesion method of the present embodiment includes a step of adhering an adherend using the one-component adhesive composition or the two-component adhesive composition set. More specifically, a method of attaching the one-component adhesive composition or the two-component adhesive composition set before curing to an adherend and curing it by heating can be mentioned. The adherend is not particularly limited, and examples thereof include heterogeneous materials such as structural materials for automobiles and structural materials for ships and aerospace.

[Structures]
The structure of the present embodiment is bonded using the one-component adhesive composition or the two-component adhesive composition set. The structure is not particularly limited, but examples thereof include structures in which different materials are bonded together, such as structural materials for automobiles and structural materials for ships and aerospace applications.

The present invention will be described in more detail below using examples and comparative examples. The present invention is not limited in any way by the following examples.

[Example A1]
Into a 300 mL four-neck glass flask equipped with a Liebig condenser, a thermometer, a silicon rubber stopper for nitrogen replacement, and a glass stopper, 44 g of 2-ethoxyethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.996 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. Furthermore, a stirrer was added to the four-neck flask, which was then placed on a magnetic stirrer with an oil bath, and the mixture was stirred at 23° C. for 30 minutes (stirring speed: 300 rpm) to completely dissolve the 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane.

9.8 g of KF-105 (Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with glycidyl at both ends, epoxy equivalent 490 g/mol, number average molecular weight 980) and 0.108 g of Curesol TBZ (2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, Shikoku Chemical Industry Co., Ltd.) were added and stirred for 10 minutes at 23°C (stirring speed: 300 rpm). Stirring was continued while nitrogen was poured in at a flow rate of 10 mL/min for 30 minutes. The nitrogen was stopped and stirring was continued for 24 hours at 100°C (stirring speed: 300 rpm) to obtain a 2-ethoxyethanol solution containing the product.

（式中、Ｒ^1''は、ポリジメチルシロキサン骨格を有する構造を示す。） The 2-ethoxyethanol solution containing the obtained product was subjected to solvent removal using an evaporator to obtain crude product 1. Next, crude product 1 was placed in a separatory funnel, and 100 mL of ion-exchanged water was added and shaken well. The mixture was left to stand until the aqueous layer and the product separated, and only the aqueous layer was removed. This was repeated three times to remove the reaction catalyst in the system, Curesol TBZ, to obtain product 1. The NMR of the obtained product 1 is shown in Figure 1. As a result, it was found that a mixture containing the following polyfunctional compounds was obtained. The GPC data is also shown in Table 1 below.

(In the formula, R ^{1 ″} represents a structure having a polydimethylsiloxane skeleton.)

[Example A2]
85 g of 2-ethoxyethanol and 0.996 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane were added to a 300 mL four-neck glass flask equipped with a Liebig condenser, a thermometer, a silicon rubber stopper for nitrogen replacement, and a glass stopper. A stirrer was then added to the four-neck flask, which was then placed on a magnetic stirrer equipped with an oil bath, and the mixture was stirred at 23°C for 30 minutes (stirring speed: 300 rpm) to completely dissolve the 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane.

（式中、Ｒ^1''は、ポリジメチルシロキサン骨格を有する構造を示す。） 20 g of X-22-163C (manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with glycidyl at both ends, epoxy equivalent 1000 g/mol, number average molecular weight 2000) and 0.210 g of Curesol TBZ (manufactured by Shikoku Chemical Industry Co., Ltd.) were added thereto, and the mixture was stirred at 23°C for 10 minutes (stirring speed: 300 rpm). Stirring was continued while nitrogen was poured in at a flow rate of 10 mL/min for 30 minutes. The nitrogen was stopped, and the mixture was stirred at 100°C for 24 hours (stirring speed: 300 rpm) to obtain a 2-ethoxyethanol solution containing the product. Except for the above, the following product 2 was obtained in the same manner as in Example A1. The GPC data are shown in Table 1 below.

(In the formula, R ^{1 ″} represents a structure having a polydimethylsiloxane skeleton.)

[Example A3]
20 g of 2-ethoxyethanol and 0.996 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane were added to a 300 mL four-neck glass flask equipped with a Liebig condenser, a thermometer, a silicon rubber stopper for nitrogen replacement, and a glass stopper. A stirrer was then added to the four-neck flask, which was then placed on a magnetic stirrer equipped with an oil bath, and the mixture was stirred at 23°C for 30 minutes (stirring speed: 300 rpm) to completely dissolve the 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane.

（式中、Ｒ^1''は、ポリジメチルシロキサン骨格を有する構造を示す。） To this was added 4 g of X-22-163 (manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with glycidyl at both ends, epoxy equivalent 200 g/mol, number average molecular weight 400) and 0.050 g of Curesol TBZ, and the mixture was stirred at 23°C for 10 minutes (stirring speed: 300 rpm). Stirring was continued while nitrogen was poured in at a flow rate of 10 mL/min for 30 minutes. The nitrogen was stopped, and the mixture was stirred at 100°C for 24 hours (stirring speed: 300 rpm) to obtain a 2-ethoxyethanol solution containing the product. Except for the above, the following product 3 was obtained in the same manner as in Example A1. The GPC data are shown in Table 1 below.

(In the formula, R ^{1 ″} represents a structure having a polydimethylsiloxane skeleton.)

（式中、Ｒ^1''は、ポリジメチルシロキサン骨格を有する構造を示す。） [Example A4]
The following product 4 was obtained in the same manner as in Example A1, except that 0.974 g of 4,4',4"-trihydroxytriphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 0.996 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. The GPC data are shown in Table 1 below.

(In the formula, R ^{1 ″} represents a structure having a polydimethylsiloxane skeleton.)

（式中、Ｒ^1''は、ポリジメチルシロキサン骨格を有する構造を示す。） [Example A5]
The following product 5 was obtained in the same manner as in Example A1, except that 1.021 g of 1,1,1-tris(4-hydroxyphenyl)ethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 0.996 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. The GPC data is shown in Table 1 below.

(In the formula, R ^{1 ″} represents a structure having a polydimethylsiloxane skeleton.)

[Example A6]
Into a 300 mL four-neck glass flask equipped with a Liebig condenser, a thermometer, a silicon rubber stopper for nitrogen replacement, and a glass stopper, 45 g of 2-ethoxyethanol and 1.415 g of 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene}bisphenol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added in place of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Further, a stirrer was added to the four-neck flask, which was then placed on a magnetic stirrer with an oil bath, and the mixture was stirred at 23°C for 30 minutes (stirring speed: 300 rpm) to completely dissolve 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene}bisphenol.

（式中、Ｒ^1''は、ポリジメチルシロキサン骨格を有する構造を示す。） To this was added 9.8 g of KF-105 and 0.112 g of Curesol TBZ (manufactured by Shikoku Chemical Industries Co., Ltd.), and the mixture was stirred at 23°C for 10 minutes (stirring speed: 300 rpm). Stirring was continued while nitrogen was introduced at a flow rate of 10 mL/min for 30 minutes. The nitrogen was stopped, and stirring was continued at 100°C for 24 hours (stirring speed: 300 rpm), yielding a 2-ethoxyethanol solution containing the product. Except for the above, the following Product 6 was obtained in the same manner as in Example A1. The GPC data is shown in Table 1 below.

(In the formula, R ^{1 ″} represents a structure having a polydimethylsiloxane skeleton.)

[Example A7]
125 g of 2-ethoxyethanol and 1.557 g of tetrakis(glycidyloxyphenyl)ethane (GTR-1800, manufactured by Nippon Kayaku Co., Ltd.) were added to a 300 mL four-neck glass flask equipped with a Liebig condenser, a thermometer, a silicon rubber stopper for nitrogen replacement, and a glass stopper. A stirrer was then added to the four-neck flask, which was then placed on a magnetic stirrer equipped with an oil bath, and the tetrakis(glycidyloxyphenyl)ethane was completely dissolved by stirring at 23° C. for 30 minutes (stirring speed: 300 rpm).

（式中、Ｒ^1''は、ポリジメチルシロキサン骨格を有する構造を示す。また、Ｒ^1''は、フェニレン骨格も有する。） 29.5 g of KF-2201 (Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with phenol at both ends, phenol equivalent: 1474 g/eq) and 0.311 g of Curesol TBZ were added thereto and stirred at 23°C for 10 minutes (stirring speed: 300 rpm). Stirring was continued while nitrogen was poured in at a flow rate of 10 mL/min for 30 minutes. The nitrogen was stopped and stirring was continued at 100°C for 24 hours (stirring speed: 300 rpm) to obtain a 2-ethoxyethanol solution containing the product. Except for the above, the following Product 7 was obtained in the same manner as in Example A1. The GPC data are shown in Table 1 below.

(In the formula, R ^1″ represents a structure having a polydimethylsiloxane skeleton. R ^1″ also has a phenylene skeleton.)

In addition, products 1 to 7 are not limited to those having the above chemical formula, but can include each compound obtained from the reaction described in each example, and they may be separated and purified by known methods such as recycled GPC.

[GPC measurement conditions]
10 mg of the product obtained as described above was dissolved in 10 mL of tetrahydrofuran (stabilizer-free reagent grade, Fujifilm Wako Pure Chemical Industries, Ltd.), filtered through a membrane filter (PTFE, 0.50 μm), and subjected to gel permeation chromatography (GPC) analysis. The measurement conditions were as follows:
Measuring device: D5280 LCS M-PDA (Shimadzu Corporation)
Column: KF-801 (300mm x 8.0mm ID, Showa Denko)
Column temperature: 40°C
Mobile phase: Tetrahydrofuran (stabilizer-free reagent grade, Fujifilm Wako Pure Chemical Industries, Ltd.)
Flow rate: 1mL/min
Detector: RI (Differential Refractive Index Detector)
Standard material: Polystyrene Shodex STANDARD (Type: SL-105, Showa Denko)

[H ¹ -NMR measurement conditions]
The product obtained as described above was dissolved in deuterated chloroform (reagent grade, manufactured by Tokyo Chemical Industry Co., Ltd.) to prepare a 3% by mass solution, and then ¹ H-nuclear magnetic resonance ( ¹ H-NMR) was performed. went.
Measuring device: AVANCE NEO (manufactured by BRUKER)
Frequency: 500Hz
Heavy solvent: Deuterated chloroform

[Example B1]
5.40 g of Product 1 was mixed with 0.498 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 0.118 g of Curesol TBZ, and 24.1 g of 2-ethoxyethanol. The mixture was cured by heating at 200°C for 2 hours to obtain a cured product. The evaluation results of the mixture are shown in Table 2.

[Example B2]
10.60 g of Product 2 was mixed with 0.498 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 0.222 g of Curesol TBZ, and 45.3 g of 2-ethoxyethanol. The mixture was heated at 200°C for 2 hours to cure, yielding a cured product. The evaluation results of the mixture are shown in Table 2.

[Example B3]
2.50 g of Product 3, 0.498 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 0.060 g of Curesol TBZ, and 12.2 g of 2-ethoxyethanol were mixed. The mixture was heated at 200°C for 2 hours to cure, and a cured product was obtained. The evaluation results of the mixture are shown in Table 2.

[Example B4]
5.39 g of Product 4, 0.487 g of 4,4',4"-trihydroxytriphenylmethane, 0.117 g of Curesol TBZ, and 24.0 g of 2-ethoxyethanol were mixed. The resulting mixture was heated at 200°C for 2 hours to cure, yielding a cured product. The evaluation results of the resulting mixture are shown in Table 2.

[Example B5]
5.41 g of Product 5 was mixed with 0.511 g of 1,1,1-tris(4-hydroxyphenyl)ethane, 0.118 g of Curesol TBZ, and 24.2 g of 2-ethoxyethanol. The mixture was heated at 200°C for 2 hours to cure, yielding a cured product. The evaluation results of the mixture are shown in Table 2.

[Example B6]
5.61 g of Product 6, 0.708 g of 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene}bisphenol, 0.126 g of Curesol TBZ, and 25.8 g of 2-ethoxyethanol were mixed. The mixture was heated at 200°C for 2 hours to cure, and a cured product was obtained. The evaluation results of the mixture are shown in Table 2.

[Example B7]
15.53 g of Product 7, 0.779 g of tetrakis(glycidyloxyphenyl)ethane, 0.311 g of Curesol TBZ, and 66.5 g of 2-ethoxyethanol were mixed. The mixture was heated at 200° C. for 2 hours to cure, and a cured product was obtained. The evaluation results of the mixture are shown in Table 2.

[Example B8]
5.40 g of Product 1, 0.520 g of TD-2131 (phenol novolac resin manufactured by DIC, hydroxyl group equivalent: 104 g/eq), 0.118 g of Curesol TBZ, and 24.1 g of 2-ethoxyethanol were mixed. The mixture obtained was heated at 200°C for 2 hours to cure, and a cured product was obtained. The evaluation results of the mixture obtained are shown in Table 2.

[Example B9]
10.00 g of Product 1, 0.200 g of Curesol 2MZ-H (2-methylimidazole, manufactured by Shikoku Chemical Industries, Ltd.), and 40.8 g of 2-ethoxyethanol were mixed. The mixture obtained was heated at 200°C for 2 hours to cure, and a cured product was obtained. The evaluation results of the mixture obtained are shown in Table 2.

[Comparative Example B1]
1.89 g of bisphenol A diglycidyl ether (jER828 manufactured by Mitsubishi Chemical Holdings, epoxy equivalent: 189 g/eq), 1.016 g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 0.058 g of Curesol TBZ, and 11.9 g of 2-ethoxyethanol were mixed. The mixture obtained was heated at 200°C for 2 hours to cure, and a cured product was obtained. The evaluation results of the mixture obtained are shown in Table 2.

[Comparative Example B2]
9.80g of KF-105, 1.992g of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 0.108g of Curesol TBZ, and 44.0g of 2-ethoxyethanol were mixed. The mixture was cured by heating at 200°C for 2 hours to obtain a cured product. The evaluation results of the mixture are shown in Table 2.

[Comparative Example B3]
11.24 g of a copolymer of bisphenol F and 1,6-hexanediol glycidyl ether (flexible epoxy resin YX7110 manufactured by Mitsubishi Chemical Holdings, epoxy equivalent: 1124 g/eq), 1.04 g of TD-2131, 0.246 g of Curesol TBZ, and 50.1 g of 2-ethoxyethanol were mixed. The mixture obtained was heated at 200°C for 2 hours to cure, and a cured product was obtained. The evaluation results of the mixture obtained are shown in Table 2.

[Appearance of the cured product]
The transparency of the cured product was visually observed.

[Tensile elongation]
The test specimens were prepared according to JIS K 7161-1:2014 in an atmosphere of 23°C or -40°C, and the hardened specimens were shaped as 1BA dumbbell test specimens as specified in Appendix A of JIS K 7161-1:2014. A tensile test was performed using a universal testing machine Instron model 3365 (manufactured by Instron Corporation), and the measured tensile strain was calculated in %.

[Glass transition temperature]
A rectangular cured body with dimensions of 0.5×5×40 mm was used as a test piece. The data was measured using a dynamic viscoelasticity measuring device (DMS7100, manufactured by SII) at a heating rate of 2° C./min, in a temperature range of −100 to 250° C., at a frequency of 1 Hz, and in a tensile mode. The glass transition temperature (Tg) was calculated in ° C. as the peak top temperature of the loss tangent (tan δ).

The above results show that by using the multifunctional compound of Example 1, an adhesive with excellent flexibility is obtained, and the temperature dependence of the tensile breaking elongation is low, especially at temperatures around the glass transition temperature. In Comparative Examples B1 and B3, n in formula (1) is small at 2, and the temperature dependence of the tensile breaking elongation is high. In Comparative Example B2, n in formula (1) is small at 2, the cured product had an opaque appearance, cured poorly, and the tensile breaking elongation could not be measured.

The multifunctional compound of the present invention has industrial applicability as a component of an adhesive.

Claims (13)

A polyfunctional compound represented by the following formula (1):
... (1)
(In the formula, X represents a linking group represented by any one of the following formulas :
Each of the substituents R ^x1 independently represents a hydrocarbon group having 2 to 8 carbon atoms.
Ar represents an arylene group;
Each R ¹ independently represents a divalent group having a number average molecular weight of 200 to 20,000 and including a polymer block having a polysiloxane skeleton ;
^R2 each independently represents a glycidyl group, a phenol group, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a cyano group, a nitro group, or an acid anhydride group;
n represents an integer of 3 to 8. The glass transition temperature of the polymer block is 50° C. or less.
The polyfunctional compound according to claim 1 . The polymer block has no melting point;
The polyfunctional compound according to claim 1 or 2 . A plurality of the polyfunctional compounds having different n are included.
The polyfunctional compound according to any one of claims 1 to 3 . The number average molecular weight of the polyfunctional compound is 800 to 100,000.
The polyfunctional compound according to any one of claims 1 to 4 . The molecular weight distribution (Mw/Mn) of the polyfunctional compound is 1.5 or more.
The polyfunctional compound according to any one of claims 1 to 5 . The Ar represents an arylene group having 6 to 10 carbon atoms.
The polyfunctional compound according to any one of claims 1 to 6 . A polyfunctional compound according to any one of claims 1 to 7 ,
and a curing accelerator,
Composition. Further comprising a curing agent having a functional group that reacts with the ^R2 to form a chemical bond;
The composition of claim 8 . The composition according to claim 8 or 9 ,
Adhesive composition. A first agent containing the polyfunctional compound according to any one of claims 1 to 7 ;
and a second agent including a curing agent.
Adhesive composition set. The method includes a step of adhering an adherend by using the adhesive composition according to claim 10 or the adhesive composition set according to claim 11 .
Gluing method. A laminate bonded using the adhesive composition according to claim 10 or the adhesive composition set according to claim 11 .
Structure.

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